National Library of Energy BETA

Sample records for butane butylene c4h8

  1. Normal butane/iso-butane separation

    SciTech Connect (OSTI)

    Volles, W.K.; Cusher, N.A.

    1986-08-26

    This patent describes an improved pressure swing adsorption process for the separation of iso-butane from normal butane in an adsorption system having at least three adsorbent beds, each bed of which undergoes, on a cyclic basis and a processing sequence comprising: introducing a feed gas mixture of iso-butane and normal butane at an upper adsorption pressure to the feed end of the bed capable of selectively adsorbing normal butane as the more selectivity adsorbable component of the gas mixture. The iso-butane as the less readily adsorbable component passes through the bed and is discharged from the discharge end. The feed gas introduction is continued as a normal butane adsorption front is formed in the bed and passes through the bed from the feed end and breaks through at the discharge end of the bed, a portion of the iso-butane effluent stream thus discharged being diverted for passage as purge gas to another bed in the system; and countercurrently depressurizing the bed with release of gas from the feed end.

  2. Emissions with butane/propane blends

    SciTech Connect (OSTI)

    1996-11-01

    This article reports on various aspects of exhaust emissions from a light-duty car converted to operate on liquefied petroleum gas and equipped with an electrically heated catalyst. Butane and butane/propane blends have recently received attention as potentially useful alternative fuels. Butane has a road octane number of 92, a high blending vapor pressure, and has been used to upgrade octane levels of gasoline blends and improve winter cold starts. Due to reformulated gasoline requirements for fuel vapor pressure, however, industry has had to remove increasing amounts of butane form the gasoline pool. Paradoxically, butane is one of the cleanest burning components of gasoline.

  3. Ignition properties of n-butane and iso-butane in a rapid compression machine

    SciTech Connect (OSTI)

    Gersen, S.; Darmeveil, J.H.; Mokhov, A.V.; Levinsky, H.B.

    2010-02-15

    Autoignition delay times of n-butane and iso-butane have been measured in a Rapid Compression Machine in the temperature range 660-1010 K, at pressures varying from 14 to 36 bar and at equivalence ratios {phi} = 1.0 and {phi} = 0.5. Both butane isomers exhibit a negative-temperature-coefficient (NTC) region and, at low temperatures, two-stage ignition. At temperatures below {proportional_to}900 K, the delay times for iso-butane are longer than those for the normal isomer, while above this temperature both butanes give essentially the same results. At temperatures above {proportional_to}720 K the delay times of the lean mixtures are twice those for stoichiometric compositions; at T < 720 K, the equivalence ratio is seen to have little influence on the ignition behavior. Increasing the pressure from 15 bar to 30 bar decreases the amplitude of the NTC region, and reduces the ignition delay time for both isomers by roughly a factor of 3. In the region in which two-stage ignition is observed, 680-825 K, the duration of the first ignition stage decreases sharply in the range 680-770 K, but is essentially flat above 770 K. Good quantitative agreement is found between the measurements and calculations for n-butane using a comprehensive model for butane ignition, including both delay times in the two-stage region, with substantial differences being observed for iso-butane, particularly in the NTC region. (author)

  4. New butane isomerization unit is unvieled by Andrews Petroleum

    SciTech Connect (OSTI)

    McWilliams, H.

    1990-06-01

    This article discusses the development of a butane isomerization unit which will help reduce butane surplus by fractionating it into other LPG products. Other features of this California project increase on-site storage.

  5. Distillation efficiencies of an industrial-scale i-butane/n-butane fractionator

    SciTech Connect (OSTI)

    Klemola, K.T.; Ilme, J.K.

    1996-12-01

    Rarely published industrial-scale distillation efficiency data are presented. The Murphree tray efficiencies are determined from the i-butane/n-butane fractionator performance data. Point efficiencies, numbers of overall vapor phase transfer units, numbers of vapor and liquid phase transfer units, and liquid phase resistances of mass transfer are backcalculated from the Murphree tray efficiencies. Various efficiency prediction and scale-up methods have been tested against experimental results. A new model for the prediction of the numbers of vapor and liquid phase transfer units has been developed. The model can be applied to hydrocarbon systems at high pressure. The influence of the mass-transfer coefficients, the interfacial area, and the vapor and liquid residence times on mass transfer has been analyzed separately, and as a result the NTU correlations for vapor and liquid phases are obtained. The constants of the model can be obtained by fitting the model to experimental efficiency data from a similar system.

  6. Coupling of oxidative dehydrogenation and aromatization reactions of butane

    SciTech Connect (OSTI)

    Xu, Wen-Qing; Suib, S.L. )

    1994-01-01

    Coupling of oxidative dehydrogenation and aromatization of butane by using a dual function catalyst has led to a significant enhancement of the yields (from 25 to 40%) and selectivities to aromatics (from 39 to 64%). Butane is converted to aromatics by using either zinc-promoted [Ga]-ZSM-5 or zinc and gallium copromoted [Fe]-ZSM-5 zeolite as a catalyst. However, the formation of aromatics is severely limited by hydrocracking of butane to methane, ethane, and propane due to the hydrogen formed during aromatization reactions. On the other hand, the oxidative dehydrogenation of butane to butene over molybdate catalysts is found to be accompanied by a concurrent undesirable reaction, i.e., total oxidation. When two of these reactions (oxidative dehydrogenation and aromatization of butane) are coupled by using a dual function catalyst they have shown to complement each other. It is believed that the rate-limiting step for aromatization (butane to butene) is increased by adding an oxidative dehydrogenation catalyst (Ga-Zn-Mg-Mo-O). The formation of methane, ethane, and propane was suppressed due to the removal of hydrogen initially formed as water. Studies of ammonia TPD show that the acidities of [Fe]-ZSM-5 are greatly affected by the existence of metal oxides such as Ga[sub 2]O[sub 3], MgO, ZnO, and MoO[sub 3]. 40 refs., 9 figs., 1 tab.

  7. Biofiltration control of VOC emissions: Butane and benzene

    SciTech Connect (OSTI)

    Allen, E.R.

    1995-12-31

    Laboratory studies were conducted on the biological elimination of n-butane and benzene from air streams using activated sludge-treated compost biofilters. Four types of experimental biofilter systems were developed: a bench scale packed tower system used primarily for kinetic studies; a small scale column system used to study the effects of different filter media on n-butane removal; a three stage system used to study benzene elimination; and a static batch biofilter system used to study the effects of temperature, compost water content, compost pH, and initial benzene concentrations on benzene elimination. Removal efficiencies greater than 90% were obtained for n-butane. Removal followed first order kinetics at inlet concentrations less than 25 ppM n-butane and zero order kinetics above 100 ppM n-butane. Removal of benzene followed fractional order kinetics for inlet concentrations from 15 to 200 ppM benzene. Thus, the removal of benzene is both mass transfer and bioreaction limited for the concentration range studied. The removal efficiency of benzene was found to be highly dependent on compost water content, compost pH, and temperature. Compost showed a low capacity for benzene removal, which suggested that degradation of these hydrocarbons required different species of microorganisms.

  8. Kinetics and deactivation of sulfated zirconia catalysts for butane isomerization

    SciTech Connect (OSTI)

    Fogash, K.B.; Larson, R.B.; Gonzalez, M.R.

    1996-09-15

    Reaction kinetics studies were conducted of n-butane and isobutane isomerization over sulfated zirconia at 423 K. The kinetic data can be described well by a rate expression based on a reversible, bimolecular surface reaction between two adsorbed n-C{sub 4} species, probably through a C{sub 8} intermediate, to produce one i-C{sub 4} species, as well as surface reaction between two adsorbed i-C{sub 4} species to produce one n-C{sub 4} species. This reaction sequence also describes well the rates of C{sub 4}-disproportionation reactions to produce C{sub 3} and C{sub 5} species. The initial rate of catalyst deactivation is faster during n-butane isomerization than during isobutane isomerization, and the longer-term rate of deactivation during n-butane isomerization increases with the pressures of n-butane. The more rapid catalyst deactivation during n-butane isomerization may be related to the formation of n-C{sub 4}-diene species. 25 refs., 10 figs., 4 tabs.

  9. Transient FTIR studies of the reaction pathway for n-butane selective oxidation over vanadyl pyrophosphate

    SciTech Connect (OSTI)

    Xue, Z.Y.; Schrader, G.L.

    1999-05-15

    New information has been provided about the reaction pathway for n-butane partial oxidation to maleic anhydride over vanadyl pyrophosphate (VPO) catalysts using FTIR spectroscopy under transient conditions. Adsorption studies of n-butane, 1,3-butadiene, and related oxygenates were performed to gain information about reaction intermediates. n-Butane was found to adsorb on the VPO catalyst to form olefinic species at low temperatures. Unsaturated, noncyclic carbonyl species were determined to be precursors to maleic anhydride.

  10. Availability of Canadian imports to meet U.S. demand for ethane, propane and butane

    SciTech Connect (OSTI)

    Hawkins, D.J.

    1996-12-31

    Historically, Canada has had a surplus of ethane, propane and butane. Almost all of the available propane and butane in Canadian natural gas streams is recovered. While there is significant ethane recovery in Canada, ethane that cannot be economically sold is left in the gas streams. All of the surplus Canadian ethane and most of the Canadian surplus propane and butane is exported to the US. Some volumes of Canadian propane and butane have been moved offshore by marine exports to the Asia-Pacific region or South America, or directly to Mexico by rail. Essentially all of the Canadian ethane, 86% of the propane and 74% of the butane are recovered by gas processing. Canadian natural gas production has increased significantly over the last 10 years. Canadian gas resources in the Western Canadian Sedimentary Basin should permit further expansion of gas exports, and several gas pipeline projects are pending to expand the markets for Canadian gas in the US. The prospective increase in Canadian gas production will yield higher volumes of ethane, propane and butane. While there is a potential to expand domestic markets for ethane, propane and butane, a significant part of the incremental production will move to export markets. This paper provides a forecast of the expected level of ethane, propane and butane exports from Canada and discusses the supply, demand and logistical developments which may affect export availability from Canada.

  11. Experimental and DFT studies of initiation processes for butane isomerization over sulfated-zirconia catalysts

    SciTech Connect (OSTI)

    Hong, Z.; Watwe, R.M.; Natal-Santiago, M.A.; Hill, J.M.; Dumesic, J.A.; Fogash, K.B.; Kim, B.; Masqueda-Jimenez, B.I.

    1998-09-10

    Reaction kinetics studies were conducted of isobutane and n-butane isomerization at 423 K over sulfated-zirconia, with the butane feeds purified of olefins. Dihydrogen evolution was observed during butane isomerization over fresh catalysts, as well as over catalysts selectively poisoned by preadsorbed ammonia. Butane isomerization over sulfated-zirconia can be viewed as a surface chain reaction comprised of initiation, propagation, and termination steps. The primary initiation step in the absence of feed olefins is considered to be the dehydrogenation of butane over sulfated-zirconia, generating butenes which adsorb onto acid sites to form protonated olefinic species associated with the conjugate base form of the acid sites. Quantum-chemical calculations, employing density-functional theory, suggest that the dissociative adsorption of dihydrogen, isobutylene hydrogenation, and dissociative adsorption of isobutane are feasible over the sulfated-zirconia cluster, and these reactions take place over Zr-O sites.

  12. Ionization of ethane, butane, and octane in strong laser fields

    SciTech Connect (OSTI)

    Palaniyappan, Sasi; Mitchell, Rob; Ekanayake, N.; Watts, A. M.; White, S. L.; Sauer, Rob; Howard, L. E.; Videtto, M.; Mancuso, C.; Wells, S. J.; Stanev, T.; Wen, B. L.; Decamp, M. F.; Walker, B. C.

    2010-10-15

    Strong-field photoionization of ethane, butane, and octane are reported at intensities from 10{sup 14} to 10{sup 17} W/cm{sup 2}. The molecular fragment ions, C{sup +} and C{sup 2+}, are created in an intensity window from 10{sup 14} to 10{sup 15} W/cm{sup 2} and have intensity-dependent yields similar to the molecular fragments C{sub m}H{sub n}{sup +} and C{sub m}H{sub n}{sup 2+}. In the case of C{sup +}, the yield is independent of the molecular parent chain length. The ionization of more tightly bound valence electrons in carbon (C{sup 3+} and C{sup 4+}) has at least two contributing mechanisms, one influenced by the parent molecule size and one resulting from the tunneling ionization of the carbon ion.

  13. Promotion of n-Butane isomerization activity by hydration of sulfated zirconia

    SciTech Connect (OSTI)

    Gonzalez, M.R.; Kobe, J.M.; Fogash, K.B.; Dumesic, J.A.

    1996-05-01

    The effects of sulfated zirconia catalyst hydration on the activity for n-butane isomerization is reported. The catalytic activity of of a partially hydrated catalyst is enhanced. 66 refs., 11 figs.

  14. Improving the stability of H-mordenite for n-butane isomerization

    SciTech Connect (OSTI)

    Asuquo, R.A.; Eder-Mirth, G.; Lercher, J.A.

    1997-06-01

    The conversion of n-butane over mordenite-based catalysts in the presence of hydrogen and water was investigated for reaction temperatures between 523 and 623 K. Special attention was given to the influence of Pt upon catalytic activity, selectivity, and stability. With parent mordenite the catalytic activity for n-butane conversion decreased markedly after a short time on stream. Deactivation can be minimized by hydrogen (in the presence of Pt) and water addition. Both measures are thought to reduce the concentration of intermediate olefins in the zeolite pores. The best results with respect to selective conversion of n-butane to isobutane were obtained for 0.25 wt% Pt on mordenite in the presence of hydrogen. Higher concentrations of Pt in the catalyst are shown to be detrimental for n-butane isomerization, because of increasing selectivity to hydrogenolysis. A detailed mechanistic scheme for n-butane conversion over Pt-containing mordenites is presented. n-Butane conversion is concluded to occur via a bimolecular mechanism involving a complex network of hydrogen transfer, oligomerization/cracking, isomerization, hydrogenation/dehydrogenation, and hydrogenolysis. 23 refs., 14 figs., 5 tabs.

  15. Low temperature n-butane oxidation skeletal mechanism, based on multilevel approach

    SciTech Connect (OSTI)

    Strelkova, M.I.; Sukhanov, L.P.; Kirillov, I.A.; Safonov, A.A.; Umanskiy, S.Ya.; Potapkin, B.V.; Pasman, H.J.; Tentner, A.M.

    2010-04-15

    In order to reconcile an increasingly large deviation (order of magnitude) of the ignition delay time at decreasing initial temperature, computed using the prior art kinetic schemes, with the available experimental values, a new skeletal mechanism (54 species, 94 reactions) for low-temperature (500-800 K) ignition of n- butane in air based on ab initio calculations is developed. The skeletal mechanism obtained accurately reproduces n-butane combustion kinetics for the practically important ranges of pressure, temperature and fuel-air equivalence ratio, especially in the low-temperature range. The elaborated first principal skeletal chemical kinetic mechanism of n-butane oxidation was validated against available experimental results for normal and elevated initial pressure (1-15 atm) using the Chemical Work Bench code. A good agreement with experiments was shown. (author)

  16. Alternative descriptions of catalyst deactivation in aromatization of propane and butane

    SciTech Connect (OSTI)

    Koshelev, Yu.N.; Vorob`ev, B.L.; Khvorova, E.P.

    1995-08-20

    Deactivation of a zeolite-containing catalyst has been studied in aromatization of propane and butane. Various descriptions of the dependence of the alkane conversion on the coke concentration on the catalyst have been considered, and using a statistical method of estimating the model validity, the most preferable form of the deactivation function has been proposed.

  17. Influence of temperature and process duration on composition of products of butane aromatization on zeolitic catalyst

    SciTech Connect (OSTI)

    Vorob`ev, B.L.; Trishin, P.Yu.; Koshelev, Yu.N.

    1995-06-10

    A study has been made of the influence of catalyst deactivation in the course of its service. The composition of products of butane aromatization on zeolitic catalyst and on selectivity of formation of target products and by-products is reported.

  18. Vapor-liquid equilibria and densities for the system butane + hexacontane

    SciTech Connect (OSTI)

    Nieuwoudt, I.

    1996-09-01

    Liquid and vapor phase compositions and densities have been measured with a variable volume cell for the binary system butane + hexacontane (n-C{sub 60}H{sub 122}). Data sets at 433.15 K, 438.15 K, and 453.15 K are presented and include measurements in the mixture critical region.

  19. Selective oxidation of n-butane and butenes over vanadium-containing catalysts

    SciTech Connect (OSTI)

    Nieto, J.M.L.; Concepcion, P.; Dejoz, A.; Knoezinger, H.; Melo, F.; Vazquez, M.I.

    2000-01-01

    The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg-Al mixed oxides with Mg/(Al + Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C{sub 4}-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reaction with the selective way, i.e., the oxydehydrogenation process by a redox mechanism. Infrared spectroscopy data of 1-butene adsorbed on supported vanadium oxide catalysts suggest the presence of different adsorbed species. O-containing species (carbonyl and alkoxide species) are observed on catalysts with acid sites while adsorbed butadiene species are observed on catalysts with basic sites. According to these results a reaction network for the oxydehydrogenation of n-butane is proposed with parallel and consecutive reactions.

  20. Cracking of n-butane catalyzed by iron- and maganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; d`Itri, J.L.; Gates, B.C.

    1995-05-01

    Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, the significant reactions were isomerization and disproportionation; in the range of 225-300{degrees}C, these reactions were accompanied by cracking, and at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup {minus}9}mol/(g of catalyst {center_dot}s). This comparison suggests that the catalytic activity of the promoted sulfated zirconia at 450{degrees}C is about the same as that of the zeolite, although its activity for n-butane isomerization and disproportionation at temperatures <100{degrees}C is orders of magnitude greater than those of zeolites. Thus the indication of superacidity of the promoted sulfated zirconia does not extend to high temperatures. The results raise questions about the nature of the presumed superacidity: perhaps the low-temperature reactions may involve catalyst functions other than the acidic function responsible for high-temperature cracking reactions or perhaps superacidic sites may be very rapidly poisoned at cracking temperatures. 14 refs., 8 figs., 3 tabs.

  1. Diamond/diamond-like thin film growth in a butane plasma on unetched, unheated, N-type Si(100) substrates

    SciTech Connect (OSTI)

    Williams, E.S.; Richardson, J.S. Jr.; Anderson, D.; Starkey, K.

    1995-06-01

    Deposition of diamond/diamond-like thin films on unetched, unheated, n-type Si(100) substrates in a butane plasma is reported. An interconnection between values of index of refraction, hydrogen flow rate, butane flow rate and Rf power was determined. The H{sub 2} and C{sub 4}H{sub 10} molecules are disassociated by Rf energy to create a plasma. Carbon from the butane forms a thin diamond/diamond-like film on a suitable substrate, which in the current investigation, is n-type Si(100).

  2. Low-temperature superacid catalysis: Reactions of n-butane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; D`Itri, J.L.; Gates, B.C.

    1995-02-01

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline with high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether, which is produced from methanol and isobutylene. The latter can be formed from n-butane by isomerization followed by dehydrogenation. To meet the need for improved catalysts for isomerization of n-butane and other paraffins, researchers identified solid acids that are noncorrosive and active at low temperatures. Sulfated zirconia catalyzes the isomerization of n-butane even at 25{degrees}C, and the addition of Fe and Mn promoters increases its activity by three orders of magnitude. Little is known about this new catalyst. Here the authors provide evidence of its performance for n-butane conversion, demonstrating that isomerization is accompanied by disproportionation and other, less well understood, acid-catalyzed reactions and undergoes rapid deactivation associated with deposition of carbonaceous material. 10 refs., 3 figs.

  3. Formative time of breakdown modeled for the ignition of air and n-butane mixtures using effective ionization coefficients

    SciTech Connect (OSTI)

    Kudryavtsev, A. A.; Popugaev, S. D.; Demidov, V. I.; Adams, S. F.; Jiao, C. Q.

    2008-12-15

    It is shown that simulations of ignition by electric arc discharge in n-butane and air mixtures have interesting features, which deviate from results obtained by simple extension of calculations based on methanelike fuels. In particular, it is demonstrated that lowering the temperature of the n-butane-air mixture before ignition under certain conditions will actually decrease the ignition stage time as well as the required electric field.

  4. TABLE56.CHP:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    ... 2,153 0 2,153 1,884 1,514 370 Normal ButaneButylene ... 0 0 0 527 415 112 IsobutaneIsobutylene...

  5. untitled

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    The principal constituents are methane, ethane, ethylene, normal butane, butylene, propane, propylene, etc. Still gas is used as a refinery fuel and a petrochemical...

  6. ORGANIC SPECIES IN GEOTHERMAL WATERS IN LIGHT OF FLUID INCLUSION...

    Open Energy Info (EERE)

    that indicate H2 concentrations > 0.001 mol % typically have ethane > ethylene, propane > propylene, and butane > butylene. There are three end member fluid compositions:...

  7. Fluid Inclusion Analysis At Coso Geothermal Area (2003) | Open...

    Open Energy Info (EERE)

    that indicate H2 concentrations > 0.001 mol % typically have ethane > ethylene, propane > propylene, and butane > butylene. There are three end member fluid compositions...

  8. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Liquefied Refinery Gases ......370 3,534 3,363 - - 7,267 13 57 9,074 Normal ButaneButylene ......

  9. Petroleum Supply Annual

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Liquefied Refinery Gases ......416 3,228 3,170 - - 6,814 19 342 8,718 Normal ButaneButylene ......

  10. Petroleum Supply Annual

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Crude Oil ......338 80 426 3 4 851 40 140 2,029 Normal ButaneButylene ......

  11. untitled

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Liquefied Refinery Gases ......38,612 126 - 80,904 197 3,607 102,565 Normal ButaneButylene ......

  12. untitled

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Crude Oil ......1,190 83 372 3 3 1,651 81 193 4,652 Normal ButaneButylene ......

  13. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Crude Oil ......956 84 783 3 2 1,828 44 105 4,107 Normal ButaneButylene ......

  14. Dynamics of Exchange at Gas-Zeolite Interfaces 1: Pure Component n-Butane and Isobutane

    SciTech Connect (OSTI)

    CHANDROSS,MICHAEL E.; WEBB III,EDMUND B.; GREST,GARY S.; MARTIN,MARCUS G.; THOMPSON,AIDAN P.; ROTH,M.W.

    2000-07-13

    The authors present the results of molecular dynamics simulations of n-butane and isobutane in silicalite. They begin with a comparison of the bulk adsorption and diffusion properties for two different parameterizations of the interaction potential between the hydrocarbon species, both of which have been shown to reproduce experimental gas-liquid coexistence curves. They examine diffusion as a function of the loading of the zeolite, as well as the temperature dependence of the diffusion constant at loading and for infinite dilution. They continue with simulations in which interfaces are formed between single component gases and the zeolite. After reaching equilibrium, they examine the dynamics of exchange between the bulk gas and the zeolite. Finally, they calculate the permeability of the zeolite for n-butane and isobutane as a function of pressure. Their simulations are performed for a number of different gas temperatures and pressures, covering a wide range of state points.

  15. Hydrogen effect on n-butane isomerization over sulfated zirconia-based catalysts

    SciTech Connect (OSTI)

    Sayari, A.; Yang, Yong; Song, Xuemin

    1997-04-15

    Iron- and manganese-promoted sulfated zirconia (SFMZ) has been tested as an n-butane isomerization catalyst in the temperature range of 35 to 180{degrees}C. The catalytic activity exhibits an induction period whose length is dependent on the reaction conditions. The presence of H{sub 2} in the feed stream strongly suppresses n-butane conversion over unprompted sulfated zirconia (SZ) and over Pt-containing SFMZ (PtSFMZ). However, hydrogen had no effect on n-butane isomerization over SFMZ. These findings were interpreted on the basis of a bimolecular mechanism where unsaturated intermediates (carbenium ions and/or butene) are formed during the break-in period. The role of promoters (Fe and Mn) is not only facilitating the formation of hydrogen-deficient intermediates and their accumulation on the catalyst surface, but also enhancing their stability. The negative effect of hydrogen over PtSFMZ is attributed to the occurrence of atomic hydrogen via the dissociative adsorption of H{sub 2} on Pt. 40 refs., 7 figs., 1 tab.

  16. Biofiltration control of VOC and air toxic emissions: n-Butane and benzene

    SciTech Connect (OSTI)

    Allen, E.R.

    1996-12-31

    n-Butane and benzene vapors are routinely observed in urban atmospheres. Their presence in urban airsheds is of concern because of their ozone production potential as volatile organic compounds (VOCs) and/or potential toxicity. Also, these saturated hydrocarbons are representative of airborne aliphatic and aromatic compounds. Separate laboratory studies have been conducted on the biological elimination of n-butane (n-C{sub 4}H{sub 10}) and benzene (C{sub 6}H{sub 6}) from airstreams using treated compost biofilters. The removal efficiencies were found to exceed 90% for a conditioned biofilter medium and pollutant low concentrations (< 25 ppm) and zeroth order kinetics at higher concentrations (> 100 ppm), whereas benzene vapor elimination followed zeroth order kinetics at concentrations up to 200 ppm. The maximum n-butane and benzene elimination capacities observed for the compost biofilters and conditions employed were 25 and 70 g pollutant m{sup -3} h{sup -1}, respectively. 13 refs., 6 figs., 2 tabs.

  17. Aromatic and polycyclic aromatic hydrocarbon formation in a laminar premixed n-butane flame

    SciTech Connect (OSTI)

    Marinov, N.M.; Pitz, W.J.; Westbrook, C.K.; Vincitore, A.M.; Castaldi, M.J.; Senkan, S.M.; Melius, C.F.

    1998-07-01

    Experimental and detailed chemical kinetic modeling work has been performed to investigate aromatic and polycyclic aromatic hydrocarbon (PAH) formation pathways in a premixed, rich, sooting, n-butane-oxygen-argon burner stabilized flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.6 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer technique. Measurements were made in the main reaction and post-reaction zones for a number of low molecular weight species, aliphatics, aromatics, and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-fused aromatic rings. Reaction flux and sensitivity analysis were used to help identify the important reaction sequences leading to aromatic and PAH growth and destruction in the n-butane flame. Reaction flux analysis showed the propargyl recombination reaction was the dominant pathway to benzene formation. The consumption of propargyl by H atoms was shown to limit propargyl, benzene, and naphthalene formation in flames as exhibited by the large negative sensitivity coefficients. Naphthalene and phenanthrene production was shown to be plausibly formed through reactions involving resonantly stabilized cyclopentadienyl and indenyl radicals. Many of the low molecular weight aliphatics, combustion by-products, aromatics, branched aromatics, and PAHs were fairly well simulated by the model. Additional work is required to understand the formation mechanisms of phenyl acetylene, pyrene, and fluoranthene in the n-butane flame. 73 refs.

  18. Oxidative dehydrogenation of ethane and n-butane on VO{sub x}/Al{sub 2}O{sub 3} catalysts

    SciTech Connect (OSTI)

    Blasco, T.; Galli, A.; Lopez Neito, J.M.; Trifiro, F.

    1997-07-01

    The catalytic properties of vanadium oxides/aluminium oxides were investigated in the dehydrogenation of ethane and n-butane. The importance of Lewis acid sites is described.

  19. Pressure and concentration dependences of the autoignition temperature for normal butane + air mixtures in a closed vessel

    SciTech Connect (OSTI)

    Chandraratna, M.R.; Griffiths, J.F. . School of Chemistry)

    1994-12-01

    The condition at which autoignition occurs in lean premixed n-butane + air mixtures over the composition range 0.2%--2.5% n-butane by volume (0.06 < [phi] < 0.66) were investigated experimentally. Total reactant pressure from 0.1 to 0.6 MPa (1--6 atm) were studied in a spherical, stainless-steel, closed vessel (0.5 dm[sup 3]). There is a critical transition from nonignition to ignition, at pressures above 0.1 MPa, as the mixture is enriched in the vicinity of 1% fuel vapor by volume. There is also a region of multiplicity, which exhibits three critical temperatures at a given composition. Chemical analyses show that partially oxygenated components,including many o-heterocyclic compounds, are important products of the lean combustion of butane at temperatures up to 800 K. The critical conditions for autoignition are discussed with regard to industrial ignition hazards, especially in the context of the autoignition temperature of alkanes given by ASTM or BS tests. The differences between the behavior of n-butane and the higher n-alkanes are explained. The experimental results are also used as a basis for testing a reduced kinetic model to represent the oxidation and autoignition of n-butane or other alkanes.

  20. Effect of Pt and H{sub 2} on n-butane isomerization over Fe and Mn promoted sulfated zirconia

    SciTech Connect (OSTI)

    Song, Xuemin; Reddy, K.R.; Sayari, A.

    1996-06-01

    The activity of a 0.4 wt% Pt-containing Fe and Mn promoted sulfated zirconia (PtSFMZ) catalyst in n-butane isomerization at 35{degrees}C was compared to that of a Pt-free catalyst (SFMZ). The maximum rate of n-butane conversion observed in helium over PtSFMZ was found to be 2.5 times higher than that over the SFMZ catalyst under the same conditions. It is believed that n-butane isomerization proceeds via a bimolecular mechanism in which the formation of hydrogen-deficient intermediates (carbenium ions and butenes), is necessary and the presence of transition metals such as Pt, Fe, and Mn on sulfated zirconia facilitates the formation/accumulation of these intermediates and increases their stability on the catalyst surface. The presence of H{sub 2} had a strong negative effect on n-butane conversion over PtSFMZ, but had no effect over SFMZ. The negative effect of H{sub 2} on PtSFMZ catalyst in n-butane isomerization reaction was attributed to the decreased concentration of butenes in the presence of hydrogen atoms which are formed by the dissociation of H{sub 2} on Pt. The ability of calcined Pt-containing catalysts to activate hydrogen at 35{degrees}C was demonstrated. Reduced SFMZ with or without Pt was not active at 35{degrees}C regardless of the nature of the carrier gas. 42 refs., 5 figs.

  1. Structure of an n-butane monolayer adsorbed on magnesium oxide (100)

    SciTech Connect (OSTI)

    Arnold, T.; Chanaa, S.; Cook, R. E.; Clarke, S. M.; Larese, J. Z.

    2006-08-15

    Neutron diffraction has been used to characterize the structure of the solid phase of the completed monolayer of n butane on the MgO(100) surface at low temperature. The monolayer is found to adopt a commensurate (7{radical}(2)x{radical}(2)R45 deg. ) structure with lattice constants a=29.47 A ring and b=4.21 A ring , P{sub 2gg} symmetry and four molecules in the unit cell. Excellent agreement with the experimental diffraction pattern is realized, using a Lorenztian profile to describe the line shape.

  2. Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  3. n-Butane: Ignition delay measurements at high pressure and detailed chemical kinetic simulations

    SciTech Connect (OSTI)

    Healy, D.; Curran, H.J.; Donato, N.S.; Aul, C.J.; Petersen, E.L.; Zinner, C.M.; Bourque, G.

    2010-08-15

    Ignition delay time measurements were recorded at equivalence ratios of 0.3, 0.5, 1, and 2 for n-butane at pressures of approximately 1, 10, 20, 30 and 45 atm at temperatures from 690 to 1430 K in both a rapid compression machine and in a shock tube. A detailed chemical kinetic model consisting of 1328 reactions involving 230 species was constructed and used to validate the delay times. Moreover, this mechanism has been used to simulate previously published ignition delay times at atmospheric and higher pressure. Arrhenius-type ignition delay correlations were developed for temperatures greater than 1025 K which relate ignition delay time to temperature and concentration of the mixture. Furthermore, a detailed sensitivity analysis and a reaction pathway analysis were performed to give further insight to the chemistry at various conditions. When compared to existing data from the literature, the model performs quite well, and in several instances the conditions of earlier experiments were duplicated in the laboratory with overall good agreement. To the authors' knowledge, the present paper presents the most comprehensive set of ignition delay time experiments and kinetic model validation for n-butane oxidation in air. (author)

  4. Studies of n-butane conversion over silica-supported platinum, platinum-silver and platinum-copper catalysts

    SciTech Connect (OSTI)

    Gu, Junhua

    1992-06-09

    The present work was undertaken to elucidate effect of adding silver and copper to silica-supported platinum catalyst on the activity and selectivity in the n-butane reactions. At the conditions of this study n-butane underwent both hydrogenolysis and structural isomerization. The catalytic activity and selectivities between hydrogenolysis and isomerization and within hydrogenolysis were measured at temperature varying from 330 C to 370 C. For platinum-silver catalysts, at lower temperatures studied the catalytic activity per surface platinum atom (turnover frequency) remained constant at lower silver content (between 0 at. % and 30 at. %) and decreased with further increased silver loading, suggesting that low- index planes could be dominant in the hydrogenolysis of n-butane. Moreover, increasing silver content resulted in an enhancement of the selectivity of isomerization products relative to hydrogenolysis products. At the higher temperature studied, no suppression in catalytic activity was observed. It is postulated that surface structure could change due to the mobility of surface silver atoms, leading to surface silver atoms forming islands or going to the bulk, and leaving large portions of basal planes exposed with active platinum atoms. It is also suggested that the presence of inert silver atoms results in weakening of the H-surface bond. This results in increased mobility of hydrogen atoms on the surface and hence, higher reactivity with other adsorbed species. For platinum copper catalysts, the mixed ensembles could play an active role in the hydrogenolysis of n-butane.

  5. Support shape effect in metal oxide catalysis: ceria nanoshapes supported vanadia catalysts for oxidative dehydrogenation of iso-butane

    SciTech Connect (OSTI)

    Wu, Zili; Schwartz, Viviane; Li, Meijun; Rondinone, Adam Justin; Overbury, Steven {Steve} H

    2012-01-01

    The activation energy of VOx/CeO2 catalysts in oxidative dehydrogenation of iso-butane was found dependent on the shape of ceria support: rods < octahedra, closely related to the surface oxygen vacancy formation energy and defects amount of the two ceria supports with different crystallographic surface planes.

  6. Adsorption of iso-/n-butane on an Anatase Thin Film: A Molecular Beam Scattering and TDS Study

    SciTech Connect (OSTI)

    Goering, J.; Kadossov, E.; Burghaus, Uwe; Yu, Zhongqing; Thevuthasan, Suntharampillai; Saraf, Laxmikant V.

    2007-07-01

    Binding energies and adsorption probabilities have been determined for n/iso-butane adsorption on an anatase thin film grown on SrTiO3(001) by means of thermal desorption spectroscopy (TDS) and molecular beam scattering. The sample has been characterized by x-ray diffraction (XRD) and Auger electrons spectroscopy (AES).

  7. Skeletal isomerization of n-butane on zeolites and sulfated zirconium oxide promoted by platinum: Effect of reaction pressure

    SciTech Connect (OSTI)

    Kuei-jung Chao; Hung-chung Wu; Li-jen Leu

    1995-12-01

    The isomerization of n-butane catalyzed by sulfated zirconium oxide and H-form zeolites with the promotion of platinum has been studied by measurements of the conversion and product distribution at temperatures of between 240 and 390{degrees}C at atmospheric pressure and at 20.4 atm. The skeletal isomerization proceeds mainly via the bimolecular disproportionation mechanism on Pt/H-zeolite at 1 atm and via the monomolecular carbocation mechanism on Pt/SO{sub 4}{sup 2}-ZrO{sub 2} at temperatures of 300{degrees}C at both 1 and 20.4 atm. At 20.4 atm pressure, the monomolecular cracking and isomerization of butane can also occur on Pt/H-zeolite. Hydrogen molecules may be dissociated and converted to hydride and proton ions on Pt/SO{sub 4}{sup -2}--ZrO{sub 2}, promoting the desorption of surface carbenium ions and the cracking of butane molecules, which have been enhanced under high reaction pressures. 16 refs., 1 fig., 2 tabs.

  8. n-Alkanes on MgO(100). I: Coverage-Dependent Desorption Kinetics of n-Butane

    SciTech Connect (OSTI)

    Tait, Steven L.; Dohnalek, Zdenek; Campbell, C T.; Kay, Bruce D.

    2005-04-22

    High quality temperature programmed desorption (TPD) measurements of n-butane from MgO(100) have been made for a large number of initial butane coverages (0-3.70 ML) and a wide range of heating ramp rates (0.3-10 K/s). We present a TPD analysis technique which allows the coverage-dependent desorption energy to be accurately determined by mathematical inversion of a TPD spectrum, assuming only that the prefactor is coverage-independent. A variational method is used to determine the prefactor that minimizes the difference between a set of simulated TPD spectra and corresponding experimental data. The best fit for butane desorption from MgO is obtained with a prefactor of 1015.7?1.6 s-1. The desorption energy is 34.9?3.4 kJ/mol at 0.5 ML coverage, and varies with coverage. Simulations based on these results can accurately reproduce TPD experiments for submonolayer initial coverages over a wide range of heating ramp rates (0.3-10 K/s). Advantages and limitations of this method are discussed.

  9. The kinetic significance of V{sup 5+} in n-butane oxidation catalyzed by vanadium phosphates

    SciTech Connect (OSTI)

    Coulston, G.W.; Harlow, R.; Herron, N.

    1997-01-10

    Maleic anhydride, a precursor to polyester resins, is made by oxidation of n-butane over vanadium phosphate catalysts. This system is of general interest because it is the only heterogeneously catalyzed, alkane-selective oxidation reaction in commercial use. Time-resolved in situ x-ray absorption spectroscopy shows that when either {alpha}{sub 1}-VOPO{sub 4}/SiO{sub 2} or (VO){sub 2}P{sub 2}O{sub 7}/SiO{sub 2} catalysts are exposed to n-butane, the rate of maleic anhydride formation is proportional to the rate of decay of V{sup 5+} species in the catalyst. Thus V{sup 5+} species are kinetically significant for the production of maleic anhydride and not just for the production of by-products. The results also suggest that V{sup 5+} species in the catalyst. Thus V{sup 5+} species are kinetically significant for the production of maleic anhydride and not just for the production of by-products. The results also suggest that V{sup 5+} species may play a role in the initial hydrogen abstraction from n-butane, the rate-determining step in the reaction sequence. V{sup 4+} sites appear to be responsible for by-product formation.

  10. Kinetic study of the oxidation of n-butane on vanadium oxide supported on Al/Mg mixed oxide

    SciTech Connect (OSTI)

    Dejoz, A.; Vazquez, I.; Nieto, J.M.L.; Melo, F.

    1997-07-01

    The reaction kinetics of the oxidative dehydrogenation (ODH) of n-butane over vanadia supported on a heat-treated Mg/Al hydrotalcite (37.3 wt % of V{sub 2}O{sub 5}) was investigated by both linear and nonlinear regression techniques. A reaction network including the formation of butenes (1-, 2-cis-, and 2-trans-butene), butadiene, and carbon oxides by parallel and consecutive reactions, at low and high n-butane conversions, has been proposed. Langmuir-Hinshelwood (LH) models can be used as suitable models which allows reproduction of the global kinetic behavior, although differences between oxydehydrogenation and deep oxidation reactions have been observed. Thus, the formation of oxydehydrogenation products can be described by a LH equation considering a dissociative adsorption of oxygen while the formation of carbon oxides is described by a LH equation with a nondissociative adsorption of oxygen. Two different mechanisms operate on the catalyst: (i) a redox mechanism responsible of the formation of olefins and diolefins and associated to vanadium species, which is initiated by a hydrogen abstraction; (ii) a radical mechanism responsible of the formation of carbon oxides from n-butane and butenes and associated to vanadium-free sites of the support. On the other hand, the selectivity to oxydehydrogenation products increases with the reaction temperature. This catalytic performance can be explained taking into account the low reducibility of V{sup 5+}-sites and the higher apparent activation energies of the oxydehydrogenation reactions with respect to deep oxidation reactions.

  11. A study of the kinetics and mechanism of the adsorption and anaerobic partial oxidation of n-butane over a vanadyl pyrophosphate catalyst

    SciTech Connect (OSTI)

    Sakakini, B.H.; Taufiq-Yap, Y.H.; Waugh, K.C.

    2000-01-25

    The interaction of n-butane with a ((VO){sub 2}P{sub 2}O{sub 7}) catalyst has been investigated by temperature-programmed desorption and anaerobic temperature-programmed reaction. n-Butane has been shown to adsorb on the (VO){sub 2}P{sub 2}O{sub 7} to as a butyl-hydroxyl pair. When adsorption is carried out at 223 K, upon temperature programming some of the butyl-hydroxyl species recombine resulting in butane desorption at 260 K. However, when adsorption is carried out at 423 K, the hydroxyl species of the butyl-hydroxyl pair migrate away from the butyl species during the adsorption, forming water which is detected in the gas phase. Butane therefore is not observed to desorb at 260 K after the authors lowered the temperature to 223 K under the butane/helium from the adsorption temperature of 423 K prior to temperature programming from that temperature to 1100 K under a helium stream. Anaerobic temperature-programmed oxidation of n-butane produces butene and butadiene at a peak maximum temperature of 1000 K; this is exactly the temperature at which, upon temperature programming, oxygen evolves from the lattice and desorbs as O{sub 2}. This, and the fact that the amount of oxygen desorbing from the (VO){sub 2}P{sub 2}O{sub 7} at {approximately}1000 K is the same as that required for the oxidation of the n-butane to butene and butadiene, strongly suggests (1) that lattice oxygen as it emerges at the surface is the selective oxidant and (2) that its appearance at the surface is the rate-determining step in the selective oxidation of n-butane. The surface of the (VO){sub 2}P{sub 2}O{sub 7} catalyst on which this selective oxidation takes place has had approximately two monolayers of oxygen removed from it by unselective oxidation of the n-butane to CO, CO{sub 2}, and H{sub 2}O between 550 and 950 K and has had approximately one monolayer of carbon deposited on it at {approximately}1000 K. It is apparent, therefore, that the original crystallography of the (VO){sub 2}P{sub 2}O{sub 7} catalyst will not exist during this selective oxidation and that theories that relate selectivity in partial oxidation to the (100) face of the (VO){sub 2}P{sub 2}O{sub 7} catalyst cannot apply in this case.

  12. Ignition of ethane, propane, and butane in counterflow jets of cold fuel versus hot air under variable pressures

    SciTech Connect (OSTI)

    Fotache, C.G.; Wang, H.; Law, C.K.

    1999-06-01

    This study investigates experimentally the nonpremixed ignition of ethane, propane, n-butane, and isobutane in a configuration of opposed fuel versus heated air jets. For each of these fuels the authors explore the effects of inert dilution, system pressure, and flow strain rate, for fuel concentrations ranging between 3--100% by volume, pressures between 0.2 and 8 atm, and strain rates of 100--600 s{sup {minus}1}. Qualitatively, these fuels share a number of characteristics. First, flame ignition typically occurs after an interval of mild oxidation, characterized by minimal heat release, fuel conversion, and weak light emission. The temperature extent of this regime decreases with increasing the fuel concentration, the ambient pressure, or the flow residence time. Second, the response to strain rate, pressure, and fuel concentration is similar for all investigated fuels, in that the ignition temperatures monotonically decrease with increasing fuel content, decreasing flow strain, and increasing ambient pressure. The C{sub 4} alkanes, however, exhibit three distinct p-T ignition regimes, similar to the homogeneous explosion limits. Finally, at 1 atm, 100% fuel, and a fixed flow strain rate the ignition temperature increases in the order of ethane < propane < n-butane < i-butane. Numerical simulation was conducted for ethane ignition using detailed reaction kinetics and transport descriptions. The modeling results suggest that ignition for all fuels studied at pressures below 5 atm is initiated by fuel oxidation following the high-temperature mechanism of radical chain branching and with little contribution by low-to-intermediate temperature chemistry.

  13. Selective aromatization of C[sub 3]- and C[sub 4]-paraffins over modified encilite catalysts: 2. Kinetics of n-butane aromatization

    SciTech Connect (OSTI)

    Jana, A.K.; Rao, M.S. . Dept. of Chemical Engineering)

    1993-11-01

    The kinetics of the aromatization of n-butane over Zn-encilite catalyst was studied in a fixed bed reactor under steady-state conditions at atmospheric pressure and in the temperature range of 480--540 C. The experimental data were analyzed, and a dual-site mechanism was proposed. Six rate equations of the Langmuir-Hinshelwood type were tested. The unknown parameters in the rate equations were estimated by a nonlinear regression method. A kinetic equation for n-butane aromatization is proposed.

  14. Solvent vapor recovery by pressure swing adsorption. 1: Experimental transient and periodic dynamics of the butane-activated carbon system

    SciTech Connect (OSTI)

    Liu, Y.; Holland, C.E.; Ritter, J.A.

    1998-11-01

    An experimental investigation was carried out for the separation and recovery of butane vapor (10 to 40 vol%) from nitrogen using Westvaco BAX activated carbon in a twin-bed pressure swing adsorption (PSA) system utilizing a 4-step Skarstrom-type cycle. Twenty-four runs, covering a broad range of process and initial column conditions, were performed to investigate the transient and period process dynamics. In all cases the approach to the periodic state was very slow, taking up to 160 cycles depending on the initial condition of the beds; and peak bed temperatures of up to 105 C were observed depending on both the initial condition of the beds and the process conditions. Also, the periodic state of each run was unique when approaching a new periodic state from less contaminated beds. The uniqueness of the periodic states, together with the exceedingly high peak temperatures, inferred much about the practice of preconditioning beds to avoid high temperature excursions. The periodic enriched butane vapor concentration histories also gave considerable insight into new cycle designs for improved solvent vapor enrichment.

  15. Toward Understanding the Nature of Internal Rotation Barriers with a New Energy Partition Scheme: Ethane and n-Butane

    SciTech Connect (OSTI)

    Liu, Shubin; Govind, Niri

    2008-07-24

    Based on an alternative energy partition scheme where density-based quantification of the steric effect was proposed [S.B. Liu, J. Chem. Phys. 126, 244103 (2007)], the origin of the internal rotation barrier between the eclipsed and staggered conformers of ethane and n-butane is systematically investigated in this work. The new definition is repulsive, exclusive, and extensive, and is intrinsically related to Bader’s atoms in molecules approach. Two kinds of differences, adiabatic (with optimal structure) and vertical (with fixed geometry), are considered in this work. We find that in the adiabatic case the eclipsed conformer possesses a larger steric repulsion than the staggered conformer for both molecules, but in the vertical cases the staggered conformer retains a larger steric repulsion. For ethane, a strong correlation between the total energy difference and the fermionic quantum energy difference is discovered. This linear relationship, however, does not hold for n-butane, whose behaviors in energy component differences are found to be more complicated. The impact of basis set and density functional choices on energy components from the new energy partition scheme has been investigated, as has its comparison with another definition of the steric effect in the literature in terms of the natural bond orbital analysis through the Pauli Exclusion Principle. Profiles of conceptual DFT reactivity indices as a function of dihedral angle changes have also been examined. Put together, these results suggest that the new energy partition scheme provides insights from a different perspective of internal rotation barriers.

  16. Short-Term Energy Outlook March 2016

    U.S. Energy Information Administration (EIA) Indexed Site

    ... 0.48 0.46 0.43 0.44 0.46 Refinery and Blender Net Production EthaneEthylene ... HGL Refinery and Blender Net Inputs ButanesButylenes ......

  17. Short-Term Energy Outlook - U.S. Energy Information Administration...

    U.S. Energy Information Administration (EIA) Indexed Site

    ... PADD 1 (East Coast) PADD 2 (Midwest) PADD 3 (Gulf Coast) PADD 4 (Rocky Mountain) PADD 5 (West Coast) U.S. Total Refining Refinery and Blender Net Inputs Crude Oil ButanesButylenes ...

  18. 4btab.xlsx

    U.S. Energy Information Administration (EIA) Indexed Site

    0.48 0.46 0.43 0.44 0.46 Refinery and Blender Net Production EthaneEthylene ... HGL Refinery and Blender Net Inputs ButanesButylenes ......

  19. U.S. Crude Oil and Petroleum Products Stocks by Type

    Gasoline and Diesel Fuel Update (EIA)

    Product: Crude Oil and Petroleum Products Crude Oil All Oils (Excluding Crude Oil) Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Ethylene Propane/Propylene Propylene (Nonfuel Use) Normal Butane/Butylene Refinery Grade Butane Isobutane/Butylene Other Hydrocarbons Oxygenates (excluding Fuel Ethanol) MTBE Other Oxygenates Renewables (including Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Unfinished Oils Unfinished Oils, Naphthas & Lighter Unfinished Oils,

  20. Refinery Net Production of Total Finished Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    Product: Total Finished Petroleum Products Liquefied Refinery Gases Ethane/Ethylene Ethane Ethylene Propane/Propylene Propane Propylene Normal Butane/Butylene Normal Butane Butylene Isobutane/Isobutylene Isobutane Isobutylene Finished Motor Gasoline Reformulated Gasoline Reformulated Blended w/ Fuel Ethanol Reformulated Other Conventional Gasoline Conventional Blended w/ Fuel Ethanol Conventional Blended w/ Fuel Ethanol, Ed55 and Lower Conventional Blended w/ Fuel Ethanol, Greater than Ed55

  1. Ethane and n-butane oxidation over supported vanadium oxide catalysts: An in situ UV-visible diffuse reflectance spectroscopic investigation

    SciTech Connect (OSTI)

    Gao, X.; Banares, M.A.; Wachs, I.E.

    1999-12-10

    The coordination/oxidation states of surface vanadium oxide species on several oxide supports (Al{sub 2}O{sub 3}, ZrO{sub 2}, SiO{sub 2}) during ethane and n-butane oxidation were examined by in situ UV-vis diffuse reflectance spectroscopy (DRS). Only a small amount of the surface V(V)cations are reduced to V(IV)/V(III) cations under present steady-state reaction conditions. The extents of reduction of the surface V(V) species are a strong function of the specific oxide support, V{sub 2}O{sub 5}/ZrO{sub 2} {gt} V{sub 2}O{sub 5}/Al{sub 2}O{sub 5}/Al{sub 2}O{sub 3} {gt} V{sub 2}O{sub 5}/SiO{sub 2}, and also correlate with their reactivities (turnover frequencies) for ethane and n-butane oxidation reactions. For ZrO{sub 2}-supported samples, the polymerized surface vanadia species were found to be more easily reduced than the isolated surface vanadia species in reducing environments (i.e., ethane or n-butane in He), but no significant differences in the extents of reduction were observed under present steady-state reaction conditions (i.e., ethane/O{sub 2}/He or n-butane/O{sub 2}/He). This observation is also consistent with the ethane oxidation catalytic study, which revealed that the polymerization degree, the domain size, of the surface vanadia species does not appear to significantly affect the reactivity of the supported vanadia catalysts for ethane oxidation.

  2. Initial activity of reduced chromia/alumina catalyst in n-butane dehydrogenation monitored by on-line FT-IR gas analysis

    SciTech Connect (OSTI)

    Hakuli, A.; Kytoekivi, A.; Suntola, T.

    1996-06-01

    The initial activity of chromia/alumina catalyst (13 wt% Cr) in n-butane dehydrogenation was studied in a flow reactor at 853 K. The initial activity was determined by on-line FT-IR gas analysis, which enabled sampling of the gaseous product mixture at a time resolution of seconds. The catalysts were processed in repeated cycles of oxidation, reduction, and dehydrogenation using n-butane, methane, hydrogen, or carbon monoxide as reducing agents. With n-butane, methane, and hydrogen and dehydrogenation activity was associated with Cr{sup 3+} species apparently formed in the reduction of high-valence Cr species. The catalyst reduced with carbon monoxide at 853 K showed poor initial selectivity for butenes and, relative to the other catalysts. Simultaneous data relating the initial activity, coke content, and some of the physicochemical properties of the catalyst indicated that the surfaces of all catalysts were modified to some extent by the successive reaction cycles. 33 refs., 7 figs., 2 tabs.

  3. Role of metal-support interactions on the activity of Pt and Rh catalysts for reforming methane and butane.

    SciTech Connect (OSTI)

    Rossignol, C.; Krause, T.; Krumpelt, M.

    2002-01-11

    For residential fuel cell systems, reforming of natural gas is one option being considered for providing the H{sub 2} necessary for the fuel cell to operate. Industrially, natural gas is reformed using Ni-based catalysts supported on an alumina substrate, which has been modified to inhibit coke formation. At Argonne National Laboratory, we have developed a new family of catalysts derived from solid oxide fuel cell technology for reforming hydrocarbon fuels to generate H{sub 2}. These catalysts consist of a transition metal supported on an oxide-ion-conducting substrate, such as ceria, that has been doped with a small amount of a non-reducible element, such as gadolinium, samarium, or zirconium. Unlike alumina, the oxide-ion-conducting substrate has been shown to induce strong metal-support interactions. Metal-support interactions are known to play an important role in influencing the catalytic activity of many metals supported on oxide supports. Based on results from temperature-programmed reduction/oxidation and kinetic reaction studies, this paper discusses the role of the metal and the substrate in the metal-support interactions, and how these interactions influence the activity and the selectivity of the catalyst in reforming methane and butane to hydrogen for use in fuel cell power systems.

  4. Autoignited laminar lifted flames of methane, ethylene, ethane, and n-butane jets in coflow air with elevated temperature

    SciTech Connect (OSTI)

    Choi, B.C.; Chung, S.H.

    2010-12-15

    The autoignition characteristics of laminar lifted flames of methane, ethylene, ethane, and n-butane fuels have been investigated experimentally in coflow air with elevated temperature over 800 K. The lifted flames were categorized into three regimes depending on the initial temperature and fuel mole fraction: (1) non-autoignited lifted flame, (2) autoignited lifted flame with tribrachial (or triple) edge, and (3) autoignited lifted flame with mild combustion. For the non-autoignited lifted flames at relatively low temperature, the existence of lifted flame depended on the Schmidt number of fuel, such that only the fuels with Sc > 1 exhibited stationary lifted flames. The balance mechanism between the propagation speed of tribrachial flame and local flow velocity stabilized the lifted flames. At relatively high initial temperatures, either autoignited lifted flames having tribrachial edge or autoignited lifted flames with mild combustion existed regardless of the Schmidt number of fuel. The adiabatic ignition delay time played a crucial role for the stabilization of autoignited flames. Especially, heat loss during the ignition process should be accounted for, such that the characteristic convection time, defined by the autoignition height divided by jet velocity was correlated well with the square of the adiabatic ignition delay time for the critical autoignition conditions. The liftoff height was also correlated well with the square of the adiabatic ignition delay time. (author)

  5. Carbon nanotube-induced preparation of vanadium oxide nanorods: Application as a catalyst for the partial oxidation of n-butane

    SciTech Connect (OSTI)

    Chen Xiaowei; Zhu Zhenping; Haevecker, Michael; Su Dangsheng . E-mail: dangsheng@fhi-berlin.mpg.de; Schloegl, Robert

    2007-02-15

    A vanadium oxide-carbon nanotube composite was prepared by solution-based hydrolysis of NH{sub 4}VO{sub 3} in the presence of carbon nanotubes. The carbon nanotubes induce the nucleation of the 1D vanadium oxide nanostructures, with the nuclei growing into long freestanding nanorods. The vanadium oxide nanorods with the lengths up to 20 {mu}m and the widths of 5-15 nm exhibit a well-ordered crystalline structure. Catalytic tests show that the composite with nanostructured vanadium oxide is active for the partial oxidation of n-butane to maleic anhydride at 300 deg. C.

  6. Host cells and methods for producing 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, and 3-methyl-butan-1-ol

    DOE Patents [OSTI]

    Chou, Howard H.; Keasling, Jay D.

    2011-07-26

    The invention provides for a method for producing a 5-carbon alcohol in a genetically modified host cell. In one embodiment, the method comprises culturing a genetically modified host cell which expresses a first enzyme capable of catalyzing the dephosphorylation of an isopentenyl pyrophosphate (IPP) or dimethylallyl diphosphate (DMAPP), such as a Bacillus subtilis phosphatase (YhfR), under a suitable condition so that 5-carbon alcohol is 3-methyl-2-buten-1-ol and/or 3-methyl-3-buten-1-ol is produced. Optionally, the host cell may further comprise a second enzyme capable of reducing a 3-methyl-2-buten-1-ol to 3-methyl-butan-1-ol, such as a reductase.

  7. The V{sup 4}+/V{sup 5+} balance as a criterion of selection of vanadium phosphorus oxide catalysts for n-butane oxidation to maleic anhydride: A proposal to explain the role of Co and Fe dopants

    SciTech Connect (OSTI)

    Sananes-Schulz, M.T.; Tuel, A.; Volta, J.C.; Hutchings, G.J.

    1997-03-01

    Vanadium phosphorous oxide catalysts (VPO) are well known for the oxidation of n-butane to maleic anhydride, and many papers and patents have been published in the literature on this catalytic system. Concerning the valence state of vanadium in the active surface, a V{sup 4+}/V{sup 5+} equilibrium on the surface of a vanadyl pyrophosphate during n-butane oxidation has been demonstrated which is dependent on the time of activation. In the present note, we study the modifications, as determined by {sup 31}P NMR by spin echo mapping, which are induced in the physicochemical characteristics of VPO catalysts which have major differences in their morphologies when doped with iron and cobalt at a low percentage (1%) and the correlation with their catalytic performances. 21 refs., 5 figs., 2 tabs.

  8. Bimetallic Ni-Rh catalysts with low amounts of Rh for the steam and autothermal reforming of n-butane for fuel-cell applications.

    SciTech Connect (OSTI)

    Ferrandon, M.; Kropf, A. J.; Krause, T.; Chemical Sciences and Engineering Division

    2010-05-15

    Mono-metallic nickel and rhodium catalysts and bimetallic Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}, CeZrO{sub 2} and CeMgOx were prepared and evaluated for catalyzing the steam and autothermal reforming of n-butane. The binary Ni-Rh supported on La-Al{sub 2}O{sub 3} catalysts with low weight loading of rhodium exhibited higher H{sub 2} yields than Ni or Rh alone. The Ni-Rh/CeZrO{sub 2} catalyst exhibited higher performance and no coke formation, compared to the same metals on other supports. A NiAl{sub 2}O{sub 4} spinel phase was obtained on all Ni and Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}. The presence of rhodium stabilized the spinel phase as well as NiOx species upon reforming while Ni alone was mostly reduced into metallic species. Extended X-ray absorption fine-structure analysis showed evidence of Ni-Rh alloy during preparation and even further after an accelerated aging at 900C in a H{sub 2}/H{sub 2}O atmosphere.

  9. Role of the reaction intermediates in determining PHIP (parahydrogen induced polarization) effect in the hydrogenation of acetylene dicarboxylic acid with the complex [Rh (dppb)]{sup +} (dppb: 1,4-bis(diphenylphosphino)butane)

    SciTech Connect (OSTI)

    Reineri, F.; Aime, S.; Gobetto, R.; Nervi, C.

    2014-03-07

    This study deals with the parahydrogenation of the symmetric substrate acetylene dicarboxylic acid catalyzed by a Rh(I) complex bearing the chelating diphosphine dppb (1,4-bis(diphenylphosphino)butane). The two magnetically equivalent protons of the product yield a hyperpolarized emission signal in the {sup 1}H-NMR spectrum. Their polarization intensity varies upon changing the reaction solvent from methanol to acetone. A detailed analysis of the hydrogenation pathway is carried out by means of density functional theory calculations to assess the structure of hydrogenation intermediates and their stability in the two solvents. The observed polarization effects have been accounted on the basis of the obtained structures. Insights into the lifetime of a short-lived reaction intermediate are also obtained.

  10. Pt3Ru6 Clusters Supported on gamma-Al2O3: Synthesis from Pt3Ru6(Cu)21(u3-H)(u-H)3, Structural Characterization, and Catalysis of Ethylene Hydrogenation and n-Butane Hydrogenolysis

    SciTech Connect (OSTI)

    Chotisuwan,S.; Wittayakun, J.; Gates, B.

    2006-01-01

    The supported clusters Pt-Ru/{gamma}-Al{sub 2}O{sub 3} were prepared by adsorption of the bimetallic precursor Pt{sub 3}Ru{sub 6}(Cu){sub 21}({mu}{sub 3}-H)({mu}-H){sub 3} from CH{sub 2}Cl{sub 2} solution onto {gamma}-Al{sub 2}O{sub 3} followed by decarbonylation in He at 300 C. The resultant supported clusters were characterized by infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies and as catalysts for ethylene hydrogenation and n-butane hydrogenolysis. After adsorption, the {nu}{sub CO} peaks characterizing the precursor shifted to lower wavenumbers, and some of the hydroxyl bands of the support disappeared or changed, indicating that the CO ligands of the precursor interacted with support hydroxyl groups. The EXAFS results show that the metal core of the precursor remained essentially unchanged upon adsorption, but there were distortions of the metal core indicated by changes in the metal-metal distances. After decarbonylation of the supported clusters, the EXAFS data indicated that Pt and Ru atoms interacted with support oxygen atoms and that about half of the Pt-Ru bonds were maintained, with the composition of the metal frame remaining almost unchanged. The decarbonylated supported bimetallic clusters reported here are the first having essentially the same metal core composition as that of a precursor metal carbonyl, and they appear to be the best-defined supported bimetallic clusters. The material was found to be an active catalyst for ethylene hydrogenation and n-butane hydrogenolysis under conditions mild enough to prevent substantial cluster disruption.

  11. Rhenium Complexes and Clusters Supported on c-Al2O3: Effects of Rhenium Oxidation State and Rhenium Cluster Size on Catalytic Activity for n-butane Hydrogenolysis

    SciTech Connect (OSTI)

    Lobo Lapidus, R.; Gates, B

    2009-01-01

    Supported metals prepared from H{sub 3}Re{sub 3}(CO){sub 12} on {gamma}-Al{sub 2}O{sub 3} were treated under conditions that led to various rhenium structures on the support and were tested as catalysts for n-butane conversion in the presence of H{sub 2} in a flow reactor at 533 K and 1 atm. After use, two samples were characterized by X-ray absorption edge positions of approximately 5.6 eV (relative to rhenium metal), indicating that the rhenium was cationic and essentially in the same average oxidation state in each. But the Re-Re coordination numbers found by extended X-ray absorption fine structure spectroscopy (2.2 and 5.1) show that the clusters in the two samples were significantly different in average nuclearity despite their indistinguishable rhenium oxidation states. Spectra of a third sample after catalysis indicate approximately Re{sub 3} clusters, on average, and an edge position of 4.5 eV. Thus, two samples contained clusters approximated as Re{sub 3} (on the basis of the Re-Re coordination number), on average, with different average rhenium oxidation states. The data allow resolution of the effects of rhenium oxidation state and cluster size, both of which affect the catalytic activity; larger clusters and a greater degree of reduction lead to increased activity.

  12. table07.chp:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    558 - 893 -73 1,935 -111 0 3,387 38 0 Natural Gas Liquids and LRGs ....... 283 89 116 - 9 -210 - 123 24 558 Pentanes Plus .................................. 37 - 1 - 17 7 - 25 15 9 Liquefied Petroleum Gases .............. 246 89 115 - -8 -217 - 98 10 550 Ethane/Ethylene ........................... 94 0 (s) - -71 -4 - 0 0 26 Propane/Propylene ....................... 100 116 86 - 31 -155 - 0 3 485 Normal Butane/Butylene .............. 37 -27 16 - 18 -48 - 74 6 12 Isobutane/Isobutylene

  13. Total Crude Oil and Petroleum Products Exports

    Gasoline and Diesel Fuel Update (EIA)

    Exports Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Biomass-Based Diesel Unfinished Oils Naphthas and Lighter

  14. Crude Oil and Petroleum Products Movements by Pipeline between PAD

    Gasoline and Diesel Fuel Update (EIA)

    Districts Pipeline between PAD Districts Product: Crude Oil and Petroleum Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Isobutane/Isobutylene Normal Butane/Butylene Motor Gasoline Blend. Comp. (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other Renewable Fuels Renewable Diesel Fuel Finished Motor Gasoline

  15. East Coast (PADD 1) Total Crude Oil and Petroleum Products Net Receipts by

    Gasoline and Diesel Fuel Update (EIA)

    Pipeline, Tanker, Barge and Rail Product: Total Crude Oil and Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Unfinished Oils Motor Gasoline Blend. Comp. (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - RBOB for Blending w/ Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other

  16. Crude Oil Movements by Tanker, Pipeline, Barge and Rail between PAD

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Districts Product: Crude Oil and Petroleum Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Unfinished Oils Motor Gasoline Blend. Components (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - RBOB for Blending w/ Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other Renewable

  17. Crude Oil Net Receipts by Pipeline, Tanker, Barge and Rail between PAD

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Districts Product: Total Crude Oil and Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Unfinished Oils Motor Gasoline Blend. Comp. (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - RBOB for Blending w/ Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other Renewable Fuels Fuel

  18. Product Supplied for Total Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Liquids and LRGs Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Unfinished Oils Motor Gasoline Blend. Comp. (MGBC) MGBC - Reformulated MGBC - Conventional Aviation Gasoline Blend. Comp. Finished Petroleum Products Finished Motor Gasoline Reformulated Gasoline Conventional Gasoline Finished

  19. Refinery Stocks of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    Product: Crude Oil and Petroleum Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Other Hydrocarbons Unfinished Oils Naphthas and Lighter Kerosene and Light Gas Oils

  20. Total

    U.S. Energy Information Administration (EIA) Indexed Site

    Product: Total Crude Oil Liquefied Petroleum Gases Propane/Propylene Normal Butane/Butylene Other Liquids Oxygenates Fuel Ethanol MTBE Other Oxygenates Biomass-based Diesel Fuel Other Renewable Diesel Fuel Other Renewable Fuels Gasoline Blending Components Petroleum Products Finished Motor Gasoline Reformulated Gasoline Conventional Gasoline Kerosene-Type Jet Fuel Kerosene Distillate Fuel Oil Distillate Fuel Oil, 15 ppm Sulfur and Under Distillate Fuel Oil, Greater than 15 ppm to 500 ppm Sulfur

  1. Total

    U.S. Energy Information Administration (EIA) Indexed Site

    Product: Total Crude Oil Liquefied Petroleum Gases Propane/Propylene Normal Butane/Butylene Other Liquids Oxygenates Fuel Ethanol MTBE Other Oxygenates Biomass-based Diesel Other Renewable Diesel Fuel Other Renewable Fuels Gasoline Blending Components Petroleum Products Finished Motor Gasoline Reformulated Gasoline Conventional Gasoline Kerosene-Type Jet Fuel Kerosene Distillate Fuel Oil Distillate Fuel Oil, 15 ppm Sulfur and Under Distillate Fuel Oil, Greater than 15 ppm to 500 ppm Sulfur

  2. MAN or FA from n-butane

    SciTech Connect (OSTI)

    Di Cio, A.; Verde, L.

    1985-08-01

    Unsaturated polyester resins were first produced mostly from fumaric acid (FA) rather than from maleic anhydride (MAN). This is perfectly understandable if we consider that, using fumaric acid as raw material, polycondensates with a more homogeneous (less branched) structure are obtained, thus producing resins characterized by a more uniform and reproducible chemical and mechanical properties. Presently, for economical reasons, fumaric acid is used marginally as a MAN substitute in the production of polyester resins. These resins account for a major share (50%) of the overall MAN consumption in the U.S. and in Western Europe.

  3. (2R)-4-Oxo-4[3-(Trifluoromethyl)-5,6-diihydro:1,2,4}triazolo[4,3-a}pyrazin-7(8H)-y1]-1-(2,4,5-trifluorophenyl)butan-2-amine: A Potent, Orally Active Dipeptidyl Peptidase IV Inhibitor for the Treatment of Type 2 Diabetes

    SciTech Connect (OSTI)

    Kim, D.; Wang, L.; Beconi, M.; Eiermann, G.; Fisher, M.; He, H.; Hickey, G.; Kowalchick, Jennifer; Leiting, Barbara; Lyons, K.; Marsilio, F.; McCann, F.; Patel, R.; Petrov, A.; Scapin, G.; Patel, S.; Roy, R.; Wu, J.; Wyvratt, M.; Zhang, B.; Zhu, L.; Thornberry, N.; Weber, A.

    2010-11-10

    A novel series of {beta}-amino amides incorporating fused heterocycles, i.e., triazolopiperazines, were synthesized and evaluated as inhibitors of dipeptidyl peptidase IV (DPP-IV) for the treatment of type 2 diabetes. (2R)-4-Oxo-4-[3-(trifluoromethyl)-5,6-dihydro[1,2,4]triazolo[4,3-a]pyrazin-7(8H)-yl]-1-(2,4,5-trifluorophenyl)butan-2-amine (1) is a potent, orally active DPP-IV inhibitor (IC{sub 50} = 18 nM) with excellent selectivity over other proline-selective peptidases, oral bioavailability in preclinical species, and in vivo efficacy in animal models. MK-0431, the phosphate salt of compound 1, was selected for development as a potential new treatment for type 2 diabetes.

  4. U.S. Natural Gas Processing Plant

    Gasoline and Diesel Fuel Update (EIA)

    All Oils (Excluding Crude Oil) 6,491 6,324 6,877 6,774 5,691 4,837 1993-2015 Pentanes Plus 828 813 728 852 804 780 1993-2015 Liquefied Petroleum Gases 5,663 5,511 6,149 5,922 4,887 4,057 1993-2015 Ethane/Ethylene 1,250 999 1,243 1,336 1,311 819 1993-2015 Propane/Propylene 1,640 1,796 1,843 1,671 1,598 1,677 1993-2015 Normal Butane/Butylene 2,260 2,239 2,529 2,411 1,701 1,160 1993-2015 Isobutane/Butylene 513 477 534 504 277 40

  5. U.S. Natural Gas Processing Plant

    U.S. Energy Information Administration (EIA) Indexed Site

    All Oils (Excluding Crude Oil) 4,738 3,841 4,828 5,118 4,005 4,837 1993-2015 Pentanes Plus 619 501 383 486 924 780 1993-2015 Liquefied Petroleum Gases 4,119 3,340 4,445 4,632 3,081 4,057 1993-2015 Ethane/Ethylene 956 647 837 856 572 819 1993-2015 Propane/Propylene 1,371 1,505 1,944 2,297 1,246 1,677 1993-2015 Normal Butane/Butylene 1,292 688 907 992 678 1,160 1993-2015 Isobutane/Butylene 500 500 757 487 585 40

  6. table05.chp:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    27 - 1,721 -65 -3 170 0 1,511 0 0 Natural Gas Liquids and LRGs ....... 27 18 40 - 153 -28 - 8 1 257 Pentanes Plus .................................. 3 - 0 - 0 (s) - 0 (s) 2 Liquefied Petroleum Gases .............. 24 18 40 - 153 -28 - 8 1 254 Ethane/Ethylene ............................ 8 0 0 - 0 0 - 0 0 8 Propane/Propylene ........................ 11 54 39 - 149 -8 - 0 1 261 Normal Butane/Butylene ............... 4 -27 1 - 3 -18 - 5 (s) -7 Isobutane/Isobutylene ................... 1 -9 0 - 0 -2

  7. table09.chp:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    3,434 - 5,080 -9 -1,729 230 0 6,546 0 0 Natural Gas Liquids and LRGs ....... 1,272 347 65 - -68 -208 - 229 29 1,566 Pentanes Plus .................................. 188 - 33 - -5 30 - 66 0 119 Liquefied Petroleum Gases .............. 1,084 347 31 - -63 -238 - 163 29 1,446 Ethane/Ethylene ........................... 503 24 18 - 112 -52 - 0 0 709 Propane/Propylene ....................... 363 301 4 - -158 -120 - 0 21 610 Normal Butane/Butylene .............. 76 3 6 - -11 -89 - 100 8 54

  8. table10.chp:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    1,049 - 6,332 1,608 -4,050 -23 0 14,962 0 0 12,816 Natural Gas Liquids and LRGs ......... 4,049 -11 536 - -2,893 -15 - 595 6 1,095 1,354 Pentanes Plus ................................... 771 - 112 - -352 -8 - 163 5 371 219 Liquefied Petroleum Gases ............... 3,278 -11 424 - -2,541 -7 - 432 (s) 725 1,135 Ethane/Ethylene ............................ 950 0 0 - -1,270 0 - 0 0 -320 213 Propane/Propylene ....................... 1,473 284 233 - -705 -50 - 0 (s) 1,335 439 Normal Butane/Butylene

  9. Supply and Disposition of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    350 27 3,748 1,617 3,858 102 154 3,693 239 5,616 Crude Oil 48 - - - - 702 387 102 37 1,145 56 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 302 0 14 59 -21 - - -21 48 49 277 Pentanes Plus 35 0 - - - 0 - - 1 3 1 29 Liquefied Petroleum Gases 267 - - 14 59 -20 - - -22 45 48 248 Ethane/Ethylene 102 - - 1 - -104 - - 1 - - -2 Propane/Propylene 112 - - 39 51 84 - - -12 - 39 259 Normal Butane/Butylene 38 - - -26 3 0 - - -12 32 9 -15 Isobutane/Isobutylene 15 - - 0 5 0 - - 0 13 0 6 Other

  10. Supply and Disposition of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    2,576 962 4,466 2,693 -646 -330 113 4,240 396 4,972 Crude Oil 1,802 - - - - 2,581 -260 -368 63 3,661 29 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 775 -20 24 76 -69 - - -181 122 238 607 Pentanes Plus 90 -20 - - 0 175 - - 41 11 163 30 Liquefied Petroleum Gases 684 - - 24 76 -244 - - -222 111 75 577 Ethane/Ethylene 239 - - - - -56 - - 7 - 64 112 Propane/Propylene 292 - - 117 61 -188 - - -122 - 2 402 Normal Butane/Butylene 98 - - -88 6 -5 - - -106 63 9 45 Isobutane/Isobutylene 55 - -

  11. Supply and Disposition of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    1,035 14 648 320 -731 57 36 615 23 669 Crude Oil 715 - - - - 296 -423 50 21 600 16 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 320 0 5 22 -293 - - -19 27 6 39 Pentanes Plus 56 0 - - - -44 - - -1 5 5 2 Liquefied Petroleum Gases 264 - - 5 22 -249 - - -18 22 2 37 Ethane/Ethylene 70 - - - - -74 - - 0 - - -4 Propane/Propylene 124 - - 9 21 -110 - - -6 - 0 50 Normal Butane/Butylene 51 - - -5 0 -40 - - -13 13 1 5 Isobutane/Isobutylene 20 - - 1 1 -25 - - 1 9 - -13 Other Liquids - - 14 - - 1

  12. Supply and Disposition of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    1,158 20 2,921 1,258 550 42 -236 2,766 460 2,958 Crude Oil 1,092 - - - - 1,042 166 3 -59 2,362 0 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 67 0 -4 11 0 - - -60 82 36 16 Pentanes Plus 31 0 - - - - - - 0 26 0 4 Liquefied Petroleum Gases 36 - - -4 11 0 - - -60 56 35 13 Ethane/Ethylene 0 - - - - - - - - - - 0 Propane/Propylene 12 - - 29 11 - - - -28 - 31 49 Normal Butane/Butylene 14 - - -33 0 - - - -31 39 4 -31 Isobutane/Isobutylene 10 - - 1 0 0 - - -1 17 0 -5 Other Liquids - - 21 - -

  13. LPG--a direct source of C/sub 3/-C/sub 4/ olefins

    SciTech Connect (OSTI)

    Pujado, P.R.; Berg, R.C.; Vora, B.V.

    1983-03-28

    This article describes the selective production of olefins by the catalytic dehydrogenation of the corresponding paraffins by means of UOP's Oleflex process. In this process, propylene can be obtained at about 85 mol % selectivity by the catalytic dehydrogenation of propane. Isobutylene can be obtained at selectivities in excess of 90 mol % from isobutane, and n-butenes (1-butene plus 2-butene) at about 80 mol % from n-butane. The availability of this technology, coupled with an abundant supply of LPG (C/sub 3/ and C/sub 4/ paraffins), opens new avenues for the selective production of propylene and butylenes.

  14. Supply and Disposition of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    1,070 15 662 340 -704 -26 10 637 18 693 Crude Oil 746 - - - - 326 -421 -32 9 602 8 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 323 0 13 10 -297 - - 1 20 7 21 Pentanes Plus 55 0 - - - -45 - - 0 6 5 -1 Liquefied Petroleum Gases 268 - - 13 10 -252 - - 1 14 2 22 Ethane/Ethylene 77 - - - - -76 - - 0 - - 1 Propane/Propylene 122 - - 9 9 -110 - - 0 - 0 29 Normal Butane/Butylene 50 - - 3 0 -40 - - 1 7 2 5 Isobutane/Isobutylene 19 - - 0 1 -25 - - 0 7 0 -13 Other Liquids - - 15 - - 1 16 -12 1

  15. Jet fuel from LPG

    SciTech Connect (OSTI)

    Maples, R.E.; Jones, J.R.

    1983-02-01

    Explains how jet fuel can be manufactured from propane and/or butane with attractive rates of return. This scheme is advantageous where large reserves of LPG-bearing gas is available or LPG is in excess. The following sequence of processes in involved: dehydrogenation of propane (and/or butane) to propylene (and/or butylene); polymerization of this monomer to a substantial yield of the desired polymer by recycling undesired polymer; and hydrotreating the polymer to saturate double bonds. An attribute of this process scheme is that each of the individual processes has been practiced commercially. The process should have appeal in those parts of the world which have large reserves of LPG-bearing natural gas but little or no crude oil, or where large excesses of LPG are available. Concludes that economic analysis shows attractive rates of return in a range of reasonable propane costs and product selling prices.

  16. Fueling Requirements for Steady State high butane current fraction discharges

    SciTech Connect (OSTI)

    R.Raman

    2003-10-08

    The CT injector originally used for injecting CTs into 1T toroidal field discharges in the TdeV tokamak was shipped PPPL from the Affiliated Customs Brokers storage facility in Montreal during November 2002. All components were transported safely, without damage, and are currently in storage at PPPL, waiting for further funding in order to begin advanced fueling experiments on NSTX. The components are currently insured through the University of Washington. Several technical presentations were made to investigate the feasibility of the CT injector installation on NSTX. These technical presentations, attached to this document, were: (1) Motivation for Compact Toroida Injection in NSTX; (2) Assessment of the Engineering Feasibility of Installing CTF-II on NSTX; (3) Assessment of the Cost for CT Installation on NSTX--A Peer Review; and (4) CT Fueling for NSTX FY 04-08 steady-state operation needs.

  17. LIQUID BUTANE FILLED LOAD FOR A LINER DRIVEN PEGASUS EXPERIMENT

    SciTech Connect (OSTI)

    M.A. SALAZAR; W. ANDERSON; ET AL

    2001-06-01

    A hydrogen rich, low density liquid, contained within the internal volume of a cylindrical liner, was requested of the Polymers and Coatings Group (MST-7) of the Los Alamos Materials Science Division for one of the last liner driven experiments conducted on the Los Alamos Pegasus facility. The experiment was a continuation of the Raleigh-Taylor hydrodynamics series of experiments and associated liners that have been described previously [1,2].

  18. Liquid butane filled load for a liner driven Pegasus experiment.

    SciTech Connect (OSTI)

    Salazar, M. A.; Armijo, E. V.; Anderson, W. E.; Atchison, W. L.; Bartos, J. J.; Garcia, F.; Randolph, B.; Sheppard, M. G.; Stokes, J. L.

    2001-01-01

    A hydrogen rich, low density liquid, contained within the internal volume of a cylindrical liner, was requested of the Polymers and Coatings Group (MST-7) of the Los Alamos Materials Science Division for one of the last liner driven experiments conducted on the Los Alamos Pegasus facility. The experiment (Fig.1) was a continuation of the Raleigh-Taylor hydrodynamics series of experiments and associated liners that have been described previously.

  19. Supply and Disposition of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    2,637 1,124 19,833 9,726 12 -218 18,732 5,275 19,544 Crude Oil 9,262 - - - - 7,900 -200 -195 16,765 392 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 3,375 -22 330 180 - - -619 649 1,067 2,765 Pentanes Plus 409 -22 - - 10 - - 13 134 170 80 Liquefied Petroleum Gases 2,967 - - 330 170 - - -632 515 898 2,685 Ethane/Ethylene 1,210 - - 7 - - - 12 - 64 1,141 Propane/Propylene 1,134 - - 578 144 - - -251 - 751 1,356 Normal Butane/Butylene 314 - - -243 11 - - -379 304 78 79

  20. Supply and Disposition of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    7,518 100 8,051 3,839 -3,031 140 -286 7,418 4,156 5,329 Crude Oil 5,606 - - - - 3,280 130 12 -259 8,997 292 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 1,912 -1 291 12 383 - - -338 370 739 1,826 Pentanes Plus 197 -1 - - 10 -130 - - -29 88 1 16 Liquefied Petroleum Gases 1,715 - - 291 2 514 - - -309 282 738 1,811 Ethane/Ethylene 798 - - 7 - 235 - - 5 - - 1,035 Propane/Propylene 593 - - 384 - 214 - - -83 - 678 596 Normal Butane/Butylene 114 - - -92 2 46 - - -218 157 54 76

  1. From PADD 1 to PADD 2 Movements by Tanker, Pipeline, Barge and Rail

    Gasoline and Diesel Fuel Update (EIA)

    2010 2011 2012 2013 2014 2015 View History Crude Oil and Petroleum Products 112,461 113,596 110,881 113,554 139,062 150,573 1981-2015 Crude Oil 274 590 1,646 2,729 3,915 2,727 1981-2015 Petroleum Products 112,187 113,006 109,235 110,825 135,147 147,846 1981-2015 Pentanes Plus 452 113 19 2 30 121 2009-2015 Liquefied Petroleum Gases 0 0 0 236 23,034 33,098 1981-2015 Ethane/Ethylene 236 22,845 32,344 2013-2015 Propane/Propylene 0 0 0 0 135 538 2005-2015 Normal Butane/Butylene 0 0 0 0 15 60

  2. U.S. Exports of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    4,967 4,564 4,884 4,628 4,817 5,275 1973-2015 Crude Oil 526 461 409 500 320 392 1920-2015 Natural Gas Plant Liquids and Liquefied Refinery Gases 1,021 991 1,136 970 1,058 1,067 1981-2015 Pentanes Plus 200 197 234 153 201 170 1984-2015 Liquefied Petroleum Gases 821 794 903 817 857 898 1973-2015 Ethane/Ethylene 65 60 51 68 66 64 1981-2015 Propane/Propylene 624 597 739 622 676 751 1973-2015 Normal Butane/Butylene 125 128 107 116 109 78 1981-2015 Isobutane/Isobutylene 6 10 5 10 7 5 1984-2015 Other

  3. U.S. Imports of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    9,511 9,768 9,335 8,800 9,126 9,726 1973-2015 Crude Oil 7,331 7,638 7,222 7,121 7,371 7,900 1920-2015 Natural Gas Plant Liquids and Liquefied Refinery Gases 117 133 102 130 163 180 1981-2015 Pentanes Plus 0 10 0 10 22 10 1981-2015 Liquefied Petroleum Gases 117 123 101 120 141 170 1973-2015 Ethane 1993-2006 Ethylene 1993-2015 Propane 74 80 65 80 104 124 1995-2015 Propylene 22 23 14 11 13 20 1993-2015 Normal Butane 5 2 6 17 10 7 1995-2015 Butylene 4 4 5 3 2 4 1993-2015 Isobutane 12 13 11 8 12 15

  4. U.S. Product Supplied for Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    19,979 19,814 19,225 19,350 19,188 19,544 1963-2015 Crude Oil 0 0 0 0 0 0 1981-2015 Natural Gas Liquids and LRGs 2,402 2,335 2,135 2,429 2,552 2,765 1981-2015 Pentanes Plus 73 146 62 135 36 80 1981-2015 Liquefied Petroleum Gases 2,329 2,189 2,072 2,294 2,516 2,685 1973-2015 Ethane/Ethylene 1,067 971 1,035 1,068 1,170 1,141 1981-2015 Propane/Propylene 980 998 896 1,020 1,145 1,356 1973-2015 Normal Butane/Butylene 190 123 66 99 99 79 1981-2015 Isobutane/Isobutylene 93 97 75 107 102 109 1981-2015

  5. Injection of LPG into TCC unit

    SciTech Connect (OSTI)

    Chou, T.S.

    1987-02-03

    A process is described for catalytically cracking hydrocarbon feed in a bed of catalyst effective to crack the hydrocarbon feed, comprising contacting the feed under catalytic cracking conditions, with the catalyst in a first portion of the bed, to produce cracked product. Another portion of that bed of catalyst is sealed by introducing into another portion of that bed a seal selected from the group consisting of ethane, propane, butane, isobutane, ethylene, propylene, butylene, isobutylene and mixtures thereof whereby feed and cracked product are prevented from surging into another portion; whereby contact of the seal with catalyst in another portion of the bed results in conversion of the seal to the higher molecular weight adducts thereof, the condition in another portion of the bed being effective to provide the conversion.

  6. Supply and Disposition of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    12,703 1,095 19,893 9,401 343 434 18,855 4,750 19,395 Crude Oil 9,430 - - - - 7,351 136 252 16,207 458 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 3,273 -21 612 144 - - 60 516 967 2,465 Pentanes Plus 429 -21 - - 11 - - 0 146 182 91 Liquefied Petroleum Gases 2,844 - - 612 133 - - 60 369 785 2,375 Ethane/Ethylene 1,108 - - 6 0 - - -3 - 65 1,051 Propane/Propylene 1,117 - - 559 112 - - 51 - 615 1,121 Normal Butane/Butylene 324 - - 55 10 - - 12 169 98 110 Isobutane/Isobutylene 296 - - -7

  7. Supply and Disposition of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    327 28 3,799 1,686 3,728 98 96 3,748 247 5,574 Crude Oil 50 - - - - 624 436 94 3 1,121 79 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 277 -1 39 46 -12 - - 3 35 45 267 Pentanes Plus 32 -1 - - 0 0 - - 0 2 2 28 Liquefied Petroleum Gases 245 - - 39 46 -12 - - 2 33 43 239 Ethane/Ethylene 84 - - 0 - -87 - - 0 - - -2 Propane/Propylene 110 - - 37 41 76 - - 3 - 38 223 Normal Butane/Butylene 36 - - 2 1 0 - - -1 23 6 11 Isobutane/Isobutylene 14 - - -1 4 0 - - 0 10 0 7 Other Liquids - - 29 - -

  8. Supply and Disposition of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    569 926 4,517 2,414 -572 32 125 4,312 433 5,015 Crude Oil 1,873 - - - - 2,305 -426 -2 109 3,561 79 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 696 -19 112 70 -45 - - 6 92 253 463 Pentanes Plus 88 -19 - - 0 127 - - 2 18 172 3 Liquefied Petroleum Gases 608 - - 112 70 -172 - - 4 73 81 460 Ethane/Ethylene 191 - - 0 0 -27 - - 2 - 65 98 Propane/Propylene 274 - - 112 57 -122 - - -2 - 4 318 Normal Butane/Butylene 94 - - 2 7 -26 - - 4 27 12 33 Isobutane/Isobutylene 48 - - -1 6 4 - - 0 46 0

  9. Supply and Disposition of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    7,603 102 7,850 3,587 -2,973 131 193 7,261 3,647 5,199 Crude Oil 5,693 - - - - 2,974 255 8 114 8,531 284 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 1,910 -1 398 13 354 - - 51 299 625 1,699 Pentanes Plus 223 -1 - - 11 -81 - - -3 96 1 58 Liquefied Petroleum Gases 1,687 - - 398 2 435 - - 54 204 624 1,641 Ethane/Ethylene 755 - - 5 - 190 - - -4 - - 955 Propane/Propylene 599 - - 360 0 156 - - 52 - 551 512 Normal Butane/Butylene 131 - - 40 2 67 - - 6 86 66 81 Isobutane/Isobutylene 202 - -

  10. Supply and Disposition of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    1,134 24 3,064 1,374 522 108 10 2,897 404 2,915 Crude Oil 1,068 - - - - 1,122 156 69 16 2,391 8 0 Natural Gas Plant Liquids and Liquefied Refinery Gases 66 0 50 6 0 - - 0 71 36 16 Pentanes Plus 30 0 - - 0 - - - 0 25 2 3 Liquefied Petroleum Gases 36 - - 50 6 0 - - 0 46 34 13 Ethane/Ethylene 0 - - - - - - - - - - 0 Propane/Propylene 12 - - 41 5 - - - -2 - 22 39 Normal Butane/Butylene 12 - - 7 0 - - - 2 25 12 -20 Isobutane/Isobutylene 11 - - 3 0 0 - - 0 21 0 -6 Other Liquids - - 24 - - 114 314 15 3

  11. Production of biodiesel using expanded gas solvents

    SciTech Connect (OSTI)

    Ginosar, Daniel M; Fox, Robert V; Petkovic, Lucia M

    2009-04-07

    A method of producing an alkyl ester. The method comprises providing an alcohol and a triglyceride or fatty acid. An expanding gas is dissolved into the alcohol to form a gas expanded solvent. The alcohol is reacted with the triglyceride or fatty acid in a single phase to produce the alkyl ester. The expanding gas may be a nonpolar expanding gas, such as carbon dioxide, methane, ethane, propane, butane, pentane, ethylene, propylene, butylene, pentene, isomers thereof, and mixtures thereof, which is dissolved into the alcohol. The gas expanded solvent may be maintained at a temperature below, at, or above a critical temperature of the expanding gas and at a pressure below, at, or above a critical pressure of the expanding gas.

  12. From PADD 1 to PADD 2 Movements by Tanker, Pipeline, Barge and Rail

    Gasoline and Diesel Fuel Update (EIA)

    Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History Crude Oil and Petroleum Products 13,211 13,548 12,776 13,576 13,240 12,063 1986-2015 Crude Oil 197 135 121 152 136 126 1986-2015 Petroleum Products 13,014 13,413 12,655 13,424 13,104 11,937 1986-2015 Pentanes Plus 10 10 11 10 10 11 2009-2015 Liquefied Petroleum Gases 3,241 2,966 2,828 2,956 3,262 3,331 1986-2015 Ethane/Ethylene 3,178 2,904 2,766 2,893 3,200 3,269 2013-2015 Propane/Propylene 45 44 44 45 44 44 2005-2015 Normal Butane/Butylene

  13. Resonance Raman Spectroscopy of 0-A12O3- Supported Vanadium Oxide Catalysts for Butane Dehydrogenation

    SciTech Connect (OSTI)

    Wu, Zili; Kim, Hack-Sung; Stair, Peter

    2008-01-01

    This chapter contains sections titled: Introduction; Structure of Al{sub 2}O{sub 3}-Supported Vanadia Catalysts; Quantification of Surface VOx Species on Supported Vanadia Catalysts; Conclusion; Acknowledgements; and References.

  14. U.S. Product Supplied for Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    619,354 614,238 576,739 599,856 575,651 605,862 1981-2015 Crude Oil 0 0 0 0 0 0 1981-2015 Natural Gas Liquids and LRGs 74,462 72,397 64,042 75,293 76,572 85,729 1981-2015 Pentanes Plus 2,248 4,534 1,874 4,194 1,087 2,486 1981-2015 Liquefied Petroleum Gases 72,214 67,863 62,168 71,100 75,485 83,244 1981-2015 Ethane/Ethylene 33,077 30,108 31,059 33,115 35,088 35,366 1981-2015 Propane/Propylene 30,376 30,936 26,884 31,606 34,361 42,033 1981-2015 Normal Butane/Butylene 5,878 3,802 1,967 3,065 2,976

  15. NSTec Enforcement Letter

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    handling. NSTec did not identify one of the components of Entron-CE (1,2 butylene oxide) as a possible carcinogen as listed by the International Agency for Research on Cancer. ...

  16. Characterization and permeation properties of ZSM-5 tubular membranes

    SciTech Connect (OSTI)

    Coronas, J.; Falconer, J.L.; Noble, R.D.

    1997-07-01

    ZSM-5 zeolite membranes with reproducible properties were prepared by in-situ synthesis on porous {alpha}- and {gamma}-alumina tubular supports and characterized by XRD, SEM and electron microprobe analysis. Single-gas permeances for H{sub 2}, CH{sub 4}, N{sub 2}, CO{sup 2}, n-butane, and i-butane increase over some temperature range, but some gases exhibit maxima or minima. The highest ideal selectivities at room temperature are 299 for N{sub 2}/SF{sub 6}, 392 for H{sup 2}/n-butane, and 2,820 for H{sub 2}/i-butane. These membranes can separate n-butane/i-butane, H{sub 2}/n-butane and H{sub 2}/i-butane mixtures. All n-butane/i-butane separation selectivities have maxima as a function of temperature and are higher than ideal selectivities because n-butane inhibits i-butane permeation. Thus, separation is not by size selectivity, but is due to pore blocking. Temperature dependencies of single-gas permeances and separation selectivities depend strongly on the location of zeolite crystals and the location is determined by preparation procedure. Ideal selectivities also depend strongly on the preparation procedure. When the zeolite forms a continuous layer on the inside surface of the support tubes, pure i-butane permeates faster than pure n-butane so that the single-gas permeances are not determined just by molecular size. The i-butane permeance also increases much more with temperature than the n-butane permeance. The permeation behavior may be the result of permeation through nonzeolitic pores in parallel with zeolite pores. When zeolite crystals are dispersed throughout the pores of {alpha}-alumina supports, permeances are lower and gas permeation and separation properties are quite different. Ideal selectivities are lower, pure n-butane permeates faster than i-butane, and the permeances increase much less with temperature. Separation selectivities are lower but can be maintained to higher temperatures.

  17. Environmental Regulations and Changes in Petroleum Refining Operations

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Regulations and Changes in Petroleum Refining Operations By Tancred C.M. Lidderdale Contents * Introduction * Motor Gasoline Summer Volatility (RVP) Regulations o Table 1. Summer Volatility Regulations for Motor Gasoline o Table 2. Refinery Inputs and Production of Normal Butane o Figure 1. Refinery Inputs and Production of Normal Butane o Table 3. Price Relationship Between Normal Butane and Motor Gasoline o Table 4. Market Price Premium for Low Vapor Pressure (RVP) Gasoline * Oxygenate Content

  18. --No Title--

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    of legacy Compressed Gas Cylinders that contain, but not limited to: acetylene, argon, boron trifluoride, butane, carbon dioxide, Freon, helium, hydrogen, krypton, liquid...

  19. Tax Credits, Rebates & Savings | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    are those that are used for the primary purpose of converting natural gas or fuel oil to an alternate fuel or power source excluding propane, butane, napht... Eligibility:...

  20. Tax Credits, Rebates & Savings | Department of Energy

    Broader source: Energy.gov (indexed) [DOE]

    natural gas or fuel oil to an alternate fuel or power source excluding propane, butane, napht... Eligibility: Commercial, Industrial Savings Category: Geothermal Electric,...

  1. Tax Credits, Rebates & Savings | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    of converting natural gas or fuel oil to an alternate fuel or power source excluding propane, butane, napht... Eligibility: Commercial, Industrial Savings Category: Geothermal...

  2. Environment/Health/Safety (EHS)

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ethyl ketone, lacquer thinner. Ignitable compressed gases: hydrogen, methane, acetylene, propane, butane, spray-paint cans. Oxidizers: ammonium persulfate, sodium nitrate,...

  3. T

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    capabilities have led to detailed measurements on oxidation of alkanes such as propane, n-butane, heptane, etc. The earliest of these studies, performed by...

  4. Natural gas treatment process using PTMSP membrane

    DOE Patents [OSTI]

    Toy, L.G.; Pinnau, I.

    1996-03-26

    A process is described for separating C{sub 3}+ hydrocarbons, particularly propane and butane, from natural gas. The process uses a poly(trimethylsilylpropyne) membrane. 6 figs.

  5. Natural gas treatment process using PTMSP membrane

    DOE Patents [OSTI]

    Toy, Lora G. (San Francisco, CA); Pinnau, Ingo (Palo Alto, CA)

    1996-01-01

    A process for separating C.sub.3 + hydrocarbons, particularly propane and butane, from natural gas. The process uses a poly(trimethylsilylpropyne) membrane.

  6. Tax Credits, Rebates & Savings | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    conversion facilities are those that are used for the primary purpose of converting natural gas or fuel oil to an alternate fuel or power source excluding propane, butane,...

  7. Tax Credits, Rebates & Savings | Department of Energy

    Broader source: Energy.gov (indexed) [DOE]

    fuel or power source excluding propane, butane, napht... Eligibility: Commercial, Industrial Savings Category: Geothermal Electric, Solar Thermal Process Heat, Wind (All),...

  8. Tax Credits, Rebates & Savings | Department of Energy

    Broader source: Energy.gov (indexed) [DOE]

    facilities are those that are used for the primary purpose of converting natural gas or fuel oil to an alternate fuel or power source excluding propane, butane, napht......

  9. Total Blender Net Input of Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    Input Product: Total Input Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquid Petroleum Gases Normal Butane Isobutane Other Liquids OxygenatesRenewables ...

  10. Refinery & Blender Net Production of Total Finished Petroleum...

    U.S. Energy Information Administration (EIA) Indexed Site

    & Blender Net Production Product: Total Finished Petroleum Products Liquefied Refinery Gases EthaneEthylene Ethane Ethylene PropanePropylene Propane Propylene Normal Butane...

  11. Tax Credits, Rebates & Savings | Department of Energy

    Broader source: Energy.gov (indexed) [DOE]

    those that are used for the primary purpose of converting natural gas or fuel oil to an alternate fuel or power source excluding propane, butane, napht... Eligibility:...

  12. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Crude Oil ......3,882 168 175 8,239 586 1,720 14,125 Normal Butane ......

  13. Petroleum Supply Annual

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Crude Oil ......2,806 2,913 7 137 6,217 426 1,751 11,167 Normal Butane ......

  14. untitled

    U.S. Energy Information Administration (EIA) Indexed Site

    ... North Louisiana, Arkansas New Mexico Total Crude Oil ......879 1,877 68,904 4,801 17,862 119,710 Normal Butane ......

  15. This Week In Petroleum Summary Printer-Friendly Version

    Gasoline and Diesel Fuel Update (EIA)

    bbld from 2013, and a new record high. Increased exports of motor gasoline and hydrocarbon gas liquids (HGL), including propane and butane, were the main contributors to the...

  16. NGL Overview

    Gasoline and Diesel Fuel Update (EIA)

    Stakeholder Review June 14, 2013 EIA's Proposed NGL Realignment: Overview of Proposed Changes EIA's proposed approach to NGL accounting 2 EIA's Proposed NGL Realignment: Overview June 4, 2013 Butanes include normal butane and isobutane. 3 Changes proposed by EIA to realign NGL data and related terminology EIA's Proposed NGL Realignment: Overview June 4, 2013

  17. Interaction of alkanes with an amorphous methanol film at 15-180 K

    SciTech Connect (OSTI)

    Souda, Ryutaro

    2005-09-15

    The hydrogen-bond imperfections and glass-liquid transition of the amorphous methanol film have been investigated on the basis of the film dewetting and the incorporation/desorption of alkane molecules adsorbed on the surface. The butane is incorporated completely in the bulk of the porous methanol film up to 70 K. At least two distinct states exist for the incorporated butane; one is assignable to solvated molecules in the bulk and the other is weakly bound species at the surface or in the subsurface site. For the nonporous methanol film, the uptake of butane in the bulk is quenched but butane forms a surface complex with methanol above 80 K. The butane incorporated in the bulk of the glassy methanol film is released at 120 K, where dewetting of the methanol film occurs simultaneously due to evolution of the supercooled liquid phase.

  18. Superacid catalysis of light hydrocarbon conversion. Final report, August 26, 1993--August 26, 1996

    SciTech Connect (OSTI)

    Gates, B.C.

    1996-12-31

    Motivated by the goal of finding improved catalysts for low- temperature conversion of light alkanes into fuel components or precursors of fuel components, the researchers have investigated sulfated zirconia and promoted sulfated zirconia for conversion of butane, propane, and ethane. Catalyst performance data for sulfated zirconia promoted with iron and manganese show that it is the most active noncorrosive, nonhalide catalyst known for n-butane isomerization, and it is an excellent candidate catalyst for new low- temperature n-butane isomerization processes to make isobutane, which can be converted by established technology into methyl t-butyl ether (MTBE). Various transition metals have been found to work as promoters of sulfated zirconia for n-butane isomerization. The combination of iron and manganese is the best known combination of promoters yet discovered. The iron- and manganese-promoted sulfated zirconia is also a catalyst for conversion of propane and of ethane. Ethane is converted into ethylene and butanes in the presence of the iron- and manganese-promoted sulfated zirconia; propane is also converted into butane, among other products. However, the activities of the catalyst for these reactions are orders of magnitude less than the activity for n-butane conversion, and there is no evidence that the catalyst would be of practical value for conversion of alkanes lighter than butane. The product distribution data for ethane and propane conversion provide new insights into the nature of the catalyst and its acidity. These data suggest the involvement of Olah superacid chemistry, whereby the catalyst protonates the alkane itself, giving carbonium ions (as transition states). The mechanism of protonation of the alkane may also pertain to the conversion of butane, but there is good evidence that the butane conversion also proceeds via alkene intermediates by conventional mechanisms of carbenium ion formation and rearrangement.

  19. Effect of operating conditions and membrane quality on the separation performance of composite silicalite-1 membranes

    SciTech Connect (OSTI)

    Graaf, J.M. van de; Bijl, E. van der; Stol, A.; Kapteijn, F.; Moulign, J.A.

    1998-10-01

    The separation capacity of silicalite-1 membranes for various hydrocarbon mixtures is determined as a function of membrane quality, operating conditions, and orientation of the composite membrane with respect to the feed side. The quality of the membranes is judged on the basis of the n-butane/i-butane permselectivity. Membranes with a different n-butane/i-butane permselectivity showed an identical separation capacity for ethane/methane mixtures, but the quality difference was affecting separation of hydrogen from the butane isomers. The selectivity of the membrane is significantly affected by the operating conditions, such as mixture composition, temperature, and absolute pressure. These effects are shown for ethane/methane, propene/ethene, and n-butane/i-butane mixtures. The selectivity for ethane in ethane/methane mixtures, found when the zeolite layer is facing the feed side, is completely lost when the orientation of the composite membrane is reversed, due to concentration polarization. Depending on the membrane orientation, the major resistance of the composite is in the support layer or in the zeolite layer.

  20. Separation of vapour and gas mixtures using a thin zeolite MFI membrane

    SciTech Connect (OSTI)

    Vroon, Z.A.E.P.; Gilde, M.J.; Kiezer, K.

    1994-12-31

    Zeolite MFI composite membranes were prepared by in situ crystallisation. A very thin (L < 5 {mu}m) polycrystalline MFI layer was grown on a flat {alpha}-Al{sub 2}O{sub 3} support (pore radii 80 nm). XRD and SEM showed that the layer was built of small MFI particles ({+-}200 nm). The single gas flux of methane, n-butane and iso-butane are respectively 9.7, 2.7 and 0.032 10{sup -3} mol.m{sup -2}.s{sup -1} at 25{degrees}C and 100 kPa. The separation of n-butane/methane is reversible. At 25{degrees}C it is possible to separate n-butane from methane. At 200{degrees}C it is possible to separate methane from n-butane. The separation factor for 50 n-butane/50 iso-butane is 26 at 50{degrees}C. Experiments with large molecules showed that the zeolite MFI membrane contains no pores larger than inherent to the zeolite.

  1. Make aromatics from LPG

    SciTech Connect (OSTI)

    Doolan, P.C. ); Pujado, P.R. )

    1989-09-01

    Liquefied petroleum gas (LPG) consists mainly of the propane and butane fraction recovered from gas fields, associated petroleum gas and refinery operations. Apart from its use in steam cracking and stream reforming, LPG has few petrochemical applications. The relative abundance of LPG and the strong demand for aromatics - benzene, toluene and xylenes (BTX) - make it economically attractive to produce aromatics via the aromatization of propane and butanes. This paper describes the Cyclar process, which is based on a catalyst formulation developed by BP and which uses UOP's CCR catalyst regeneration technology, converts propane, butanes or mixtures thereof to petrochemical-quality aromatics in a single step.

  2. U.S. Energy Information Administration (EIA)

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    butane, and isobutane rose 2.2%, 3.0%, and 3.2%, respectively, while the prices of propane and ethane fell by 0.4% and 3.2%, respectively. more summary data PricesDemand...

  3. Short-Term Energy Outlook Model Documentation: Hydrocarbon Gas Liquids Supply and Demand

    Reports and Publications (EIA)

    2015-01-01

    The hydrocarbon gas liquids (ethane, propane, butanes, and natural gasoline) module of the Short-Term Energy Outlook (STEO) model is designed to provide forecasts of U.S. production, consumption, refinery inputs, net imports, and inventories.

  4. Energy Conversion and Thermal Efficiency Sales Tax Exemption

    Broader source: Energy.gov [DOE]

    Qualifying energy conversion facilities are those that are used for the primary purpose of converting natural gas or fuel oil to an alternate fuel or power source excluding propane, butane, napht...

  5. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    and butane; and many other products used for their energy or chemical content. F.O.B. Price (Free on Board) The price actually charged at the producing country's port of loading. ...

  6. untitled

    U.S. Energy Information Administration (EIA) Indexed Site

    28,630 28,630 21,712 18,291 43,765 83,768 Normal Butane ......North Louisiana, Arkansas New Mexico Total Natural Gas Liquids ......

  7. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    5 3,473 3,478 2,622 2,250 4,194 9,066 Normal Butane ......North Louisiana, Arkansas New Mexico Total Natural Gas Plant Liquids ......

  8. Petroleum Supply Annual

    U.S. Energy Information Administration (EIA) Indexed Site

    - 1,736 1,736 1,333 1,063 3,306 5,702 Normal Butane ......North Louisiana, Arkansas New Mexico Total Natural Gas Liquids ......

  9. Table Definitions, Sources, and Explanatory Notes

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    propane, and butane; and many other products used for their energy or chemical content. ... This "green" coke may be sold as is or further purified by calcining. Natural Gas A ...

  10. Webb report adds support for choosing LPG as a motor fuel

    SciTech Connect (OSTI)

    Not Available

    1990-01-01

    This article discusses a study on choosing propane and butane as an alternate transportation fuel (ATF). According to this article, the results of the study indicate that propane and butane have met two of the challenges facing selection of an ATF: there is a ready supply of the product and conversion equipment is easily available. Primary goals identified by the study are presented and discussed.

  11. Dehydrogenation links LPG to more octanes

    SciTech Connect (OSTI)

    Gussow, S.; Spence, D.C.; White, E.A.

    1980-01-01

    Air Products and Chemicals Inc.'s Houdry Catofin process, a new application of well-known Houdry catalytic dehydrogenation technology, is an adiabatic, fixed-bed, multireactor catalytic process which produces propylene, isobutylene, and mixed n-butylenes by dehydrogenation of the corresponding saturates. The process is very flexible in that propylene, isobutylene, and mixed n-butylenes can be produced either separately or simultaneously from the corresponding saturates. The process will be used to prepare purity propylene at a Morelos, Mex., plant, which is now in the engineering stage. Five variations of the procedure for producing propylene; methyl tert.-butyl ether; propylene and alkylate; methyl tert.-butyl ether and alkylate; and methyl tert.-butyl ether, alkylate, and 1-butylene are compared with respect to typical product yields, costs and values for process economics, the dehydrogenation route to the three products, manufacturing costs, the sensitivity of return on investment to feedstock costs, and the return on investment, which varies from a low of 11.5% for the third case to a high of 14.4% for the fourth case. The Catofin process is discussed.

  12. Selective aromatization of C[sub 3] and C[sub 4] paraffins over modified encilite catalysts. 1. Qualitative study

    SciTech Connect (OSTI)

    Jana, A.K.; Rao, M.S. . Department of Chemical Engineering)

    1993-06-01

    The catalytic activity of Zn-encilite in the aromatization of propane and n-butane has been studied by a comparative study of the yields of benzene, toluene, and xylenes (BTX) using propane and n-butane as feeds. The results showed that n-butane had better activity and selectivity to BTX than propane. The effects of reaction temperature, contact time, inlet concentration, poisoning with ammonia on H-encilite, and different degrees of ion exchange with Zn[sup 2+] ion were studied in detail in order to obtain information on the reaction mechanism. The results indicated that the activity and the selectivity were dictated by the acidity and Zn loading on the catalyst.

  13. Superacid catalysis of light hydrocarbon conversion. DOE PETC fourth quarterly report, May 25, 1994--August 24, 1994

    SciTech Connect (OSTI)

    Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments include testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. A solid superacid catalyst was prepared by addition of iron and manganese to sulfated zirconium hydroxide followed by calcination. The catalyst was tested for n-butane conversion in a packed-bed flow reactor at temperatures of 40 to 225{degrees}C with the reactant partial pressure in the range of 0.0025-0.01 attn. The predominant catalytic reaction was n-butane isomerization, and this was accompanied at 40{degrees}C by near stoichiometric disproportionation. The C3/C5 molar ratio was generally greater than 1, consistent with conversion of the secondary C5 products. As the temperature increased, the selectivity for isomerization decreased and that for disproportionation increased. In a typical experiment the activity of the catalyst increased for about 1 h on stream and then declined rapidly. The rate maxima as a function of time on stream were taken as a measure of the initial activity of the catalyst. For example, the approximate rate of isomerization of n-butane at the maximum was 4.3 x 10-8 mol/(g of catalyst {center_dot} s) with a feed n-butane partial pressure of 0.0025 atm at 75{degrees}C. With a feed n-butane partial pressure of 0.005 atm at 40{degrees}C and a conversion of 1 1%, the molar ratio of propane to i-butane was 0.03, and with the same feed composition at 100{degrees}C, this ratio at a conversion of 50% was 0.1. The iron- and manganese-promoted solid superacid catalyst is potentially of value for practical low-temperature paraffin isomerization accompanied by disproportionation of n-butane.

  14. Word Pro - Untitled1

    Gasoline and Diesel Fuel Update (EIA)

    0 Natural Gas Plant Liquids Production Total, 1949-2011 By Product, 2011 By Selected Product, 1949-2011 138 U.S. Energy Information Administration / Annual Energy Review 2011 Source: Table 5.10. 1950 1960 1970 1980 1990 2000 2010 0 500 1,000 1,500 2,000 2,500 Thousand Barrels per Day 909 618 295 208 152 Ethane Propane Pentanes Isobutane Normal 0 200 400 600 800 1,000 Thousand Barrels per Day Plus Butane Isobutane Normal Butane Propane 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005

  15. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOE Patents [OSTI]

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  16. Asia, North America lead way in growth of NGL, LPG trade

    SciTech Connect (OSTI)

    Otto, K.; Gist, R.; Whitley, C.; Haun, R.

    1998-01-12

    Recent analyses of world NGL trade indicate that important changes in LPG supply and demand are under way in Asia and North America. LPG markets in the 1990s reflect a rapidly shifting balance between East-of-Suez and West-of-Suez markets. This shift has increased concern about availability of future LPG supplies for Asia. The paper discusses world developments, East versus West of Suez, end uses and supplies in Asia, Canadian ethane, propane, butane, and natural gasoline, Mexican ethane, LPG, and natural gasoline, US ethane, propane, butanes, and iso-C{sub 4} and C{sub 5}.

  17. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOE Patents [OSTI]

    Sachtler, W.M.H.; Huang, Y.Y.

    1998-07-28

    Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

  18. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOE Patents [OSTI]

    Sachtler, Wolfgang M. H.; Huang, Yin-Yan

    1998-01-01

    Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

  19. Composites structures for bone tissue reconstruction

    SciTech Connect (OSTI)

    Neto, W.; Santos, João; Avérous, L.; Schlatter, G.; Bretas, Rosario

    2015-05-22

    The search for new biomaterials in the bone reconstitution field is growing continuously as humane life expectation and bone fractures increase. For this purpose, composite materials with biodegradable polymers and hydroxyapatite (HA) have been used. A composite material formed by a film, nanofibers and HA has been made. Both, the films and the non-woven mats of nanofibers were formed by nanocomposites made of butylene adipate-co-terephthalate (PBAT) and HA. The techniques used to produce the films and nanofibers were spin coating and electrospinning, respectively. The composite production and morphology were evaluated. The composite showed an adequate morphology and fibers size to be used as scaffold for cell growth.

  20. In situ vibrational spectroscopic investigation of C{sub 4} hydrocarbon selective oxidation over vanadium-phosphorus-oxide catalysts

    SciTech Connect (OSTI)

    Xue, Z.Y.

    1999-05-10

    n-Butane selective oxidation over the VPO catalyst to maleic anhydride is the first and only commercialized process of light alkane selective oxidation. The mechanism of this reaction is still not well known despite over twenty years of extensive studies, which can partially be attributed to the extreme difficulties to characterize catalytic reactions real-time under typical reaction conditions. In situ spectroscopic characterization techniques such as Infrared spectroscopy and laser Raman spectroscopy were used in the current mechanistic investigations of n-butane oxidation over VPO catalysts. To identify the reaction intermediates, oxidation of n-butane, 1,3-butadiene and related oxygenates on the VPO catalyst were monitored using FTIR spectroscopy under transient conditions. n-Butane was found to adsorb on the VPO catalyst to form olefinic species, which were further oxidized to unsaturated, noncyclic carbonyl species. The open chain dicarbonyl species then experienced cycloaddition to form maleic anhydride. VPO catalyst phase transformations were investigated using in situ laser Raman spectroscopy. This report contains Chapter 1: General introduction; Chapter 2: Literature review; and Chapter 5: Conclusion and recommendations.

  1. Influence of NaA Zeolite Crystal Expansion/Contraction on Zeolite Membrane Separations

    SciTech Connect (OSTI)

    Sorenson, Stephanie G; Payzant, E Andrew; Gibbons, Will T; Soydas, Belma; Kita, Hidetoshi; Noble, Richard D; Falconer, John L.

    2011-01-01

    In-situ powder XRD measurements showed that the NaA zeolite unit cell contracts and expands upon adsorption, and these changes in zeolite crystal size correlate with permeation changes through NaA zeolite membranes. These membranes had high pervaporation selectivities, even though gas permeation was mainly through defects, as indicated by Knudsen selectivities for gases. At 300 K and a thermodynamic activity of 0.03, water contracted the NaA crystals by 0.22 vol%, and this contraction increased the helium flux through two NaA membranes by approximately 80%. Crystal contraction also increased the fluxes of i-butane during vapor permeation and i-propanol (IPA) during pervaporation (~ 0.03 wt% water). At activities above 0.07, water expanded NaA crystals and correspondingly decreased the membrane fluxes of helium, i-butane, and IPA. Similarly, methanol contracted NaA crystals by 0.05 vol% at an activity of 0.02, and this contraction slightly increased the helium and i-butane fluxes through a NaA membrane. Above an activity of 0.06, methanol expanded the crystals, and the fluxes of helium and i-butane through a NaA membrane decreased. The adsorbate-induced changes explain some pervaporation behavior reported by others, and they indicate that crystal expansion and contraction may increase or decrease zeolite NaA membrane selectivity by changing the defect sizes.

  2. Engineering development of advanced physical fine coal cleaning for premium fuel applications: Subtask 3.3 - dewatering studies

    SciTech Connect (OSTI)

    Yoon, R. H.; Phillips, D. I.; Sohn, S. M.; Luttrell, G. H.

    1996-10-01

    If successful, the novel Hydrophobic Dewatering (HD) process being developed in this project will be capable of efficiently removing moisture from fine coal without the expense and other related drawbacks associated with mechanical dewatering or thermal drying. In the HD process, a hydrophobic substance is added to a coal-water slurry to displace water from the surface of coal, while the spent hydrophobic substance is recovered for recycling. For this process to have commercialization potential, the amount of butane lost during the process must be small. Earlier testing revealed the ability of the hydrophobic dewatering process to reduce the moisture content of fine coal to a very low amount as well as the determination of potential butane losses by the adsorption of butane onto the coal surface. Work performed in this quarter showed that the state of oxidation affects the amount of butane adsorbed onto the surface of the coal and also affects the final moisture content. the remaining work will involve a preliminary flowsheet of a continuous bench-scale unit and a review of the economics of the system. 1 tab.

  3. MEMS-based fuel cells with integrated catalytic fuel processor and method thereof

    DOE Patents [OSTI]

    Jankowski, Alan F. (Livermore, CA); Morse, Jeffrey D. (Martinez, CA); Upadhye, Ravindra S. (Pleasanton, CA); Havstad, Mark A. (Davis, CA)

    2011-08-09

    Described herein is a means to incorporate catalytic materials into the fuel flow field structures of MEMS-based fuel cells, which enable catalytic reforming of a hydrocarbon based fuel, such as methane, methanol, or butane. Methods of fabrication are also disclosed.

  4. Roaming radical pathways for the decomposition of alkanes.

    SciTech Connect (OSTI)

    Harding, L. B.; Klippenstein, S. J.

    2010-01-01

    CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie {approx}1 kcal/mol below the corresponding radical asymptotes.

  5. PSA Vol 1 Tables Revised Ver 2 Print.xls

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    Pentanes Plus 30 - 1 -17 - 0 6 1 6 Liquefied Petroleum Gases 172 4 9 -141 - 0 9 1 34 EthaneEthylene 82 0 0 -76 - 0 0 0 6 PropanePropylene 57 8 7 -39 - 0 0 0 33 Normal Butane...

  6. Superacid catalysis of light hydrocarbon conversion. DOE PETC third quarterly report, February 25, 1994--May 24, 1994

    SciTech Connect (OSTI)

    Gates, B.C.

    1995-12-31

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline by high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether. The ether is produced from methanol and isobutylene, and the latter can be formed from n-butane by isomerization followed by dehydrogenation. Paraffin isomerization reactions are catalyzed by very strong acids such as aluminum chloride supported on alumina. The aluminum chloride-containing catalysts are corrosive, and their disposal is expensive. Alternatively, hydroisomerization is catalyzed by zeolite-supported metals at high temperatures, but high temperatures do not favor branched products at equilibrium. Thus there is a need for improved catalysts and processes for the isomerization of n-butane and other straight-chain paraffins. Consequently, researchers have sought for solid acids that are noncorrosive and active enough to catalyze isomerization of paraffins at low temperatures. For example, sulfated zirconia catalyzes isomerization of n-butane at temperatures as low as 25{degrees}C. The addition of iron and manganese promoters has been reported to increase the activity of sulfated zirconia for n-butane isomerization by three orders of magnitude. Although the high activity of this catalyst is now established, the reaction network is not known, and the mechanism has not been investigated. The goal of this work is to investigate low-temperature reactions of light paraffins catalyzed by solid superacids of the sulfated zirconia type. The present report is concerned with catalysis of n-butane conversion catalyzed by the Fe- and Mn- promoted sulfated zirconia described in the previous report in this series.

  7. Ventilation of liquefied petroleum gas components from the Valley of Mexico

    SciTech Connect (OSTI)

    Elliott, S.; Blake, D.R.; Sherwood Rowland, F.; Lu, R.; Brown, M.J.; Williams, M.D.; Russell, A.G.; Bossert, J.E.; Streit, G.E.; Santoyo, M.R.; Guzman, F.; Porch, W.M.; McNair, L.A.; Keyantash, J.; Kao, C.J.; Turco, R.P.; Eichinger, W.E.

    1997-09-01

    The saturated hydrocarbons propane and the butane isomers are both indirect greenhouse gases and key species in liquefied petroleum gas (LPG). Leakage of LPG and its component alkanes/alkenes is now thought to explain a significant fraction of the volatile organic burden and oxidative potential in the basin which confines Mexico City. Propane and the butanes, however, are stable enough to escape from the basin. The gas chromatographic measurements which have drawn attention to their sources within the urban area are used here to estimate rates of ventilation into the free troposphere. The calculations are centered on several well studied February/March pollution episodes. Carbon monoxide observations and emissions data are first exploited to provide a rough time constant for the removal of typical inert pollutant species from the valley. The timescale obtained is validated through an examination of meteorological simulations of three-dimensional flow. Heuristic arguments and transport modeling establish that propane and the butanes are distributed through the basin in a manner analogous to CO despite differing emissions functions. Ventilation rates and mass loadings yield outbound fluxes in a box model type computation. Estimated in this fashion, escape from the Valley of Mexico constitutes of the order of half of 1{percent} of the northern hemispheric inputs for both propane and n-butane. Uncertainties in the calculations are detailed and include factors such as flow into the basin via surface winds and the size of the polluted regime. General quantification of the global propane and butane emissions from large cities will entail studies of this type in a variety of locales.{copyright} 1997 American Geophysical Union

  8. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect (OSTI)

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

    Alcohol transformation to transportation fuel range hydrocarbon on HZSM-5 (SiO2 / Al2O3 = 30) catalyst was studied at 360oC and 300psig. Product distributions and catalyst life were compared using methanol, ethanol, 1-propanol or 1-butanol as a feed. The catalyst life for 1-propanol and 1-butanol was more than double compared to that for methanol and ethanol. For all the alcohols studied, the product distributions (classified to paraffin, olefin, napthene, aromatic and naphthalene compounds) varied with time on stream (TOS). At 24 hours TOS, liquid product from 1-propanol and 1-butanol transformation primarily contains higher olefin compounds. The alcohol transformation process to higher hydrocarbon involves a complex set of reaction pathways such as dehydration, oligomerization, dehydrocyclization, and hydrogenation. Compared to ethylene generated from methanol and ethanol, oligomerization of propylene and butylene has a lower activation energy and can readily take place on weaker acidic sites. On the other hand, dehydrocyclization of propylene and butylene to form the cyclic compounds requires the sits with stronger acid strength. Combination of the above mentioned reasons are the primary reasons for olefin rich product generated in the later stage of the time on stream and for the extended catalyst life time for 1 propanol and 1 butanol compared to methanol and ethanol conversion over HZSM-5.

  9. Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Eedugurala, Naresh; Hovey, Megan; Ho, Hung -An; Jana, Barun; Lampland, Nicole L.; Ellern, Arkady; Sadow, Aaron D.

    2015-11-25

    Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. Themore » thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(μ-Cl)]2 and [{BoMCptet}TiCl(μ-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.« less

  10. Thermal decomposition of Mg/V hydrotalcites and catalytic performance of the products in oxidative dehydrogenation reactions

    SciTech Connect (OSTI)

    Holgado, M.J.; Labajos, F.M.; Montero, M.J.S.; Rives, V

    2003-11-26

    Layered double hydroxides with the hydrotalcite-type structure containing Mg{sup 2+} and V{sup 3+} in the brucite-like layers, possessing different V contents, have been prepared and characterised by elemental chemical analysis, powder X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy and specific surface area and porosity assessment by nitrogen adsorption; thermal decomposition was studied by Differential Thermal Analysis and Thermogravimetric Analysis. The solids obtained after calcination at 800 deg. C were tested as catalysts for oxidative dehydrogenation of propane and n-butane. Results indicate that the relative amounts of Mg{sub 3}(VO{sub 4}) and MgO, depending on the V content in the starting hydrotalcite, determines the performance of the catalysts in oxidative dehydrogenation of propane and n-butane.

  11. Solvothermal synthesis of vanadium phosphates in the form of xerogels, aerogels and mesostructures

    SciTech Connect (OSTI)

    Sydorchuk, V.; Zazhigalov, V.; Khalameida, S.; Diyuk, E.; Skubiszewska-Zieba, J.; Leboda, R.; Kuznetsova, L.

    2010-09-15

    Regularities and peculiarities of physicochemical changes, first of all phase transformations, during solvothermal treatment (with conventional and microwave heating) of the vanadium pentoxide and orthophosphoric acid mixture in organic solvents in the presence of reducing agents have been studied. Hemihydrate of vanadium hydrophosphate - the precursor of vanadium pyrophosphate, the active phase for n-butane to maleic anhydride oxidation, and ion exchanger with variable physicochemical characteristics, i.e. crystal structure, specific surface area, crystallite size and acidic properties - has been synthesized in the temperature range 170-200 {sup o}C. The obtained phases were examined using XRD, DTA-TG, SEM, FTIR spectroscopy, nitrogen adsorption as well as gas chromatographic determination of acidity through organic bases adsorption. The catalytic activity of prepared samples for n-butane oxidation has been investigated.

  12. Synthesis of SnO{sub 2} Nanoparticles Using Ultrasonication

    SciTech Connect (OSTI)

    Majumdar, Sanhita; Devi, P. Sujatha

    2010-10-04

    The use of ultrasonic energy for chemical synthesis has recently become an interesting and growing area of research. Using this form of energy, we have synthesized nanoparticles of SnO{sub 2}(8-30 nm) at room temperature by a sonication assisted precipitation technique. In order to understand the effect of ultrasonic energy on particle size and their distribution, the precipitation time was varied during the preparation. A sonication time of 3 h was found to be optimum to produce SnO{sub 2} nanoparticles having size below 10 nm. We found that a gradual increase of the sonication time gradually decreases the particle size with interesting morphology and increased surface area. The butane sensing properties of the synthesized powders exhibited a direct influence of the sonication time on the sensing properties. A 3 h sonicated sample, exhibited a maximum response of around 98.88% towards 5000 ppm butane at 450 deg. C with a fast recovery time.

  13. Determination of alternative fuels combustion products: Phase 2 final report

    SciTech Connect (OSTI)

    Whitney, K.A.

    1997-06-01

    This report describes the laboratory efforts to accomplish four independent tasks: (1) speciation of hydrocarbon exhaust emissions from a light-duty vehicle operated over the chassis dynamometer portion of the light-duty FTP after modifications for operation on butane and butane blends; (2) evaluation of NREL`s Variable Conductance Vacuum Insulated Catalytic Converter Test Article 4 for the reduction of cold-start FTP exhaust emissions after extended soak periods for a Ford FFV Taurus operating on E85; (3) support of UDRI in an attempt to define correlations between engine-out combustion products identified by SwRI during chassis dynamometer testing, and those found during flow tube reactor experiments conducted by UDRI; and (4) characterization of small-diameter particulate matter from a Ford Taurus FFV operating in a simulated fuel-rich failure mode on CNG, LPG, M85, E85, and reformulated gasoline. 22 refs., 18 figs., 17 tabs.

  14. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-04-01

    Concerns over air quality and greenhouse gas emissions have prompted discussion as well as action on alternative fuels and energy efficiency. Natural gas and natural gas derived fuels and fuel additives are prime alternative fuel candidates for the transportation sector. In this study, we reexamine and add to past work on energy efficiency and greenhouse gas emissions of natural gas fuels for transportation (DeLuchi 1991, Santini et a. 1989, Ho and Renner 1990, Unnasch et al. 1989). We add to past work by looking at Methyl tertiary butyl ether (from natural gas and butane component of natural gas), alkylate (from natural gas butanes), and gasoline from natural gas. We also reexamine compressed natural gas, liquified natural gas, liquified petroleum gas, and methanol based on our analysis of vehicle efficiency potential. We compare the results against nonoxygenated gasoline.

  15. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-01-01

    Concerns over air quality and greenhouse gas emissions have prompted discussion as well as action on alternative fuels and energy efficiency. Natural gas and natural gas derived fuels and fuel additives are prime alternative fuel candidates for the transportation sector. In this study, we reexamine and add to past work on energy efficiency and greenhouse gas emissions of natural gas fuels for transportation (DeLuchi 1991, Santini et a. 1989, Ho and Renner 1990, Unnasch et al. 1989). We add to past work by looking at Methyl tertiary butyl ether (from natural gas and butane component of natural gas), alkylate (from natural gas butanes), and gasoline from natural gas. We also reexamine compressed natural gas, liquified natural gas, liquified petroleum gas, and methanol based on our analysis of vehicle efficiency potential. We compare the results against nonoxygenated gasoline.

  16. U.S. LPG pipeline begins deliveries to Pemex terminal

    SciTech Connect (OSTI)

    Bodenhamer, K.C.

    1997-08-11

    LPG deliveries began this spring to the new Mendez LPG receiving terminal near Juarez, State of Chihuahua, Mexico. Supplying the terminal is the 265-mile, 8-in. Rio Grande Pipeline that includes a reconditioned 217-mile, 8-in. former refined-products pipeline from near Odessa, Texas, and a new 48-mile, 8-in. line beginning in Hudspeth County and crossing the US-Mexico border near San Elizario, Texas. Capacity of the pipeline is 24,000 b/d. The LPG supplied to Mexico is a blend of approximately 85% propane and 15% butane. Before construction and operation of the pipeline, PGPB blended the propane-butane mix at a truck dock during loading. Demand for LPG in northern Mexico is strong. Less than 5% of the homes in Juarez have natural gas, making LPG the predominant energy source for cooking and heating in a city of more than 1 million. LPG also is widely used as a motor fuel.

  17. Integrated experimental and theoretical study of the thermophysical properties of fluid mixtures. Annual report, September 1984-September 1985

    SciTech Connect (OSTI)

    Haynes, W.M.

    1985-01-01

    This report summarizes the work done in the twelve months from September 30, 1984. Results include: PVT data for methanol (to 300/sup 0/C) and benzene (to 450/sup 0/C); basic studies of a fluid in nonequilibrium; high temperature VLE data for CO/sub 2//butane; viscosity experimental data and predictive procedures on association for coal liquids, and results on the phenomenon of shear induced phase changes.

  18. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Processing Area Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Conventional Blendstock for Oxygenate Blending (CBOB)

  19. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Input Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Conventional Blendstock for Oxygenate Blending (CBOB) Motor

  20. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    and Blender Net Inputs Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Blending Plant A facility which has no

  1. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Total Stocks Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether), butane, and

  2. Getting Energized

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Getting Energized Elementary School Curriculum Created by the National Renewable Energy Laboratory (NREL) Click on the links below to take you to the Chapter heading: Materials list Activity Guide Energy Sources Energy Uses/Limits Energy Conversion Energy Conservation Energy for the Future Student Assessments Student Evaluation Getting Energized Equipment and Materials List Item/Activity Number Activity 1 Butane Lighter Coal (Bituminous) Amount Where to find 1-Demo Discount /Grocery (Target,

  3. U.S. Refineries Competitive Positions

    Gasoline and Diesel Fuel Update (EIA)

    Refineries Competitive Positions 2014 EIA Energy Conference July 14, 2014 Joanne Shore American Fuel & Petrochemical Manufacturers Refiners competitive positions Function of optimizing feedstock costs, operating costs, and revenues through mix of products sold 2 Propane/butane Chemicals Gasoline Jet Fuel Diesel/heating oil Lubes Fuel for ships Asphalt FEEDSTOCKS Qualities: - Heavy/Light - Sweet/Sour Location (Distance) - Domestic - International PROCESSING Size Complexity Treating (sulfur)

  4. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Lease Condensate Production Definitions Key Terms Definition Lease Condensate A mixture consisting primarily of pentanes and heavier hydrocarbons which is recovered as a liquid from natural gas in lease separation facilities. This category excludes natural gas plant liquids, such as butane and propane, which are recovered at downstream natural gas processing plants or facilities. Production, Lease Condensate The volume of lease condensate produced during the report year. Lease condensate volumes

  5. Refinery & Blenders Net Input of Crude Oil

    U.S. Energy Information Administration (EIA) Indexed Site

    Input Product: Total Crude Oil & Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane Normal Butane Isobutane Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Hydrogen Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Other Hydrocarbons Unfinished Oils (net) Unfinished

  6. Expansion fractionation capacity of the LPG-ULE plant

    SciTech Connect (OSTI)

    Morin, L.M.C.

    1999-07-01

    The Western Division of PDVSA has among other facilities a NGL Fractionation Complex located onshore in Ul'e. The complex consists of three plants, the first and second older plants, LPG-1 and LPG-2, which fractionate the NGL to produce propane, a butane mix and natural gasoline. The third plant, LPG-3, fractionates the butane mix from the LPG-1 and 2 plants to produce iso and normal butane. Several optimization projects already in progress will increase the NGL production to 12,200 b/d. For this reason it was decided to conduct a study of the existing fractionation facilities and utilities systems to determine their capacities. This evaluation revealed that some of the fractionation towers would have some limitations in the processing of the expected additional production. The study recommended an option to increase the capacity of the fractionation towers by lowering their operating pressure, in order to take advantage of relative volatility increase between the key components, which allows easier separation, as well as reducing the heat duty required. The completed study also determined that this option is more economically convenient than the replacement of the existing fractionation towers.

  7. Luminescence-Based Spectroelectrochemical Sensor for [Tc(dmpe)3]2+/+ (dmpe = 1,2-bis(dimethylphosphino)ethane) within a Charge-Selective Polymer Film

    SciTech Connect (OSTI)

    Chatterjee, Sayandev; Del Negro, Andrew S.; Edwards, Matthew K.; Bryan, Samuel A.; Kaval, Necati; Pantelic, Nebojsa; Morris, Laura K.; Heineman, W. R.; Seliskar, Carl J.

    2011-03-01

    A spectroelectrochemical sensor consisting of an indium tin oxide (ITO) optically transparent electrode (OTE) coated with a thin film of sulfonated polystyrene-blockpoly(ethylene-ran-butylene)-block-polystyrene (SSEBS) was developed for [Tc(dmpe)3]+.. [Tc(dmpe)3]+ preconcentrated by ion-exchange into the SSEBS film after 20 min exposure to aqueous [Tc(dmpe)3]+ solution, resulting in a 14-fold increase in cathodic peak current compared to a bare OTE. Colorless [Tc(dmpe)3]+ was reversibly oxidized to colored [Tc(dmpe)3]2+ by cyclic voltammetry. Detection of [Tc(dmpe)3]2+ was accomplished by electrochemically cycling the complex between non-emissive [Tc(dmpe)3]+ and emissive [Tc(dmpe)3]2+ and monitoring the modulated emission (?exc = 532 nm; ?em = 660 nm). The sensor gave a linear response over the range of 0.16 to 340.0 µM.

  8. Physics of the multi-functionality of lanthanum ferrite ceramics

    SciTech Connect (OSTI)

    Bhargav, K. K.; Ram, S.; Majumder, S. B.

    2014-05-28

    In the present work, we have illustrated the physics of the multifunctional characteristics of nano-crystalline LaFeO{sub 3} powder prepared using auto-combustion synthesis. The synthesized powders were phase pure and crystallized into centro-symmetric Pnma space group. The temperature dependence of dielectric constant of pure LaFeO{sub 3} exhibits dielectric maxima similar to that observed in ferroelectric ceramics with non-centrosymmetric point group. The dielectric relaxation of LaFeO{sub 3} correlates well with small polaron conduction. The occurrence of polarization hysteresis in LaFeO{sub 3} (with centro-symmetric Pnma space group) is thought to be spin current induced type. The canting of the Fe{sup 3+} spins induce weak ferromagnetism in nano-crystalline LaFeO{sub 3}. Room temperature saturation magnetization of pure LaFeO{sub 3} is reported to be 3.0?emu/g. Due to the presence of both ferromagnetic as well as polarization ordering, LaFeO{sub 3} behaves like a single phase multiferroic ceramics. The magneto-electric coupling in this system has been demonstrated through the magneto-dielectric measurements which yield about 0.8% dielectric tuning (at 10?kHz) with the application of 2?T magnetic field. As a typical application of the synthesized nano-crystalline LaFeO{sub 3} powder, we have studied its butane sensing characteristics. The efficient butane sensing characteristics have been correlated to their catalytic activity towards oxidation of butane. Through X-ray photoelectron spectroscopy analyses, we detect the surface adsorbed oxygen species on LaFeO{sub 3} surface. Surface adsorbed oxygen species play major role in their low temperature butane sensing. Finally, we have hypothesized that the desorbed H{sub 2}O and O{sub 2} (originate from surface adsorbed hydroxyl and oxygen) initiate the catalytic oxidative dehydrogenation of n-butane resulting in weakening of the electrostatics of the gas molecules.

  9. Studies on the catalytic activity of zirconia promoted with sulfate, iron, and manganese

    SciTech Connect (OSTI)

    Wan, K.T.; Khouw, C.B.; Davis, M.E.

    1996-01-01

    The catalytic properties of iron- and manganese-promoted sulfated zirconia (SFMZ) for the isomerization of n-butane to isobutane are investigated using various catalyst pretreatments and reaction conditions. The n-butane isomerization reactivity at 30{degrees}C is effected by calcination of the catalyst at 650{degrees}C in helium and vacuum treatment at room temperature indicating that superacidity is not likely to be responsible for activity. In addition, SFMZ samples exposed to dry air at over 450{degrees}C are more active than those calcined in helium at a reaction temperature of 30{degrees}C (n-butane conversions of 18.7% vs 0.4%) suggesting the presence of an active site involving a metal {open_quotes}oxy{close_quotes} species. The oxy species is capable of reacting CO to CO{sub 2} at room temperature and is present at a number density of 10-15 {mu}mol/g. At a reaction temperature of 100{degrees}C, SFMZ catalysts calcined in air then activated in helium show similar reactivities to those activated in air up to a preheating temperature of 450{degrees}C; above 450{degrees}C the metal oxy species is formed and provides additional activity (n-butane conversions of 37.1% in air vs 15.4% in He for calcinations at 650{degrees}C). The nature of the active sites on SFMZ are investigated using temperature-programmed desorption of substituted benzenes. The liberation of CO{sub 2} and SO{sub 2} in the benzene TPD profile of SFMZ is attributed to the oxidation of benzene at the redox-active metal sites, resulting in the subsequent decomposition of the reduced iron (II) sulfate. Data from the TPD studies do not suggest the presence of superacidity on SFMZ that could contribute to the low-temperature n-butane isomerization activity. Instead, a bifunctional mechanism that involves a combination of a redox-active metal site and an acid site in close proximity is proposed. 62 refs., 17 figs., 4 tabs.

  10. Hydrophobic Dewatering of Fine Coal. Topical report, March 1, 1995-March 31, 1997

    SciTech Connect (OSTI)

    Yoon, R.; Sohn, S.; Luttrell, J.; Phillips, D.

    1997-12-31

    Many advanced fine coal cleaning technologies have been developed in recent years under the auspices of the U.S. Department of Energy. However, they are not as widely deployed in industry as originally anticipated. An important reason for this problem is that the cleaned coal product is difficult to dewater because of the large surface area associated with fine particles. Typically, mechanical dewatering, such as vacuum filtration and centrifugation, can reduce the moisture to 20-35% level, while thermal drying is costly. To address this important industrial problem, Virginia Tech has developed a novel dewatering process, in which water is displaced from the surface of fine particulate materials by liquid butane. Since the process is driven by the hydrophobic interaction between coal and liquid butane, it was referred to as hydrophobic dewatering (HD). A fine coal sample with 21.4 pm median size was subjected to a series of bench-scale HD tests. It was a mid-vol bituminous coal obtained from the Microcel flotation columns operating at the Middle Fork coal preparation plant, Virginia. All of the test results showed that the HD process can reduce the moisture to substantially less than 10%. The process is sensitive to the amount of liquid butane used in the process relative to the solids concentration in the feed stream. Neither the intensity nor the time of agitation is critical for the process. Also, the process does not require long time for phase separation. Under optimal operating conditions, the moisture of the fine coal can be reduced to 1% by weight of coal.

  11. State of Terengganu: A development plan for the petrochemical industry and its associated downstream industries. Final report

    SciTech Connect (OSTI)

    Not Available

    1987-01-08

    This study, conducted by Chem Systems, Inc., was funded by the U.S. Trade and Development Agency on behalf of Terengganu's State Economic Planning Unit. The main objectives of the report are to: (1) Identify and list all medium stream and downstream activities, including services in petrochemical industries, using natural gas-derived ethane, propane, and butane as main feedstock and other linkages; (2) List the various enterprises noted above that can be economically and viably established in Terengganu; (3) Identify and locate the various sites for the projects identified. This is volume 1 of 2 and it contains the Final Report.

  12. State of Terengganu: A development plan for the petrochemical industry and its associated downstream industries. Appendix. Export trade information

    SciTech Connect (OSTI)

    Not Available

    1987-02-01

    The study, conducted by Chem Systems, Inc., was funded by the U.S. Trade and Development Agency on behalf of Terengganu's State Economic Planning Unit. The main objectives of the report are to: (1) Identify and list all medium stream and downstream activities, including services in petrochemical industries, using natural gas-derived ethane, propane, and butane as main feedstock and other linkages; (2) List the various enterprises noted above that can be economically and viably established in Terengganu; (3) Identify and locate the various sites for the projects identified. This is volume 2 of 2 and it contains the Appendix.

  13. H. R. 5916: A Bill to require the President of the United States to use the Strategic Petroleum Reserve in the event of a domestic energy supply shortage, to amend the Energy Policy and Conservation Act and the Export Administration Act of 1979 to prohibit the exportation of refined petroleum products except under certain circumstances, and for other purposes, introduced in the House of Representatives, One Hundred First Congress, Second Session, October 24, 1990

    SciTech Connect (OSTI)

    Not Available

    1990-01-01

    The bill amends the Energy Policy and Conservation Act by making mandatory the use of the Strategic Petroleum Reserve in the event of a domestic energy supply shortage. The restriction on the export of refined petroleum products refers to gasoline, kerosene, heating oils, jet fuel, diesel fuel, residual fuel oil, propane, butane, and any natural liquid or natural gas liquid product refined within the US or entered for consumption within the US. The bill also describes the appointment of special investigator to investigate possible gouging and market manipulation by oil companies and the sense of Congress concerning the cost of deployment and maintenance of United States troops in Saudi Arabia.

  14. Silicon Based Solid Oxide Fuel Cell Chip for Portable Consumer Electronics -- Final Technical Report

    SciTech Connect (OSTI)

    Alan Ludwiszewski

    2009-06-29

    LSI’s fuel cell uses efficient Solid Oxide Fuel Cell (“SOFC”) technology, is manufactured using Micro Electrical Mechanical System (“MEMS”) fabrication methods, and runs on high energy fuels, such as butane and ethanol. The company’s Fuel Cell on a Chip™ technology enables a form-factor battery replacement for portable electronic devices that has the potential to provide an order-of-magnitude run-time improvement over current batteries. Further, the technology is clean and environmentally-friendly. This Department of Energy funded project focused on accelerating the commercialization and market introduction of this technology through improvements in fuel cell chip power output, lifetime, and manufacturability.

  15. Hydrogen-assisted catalytic ignition characteristics of different fuels

    SciTech Connect (OSTI)

    Zhong, Bei-Jing; Yang, Fan; Yang, Qing-Tao

    2010-10-15

    Hydrogen-assisted catalytic ignition characteristics of methane (CH{sub 4}), n-butane (n-C{sub 4}H{sub 10}) and dimethyl ether (DME) were studied experimentally in a Pt-coated monolith catalytic reactor. It is concluded that DME has the lowest catalytic ignition temperature and the least required H{sub 2} flow, while CH{sub 4} has the highest catalytic ignition temperature and the highest required H{sub 2} flow among the three fuels. (author)

  16. Towards reproducible, scalable lateral molecular electronic devices

    SciTech Connect (OSTI)

    Durkan, Colm Zhang, Qian

    2014-08-25

    An approach to reproducibly fabricate molecular electronic devices is presented. Lateral nanometer-scale gaps with high yield are formed in Au/Pd nanowires by a combination of electromigration and Joule-heating-induced thermomechanical stress. The resulting nanogap devices are used to measure the electrical properties of small numbers of two different molecular species with different end-groups, namely 1,4-butane dithiol and 1,5-diamino-2-methylpentane. Fluctuations in the current reveal that in the case of the dithiol molecule devices, individual molecules conduct intermittently, with the fluctuations becoming more pronounced at larger biases.

  17. Future perspectives of using hollow fibers as structured packings in light hydrocarbon distillation

    SciTech Connect (OSTI)

    Yang, Dali; Orler, Bruce; Tornga, Stephanie; Welch, Cindy

    2011-01-26

    Olefin and paraffin are the largest chemical commodities. Furthermore, they are major building blocks for the petrochemical industry. Each year, petroleum refining, consumes 4,500 TBtu/yr in separation energy, making it one of the most energy-intensive industries in the United States). Just considering liquefied petroleum gas (ethane/propane/butane) and olefins (ethylene and propylene) alone, the distillation energy consumption is about 400 TBtu/yr in the US. Since petroleum distillation is a mature technology, incremental improvements in column/tray design will only provide a few percent improvements in the performance. However, each percent saving in net energy use amounts to savings of 10 TBtu/yr and reduces CO{sub 2} emissions by 0.2 MTon/yr. In practice, distillation columns require 100 to 200 trays to achieve the desired separation. The height of a transfer unit (HTU) of conventional packings is typical in the range of 36-60 inch. Since 2006, we had explored using several non-selective membranes as the structured packings to replace the conventional packing materials used in propane and propylene distillation. We obtained the lowest HTU of < 8 inch for the hollow fiber column, which was >5 times shorter than that of the conventional packing materials. In 2008, we also investigated this type of packing materials in iso-/n-butane distillation. Because of a slightly larger relative volatility of iso-/n-butane than that of propane/propylene, a wider and a more stable operational range was obtained for the iso-/n-butane pair. However, all of the experiments were conducted on a small scale with flowrate of < 25 gram/min. Recently, we demonstrated this technology on a larger scale (<250 gram/min). Within the loading range of F-factor < 2.2 Pa{sup 0.5}, a pressure drop on the vapor side is below 50 mbar/m, which suggests that the pressure drop of hollow fibers packings is not an engineering barrier for the applications in distillations. The thermal stability study suggests that polypropylene hollow fibers are stable after a long time exposure to C{sub 2} - C{sub 4} mixtures. The effects of packing density on the separation efficiency will be discussed.

  18. Urban leakage of liquefied petroleum gas and its impact on Mexico City air quality

    SciTech Connect (OSTI)

    Blake, D.R.; Rowland, F.S.

    1995-08-18

    Alkane hydrocarbons (propane, isobutane, and n-butane) from liquefied petroleum gas (LPG) are present in major quantities throughout Mexico City air because of leakage of the unburned gas from numerous urban sources. These hydrocarbons, together with olefinic minor LPG components, furnish substantial amounts of hydroxyl radical reactivity, a major precursor to formation of the ozone component of urban smog. The combined processes of unburned leakage and incomplete combustion of LPG play significant role in causing the excessive ozone characteristic of Mexico City. Reductions in ozone levels should be possible through changes in LPG composition and lowered rates of leakage. 23 refs., 3 tabs.

  19. Process for restoring membrane permeation properties

    DOE Patents [OSTI]

    Pinnau, I.; Toy, L.G.; Casillas, C.G.

    1997-05-20

    A process is described for restoring the selectivity of high-free-volume, glassy polymer membranes for condensable components over less-condensable components or non-condensable components of a gas mixture. The process involves exposing the membrane to suitable sorbent vapor, such as propane or butane, thereby reopening the microvoids that make up the free volume. The selectivity of an aged membrane may be restored to 70--100% of its original value. The selectivity of a membrane which is known to age over time can also be maintained by keeping the membrane in a vapor environment when it is not in use. 8 figs.

  20. Carbonaceous adsorbent regeneration and halocarbon displacement by hydrocarbon gases

    DOE Patents [OSTI]

    Senum, Gunnar I. (Patchogue, NY); Dietz, Russell N. (Patchogue, NY)

    1994-01-01

    This invention describes a process for regeneration of halocarbon bearing carbonaceous adsorbents through which a carbonaceous adsorbent is contacted with hydrocarbon gases, preferably propane, butane and pentane at near room temperatures and at atmospheric pressure. As the hydrocarbon gases come in contact with the adsorbent, the hydrocarbons displace the halocarbons by physical adsorption. As a result of using this process, the halocarbon concentration and the hydrocarbon eluant is increased thereby allowing for an easier recovery of pure halocarbons. By using the process of this invention, carbonaceous adsorbents can be regenerated by an inexpensive process which also allows for subsequent re-use of the recovered halocarbons.

  1. Carbonaceous adsorbent regeneration and halocarbon displacement by hydrocarbon gases

    DOE Patents [OSTI]

    Senum, G.I.; Dietz, R.N.

    1994-04-05

    This invention describes a process for regeneration of halocarbon bearing carbonaceous adsorbents through which a carbonaceous adsorbent is contacted with hydrocarbon gases, preferably propane, butane and pentane at near room temperatures and at atmospheric pressure. As the hydrocarbon gases come in contact with the adsorbent, the hydrocarbons displace the halocarbons by physical adsorption. As a result of using this process, the halocarbon concentration and the hydrocarbon eluant is increased thereby allowing for an easier recovery of pure halocarbons. By using the process of this invention, carbonaceous adsorbents can be regenerated by an inexpensive process which also allows for subsequent re-use of the recovered halocarbons. 8 figures.

  2. Bio-butanol: Combustion properties and detailed chemical kinetic model

    SciTech Connect (OSTI)

    Black, G.; Curran, H.J.; Pichon, S.; Simmie, J.M.; Zhukov, V.

    2010-02-15

    Autoignition delay time measurements were performed at equivalence ratios of 0.5, 1 and 2 for butan-1-ol at reflected shock pressures of 1, 2.6 and 8 atm at temperatures from 1100 to 1800 K. High-level ab initio calculations were used to determine enthalpies of formation and consequently bond dissociation energies for each bond in the alcohol. A detailed chemical kinetic model consisting of 1399 reactions involving 234 species was constructed and tested against the delay times and also against recent jet-stirred reactor speciation data with encouraging results. The importance of enol chemistry is highlighted. (author)

  3. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    DOE Patents [OSTI]

    Koch, Daniel J.; Arnold, Frances H.

    2013-01-29

    Cytochrome P450 CYP153A6 from Myobacterium sp. strain HXN1500 was engineered using in-vivo directed evolution to hydroxylate small-chain alkanes regioselectively. Mutant CYP153A6-BMO1 selectively hydroxylates butane and pentane at the terminal carbon to form 1-butanol and 1-pentanol, respectively, at rates greater than wild-type CYP153A6 enzymes. This biocatalyst is highly active for small-chain alkane substrates and the regioselectivity is retained in whole-cell biotransformations.

  4. Process for restoring membrane permeation properties

    DOE Patents [OSTI]

    Pinnau, Ingo (Palo Alto, CA); Toy, Lora G. (San Francisco, CA); Casillas, Carlos G. (San Jose, CA)

    1997-05-20

    A process for restoring the selectivity of high-flee-volume, glassy polymer membranes for condensable components over less-condensable components or non-condensable components of a gas mixture. The process involves exposing the membrane to suitable sorbent vapor, such as propane or butane, thereby reopening the microvoids that make up the free volume. The selectivity of an aged membrane may be restored to 70-100% of its original value. The selectivity of a membrane which is known to age over time can also be maintained by keeping the membrane in a vapor environment when it is not in use.

  5. Flame Chemistry and Diagnostics

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hansen 1 , M. R. Harper 2 , W. H. Green 2 , B. Yang 1,3 , H. Wang 3 High-Temperature Oxidation of n-Butanol, iso-Butane, and iso-Butene in Low-Pressure Premixed Flames 1 Combustion Research Facility, Sandia National Laboratories 1 st Annual Conference of the Combustion EFRC Sept. 23 rd - Sept. 24 th 2010 3 Department of Aerospace and Mechanical Engineering, University of Southern California 2 Department of Chemical Engineering, Massachusetts Institute of Technology Outline  Experimental

  6. Natural Gas Plant Field Production: Natural Gas Liquids

    Gasoline and Diesel Fuel Update (EIA)

    Product: Natural Gas Liquids Pentanes Plus Liquefied Petroleum Gases Ethane Propane Normal Butane Isobutane Period-Unit: Monthly-Thousand Barrels Monthly-Thousand Barrels per Day Annual-Thousand Barrels Annual-Thousand Barrels per Day Download Series History Download Series History Definitions, Sources & Notes Definitions, Sources & Notes Show Data By: Product Area Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History U.S. 101,809 102,880 100,283 106,269 103,071 104,629 1981-2015 PADD 1

  7. Natural Gas Plant Stocks of Natural Gas Liquids

    Gasoline and Diesel Fuel Update (EIA)

    Product: Natural Gas Liquids Pentanes Plus Liquefied Petroleum Gases Ethane Propane Normal Butane Isobutane Period: Monthly Annual Download Series History Download Series History Definitions, Sources & Notes Definitions, Sources & Notes Show Data By: Product Area Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History U.S. 6,491 6,324 6,877 6,774 5,691 4,837 1993-2015 PADD 1 260 192 186 222 215 218 1993-2015 East Coast 4 4 7 7 1993-2015 Appalachian No. 1 260 192 182 218 208 211 1993-2015

  8. New and existing gas wells promise bountiful LPG output in Michigan

    SciTech Connect (OSTI)

    Not Available

    1991-01-01

    Michigan remains the leading LP-gas producer in the Northeast quadrant of the U.S. This paper reports that boosted by a number of new natural gas wells and a couple of new gas processing plants, the state is firmly anchored in the butane/propane production business. Since 1981, more than 100 deep gas wells, most in excess of 8000 feet in depth, have been completed as indicated producers in the state. Many of these are yielding LPG-grade stock. So, combined with LPG-grade production from shallower geologic formations, the supply picture in this area looks promising for the rest of the country.

  9. LABORATORY STUDIES ON THE IRRADIATION OF SOLID ETHANE ANALOG ICES AND IMPLICATIONS TO TITAN'S CHEMISTRY

    SciTech Connect (OSTI)

    Kim, Y. S.; Bennett, C. J.; Chen, L-H; Kaiser, R. I.; O'Brien, K.

    2010-03-10

    Pure ethane ices (C{sub 2}H{sub 6}) were irradiated at 10, 30, and 50 K under contamination-free, ultrahigh vacuum conditions with energetic electrons generated in the track of galactic cosmic-ray (GCR) particles to simulate the interaction of GCRs with ethane ices in the outer solar system. The chemical processing of the samples was monitored by a Fourier transform infrared spectrometer and a quadrupole mass spectrometer during the irradiation phase and subsequent warm-up phases on line and in situ in order to extract qualitative (products) and quantitative (rate constants and yields) information on the newly synthesized molecules. Six hydrocarbons, methane (CH{sub 4}), acetylene (C{sub 2}H{sub 2}), ethylene (C{sub 2}H{sub 4}), and the ethyl radical (C{sub 2}H{sub 5}), together with n-butane (C{sub 4}H{sub 10}) and butene (C{sub 4}H{sub 8}), were found to form at the radiation dose reaching 1.4 eV per molecule. The column densities of these species were quantified in the irradiated ices at each temperature, permitting us to elucidate the temperature and phase-dependent production rates of individual molecules. A kinetic reaction scheme was developed to fit column densities of those species produced during irradiation of amorphous/crystalline ethane held at 10, 30, or 50 K. In general, the yield of the newly formed molecules dropped consistently for all species as the temperature was raised from 10 K to 50 K. Second, the yield in the amorphous samples was found to be systematically higher than in the crystalline samples at constant temperature. A closer look at the branching ratios indicates that ethane decomposes predominantly to ethylene and molecular hydrogen, which may compete with the formation of n-butane inside the ethane matrix. Among the higher molecular products, n-butane dominates. Of particular relevance to the atmosphere of Saturn's moon Titan is the radiation-induced methane production from ethane-an alternative source of replenishing methane into the atmosphere. Finally, we discuss to what extent the n-butane could be the source of ''higher organics'' on Titan's surface thus resembling a crucial sink of condensed ethane molecules.

  10. EIA-816

    Gasoline and Diesel Fuel Update (EIA)

    6281 Receipts During Month Inputs During Month Production During Month Shipments During Month Plant Fuel Use & Losses 247 Pentanes Plus Isobutane Normal Butane 249 Month 220 243 Ethane Propane Stocks End of Month Product Code Stocks Beginning of Month FORM EIA-816 MONTHLY NATURAL GAS LIQUIDS REPORT A completed form must be received by the 20th calendar day following the end of the report month. This report is mandatory under the Federal Energy Administration Act of 1974 (Public Law 93-275).

  11. An integrated process for simultaneous desulfurization, dehydration, and recovery of hydrocarbon liquids from natural gas streams

    SciTech Connect (OSTI)

    Sciamanna, S.F. ); ))

    1988-01-01

    Conventional processing schemes for desulfurizing, drying, and separation of natural gas liquids from natural gas streams require treating the gas by a different process for each separation step. In a simpler process, based on the University of California, Berkeley Sulfur Recovery Process (UCBSRP) technology, hydrogen sulfide, propane and heavier hydrocarbons, and water are absorbed simultaneously by a polyglycol ether solvent containing a homogenous liquid phase catalyst. The catalyst promotes the subsequent reaction of hydrogen sulfide with added sulfur dioxide to produce a high quality sulfur product. Hydrocarbons are separated as two product streams with the split between propane and butane. This new process offers an overall reduction in both capital and energy costs.

  12. Isobutane ignition delay time measurements at high pressure and detailed chemical kinetic simulations

    SciTech Connect (OSTI)

    Healy, D.; Curran, H.J.; Donato, N.S.; Aul, C.J.; Petersen, E.L.; Zinner, C.M.; Bourque, G.

    2010-08-15

    Rapid compression machine and shock-tube ignition experiments were performed for real fuel/air isobutane mixtures at equivalence ratios of 0.3, 0.5, 1, and 2. The wide range of experimental conditions included temperatures from 590 to 1567 K at pressures of approximately 1, 10, 20, and 30 atm. These data represent the most comprehensive set of experiments currently available for isobutane oxidation and further accentuate the complementary attributes of the two techniques toward high-pressure oxidation experiments over a wide range of temperatures. The experimental results were used to validate a detailed chemical kinetic model composed of 1328 reactions involving 230 species. This mechanism has been successfully used to simulate previously published ignition delay times as well. A thorough sensitivity analysis was performed to gain further insight to the chemical processes occurring at various conditions. Additionally, useful ignition delay time correlations were developed for temperatures greater than 1025 K. Comparisons are also made with available isobutane data from the literature, as well as with 100% n-butane and 50-50% n-butane-isobutane mixtures in air that were presented by the authors in recent studies. In general, the kinetic model shows excellent agreement with the data over the wide range of conditions of the present study. (author)

  13. Optimizing C{sup 4+} and C{sup 5+} beams of the Kei2 electron cyclotron resonance ion source using a special gas-mixing technique

    SciTech Connect (OSTI)

    Drentje, A.G.; Muramatsu, M.; Kitagawa, A.

    2006-03-15

    With the prototype electron cyclotron resonance ion source for the next carbon therapy facility in Japan a series of measurements has been performed in order (a) to find the best condition for producing high beam currents of C{sup 4+} ions, and (b) to study the effect of 'special' gas mixing by using a chemical compound as a feed gas. The effect would then appear as an increase in high charge state production in this case of C{sup 5+} ions. In 'regular' gas-mixing experiments it is well known that an isotopic phenomenon occurs: a heavier isotope of the mixing gas is increasing the production of high charge states of the beam gas ions. A similar isotopic effect has been found in the present experiment: with deuterated methane (CD{sub 4} gas) the C{sup 5+} beam currents are about 10% higher than with regular methane (CH{sub 4} gas). The 'mixing-gas' ratio D (or H) to C can be decreased by choosing, e.g., butane gas; in this case the isotopic effect for C{sup 5+} production is even stronger (>15%). For production of C{sup 4+} ions the isotopic effect appears to be absent. Clearly this is related to the much easier production. It turns out that the relative amount of carbon is much more important: butane gives about 10% higher C{sup 4+}-ion currents than methane.

  14. Ultrahigh and High Resolution Structures and Mutational Analysis of Monomeric Streptococcus pyogenes SpeB Reveal a Functional Role for the Glycine-rich C-terminal Loop

    SciTech Connect (OSTI)

    González-Páez, Gonzalo E.; Wolan, Dennis W.

    2012-09-05

    Cysteine protease SpeB is secreted from Streptococcus pyogenes and has been studied as a potential virulence factor since its identification almost 70 years ago. Here, we report the crystal structures of apo mature SpeB to 1.06 {angstrom} resolution as well as complexes with the general cysteine protease inhibitor trans-epoxysuccinyl-L-leucylamido(4-guanidino)butane and a novel substrate mimetic peptide inhibitor. These structures uncover conformational changes associated with maturation of SpeB from the inactive zymogen to its active form and identify the residues required for substrate binding. With the use of a newly developed fluorogenic tripeptide substrate to measure SpeB activity, we determined IC{sub 50} values for trans-epoxysuccinyl-L-leucylamido(4-guanidino)butane and our new peptide inhibitor and the effects of mutations within the C-terminal active site loop. The structures and mutational analysis suggest that the conformational movements of the glycine-rich C-terminal loop are important for the recognition and recruitment of biological substrates and release of hydrolyzed products.

  15. Combustion characteristics of alternative gaseous fuels

    SciTech Connect (OSTI)

    Park, O.; Veloo, Peter S.; Liu, N.; Egolfopoulos, Fokion N.

    2011-01-01

    Fundamental flame properties of mixtures of air with hydrogen, carbon monoxide, and C{sub 1}–C{sub 4} saturated hydrocarbons were studied both experimentally and numerically. The fuel mixtures were chosen in order to simulate alternative gaseous fuels and to gain insight into potential kinetic couplings during the oxidation of fuel mixtures. The studies included the use of the counterflow configuration for the determination of laminar flame speeds, as well as extinction and ignition limits of premixed flames. The experiments were modeled using the USC Mech II kinetic model. It was determined that when hydrocarbons are added to hydrogen flames as additives, flame ignition, propagation, and extinction are affected in a counterintuitive manner. More specifically, it was found that by substituting methane by propane or n-butane in hydrogen flames, the reactivity of the mixture is reduced both under pre-ignition and vigorous burning conditions. This behavior stems from the fact that propane and n-butane produce higher amounts of methyl radicals that can readily recombine with atomic hydrogen and reduce thus the rate of the H + O{sub 2} ? O + OH branching reaction. The kinetic model predicts closely the experimental data for flame propagation and extinction for various fuel mixtures and pressures, and for various amounts of carbon dioxide in the fuel blend. On the other hand, it underpredicts, in general, the ignition temperatures.

  16. Performance of a new LMRPC prototype for the STAR MTD system

    SciTech Connect (OSTI)

    Ruan, L.J.; Wang, Y.; Chen, H. S.; Ding, W. C.; Qiu, X. Z.; Wang, J. B.; Zhu, X. L.; Kang, K. J.; Cheng, J. P.; Li, Y. J.; Ruan, L.; Xu, Z.; Asselta, K.; Christie, W.; D'Agostino, C.; Dunlop, J.; Landgraf, J.; Ljubicic, T.; Scheblein, J.; Soja, R.; Tang, A. H.; Ullrich, T.; Crawford, H. J.; Engelage, J.; Sanchez, M. Calderon de la Barca; Reed, R.; Liu, H. D.; Butterworth, J.; Eppley, G.; Geurts, F.; Llope, W. J.; McDonald, D.; Nussbaum, T.; Roberts, J.; Xin, K.; Bridges, L.; Li, J. C.; Qian, S.; Ning, Z.; Chen, H. F.; Huang, B. C.; Li, C.; Shao, M.; Sun, Y. J.; Tang, Z. B.; Wang, X. L.; Xu, Y. C.; Zhang, Z. P.; Zeng, H.; Zhou, Y.; Clarke, R.; Mioduszewski, S.; Davila, A.; Hoffmann, G. W.; Li, L.; Markert, C.; Ray, L.; Schambach, J.; Thein, D.; Wada, M.; Ahammed, Z.; Bhaduri, P. P.; Chattopadhyay, S.; Dubey, A. K.; Dutt-Mazumdar, M. R.; Ghosh, P.; Khan, S. A.; Muhuri, S.; Mohanty, B.; Nayak, T. K.; Pal, S.; Singaraju, R.; Singhal, V.; Tribedy, P.; Viyogi, Y. P.

    2011-03-21

    A new prototype of a Long-Strip Multi-Gap Resistive Plate Chamber (LMRPC) for the STAR Muon Telescope Detector (MTD) at RHIC has been developed. This prototype has an active area of 52 x 90 cm{sup 2} and consists of six 250 {mu}m wide gaps. Each detector has 12 strips, read-out at both ends, which are each 3.8 cm wide and 90 cm long with 0.6 cm intervals. In cosmic-ray tests, the efficiency was larger than 95% and the time resolution was {approx}75 ps for the 94% Freon, 5% iso-butane, and 1% SF{sub 6} gas mixture. There was good uniformity in the performance across the different strips. The module was also tested in a proton beam at IHEP in Beijing. The efficiency was close to 100% and the best timing resolution achieved was 55 ps for the 90% Freon, 5% iso-butane, and 5% SF6 gas mixture. Trigger scans along and across the strip direction were also performed.

  17. Reactivity Screening of Anatase TiO2 Nanotube Arrays and Anatase Thin Films: A Surface Chemistry Point of View

    SciTech Connect (OSTI)

    Funk, S.; Hokkanen, B.; Nurkic, T.; Goering, J.; Kadossov, E.; Burghaus, Uwe; Ghicov, A.; Schmuki, P.; Yu, Zhongqing; Thevuthasan, Suntharampillai; Saraf, Laxmikant V.

    2008-09-19

    As a reactivity screening we collected thermal desorption spectroscopy (TDS) data of iso-butane, O2, CO2, and CO adsorbed on ordered TiO2 nanotube (TiNTs) arrays. As a reference system iso-butane adsorption on an anatase TiO2 thin film has been considered as well. The as-grown TiNTs are vertically aligned and amorphous. Polycrystalline (poly.) anatase or poly. anatase/rutile mixed nanotubes are formed by annealing confirmed by x-ray diffraction (XRD) and scanning electron microscopy (SEM). The anatase thin film was grown on SrTiO3(001) and characterized by XRD and atomic force microscopy (AFM). Surprisingly, oxygen distinctly interacts with the TiNTs whereas this process is not observed on fully oxidized single crystal rutile TiO2(110). Desorption temperatures of 110-150 K and 100-120 K were observed for CO2 and CO, respectively, on the TiNTs. Variations in the binding energies of the alkanes on TiNTs and anatase thin films also were present, i.e., a structure-activity relationship (SAR) is evident.

  18. Source profiles for nonmethane organic compounds in the atmosphere of Cairo, Egypt.

    SciTech Connect (OSTI)

    Doskey, P. V.; Fukui, Y.; Sultan, M.; Maghraby, A. A.; Taher, A.; Environmental Research; Cairo Univ.

    1999-07-01

    Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas (LPG), and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C{sub 5} and C{sub 6} saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in the vehicle emission profile. High levels of the C{sub 2}-C{sub 4} saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.

  19. Urban leakage of liquefied petroleum gas and its potential impact of Mexico City air quality

    SciTech Connect (OSTI)

    Blake, D.R.; Rowland, F.S.

    1995-12-01

    Seventy eight whole air samples were collected at various park locations throughout Mexico City and later assayed for methane, carbon monoxide, 20 halocarbons and 40 C{sub 2}-C{sub 10} hydrocarbons. Propane had the highest median mixing ratio value of all assayed non-methane hydrocarbon compounds (NMHCs) with a concentration as high as 0.1 ppmv. The concentration of n-butane, i-butane, n-pentane and i-pentane were all notably elevated as well. The only significant identified source of propane in Mexico City is liquefied petroleum gas (LPG), which also has a strong component of C{sub 4} and C{sub 5} alkanes. All of these alkanes were present at concentrations well above those observed in other cities where LPG is not the main domestic fuel. Data strongly suggest that as much as 50% of total Mexico City NMHCs is a result of losses associated with the transfer, storage and delivery of LPG. Additionally, using median concentrations and laboratory determined hydroxyl reaction rate constants, LPG emissions account for about 20% of initial reactivities. This suggests that LPG losses may significantly impact photochemical oxidant levels in Mexico City.

  20. Diffusion of methane and other alkanes in metal-organic frameworks for natural gas storage

    SciTech Connect (OSTI)

    Borah, B; Zhang, HD; Snurr, RQ

    2015-03-03

    Diffusion of methane, ethane, propane and n-butane was studied within the micropores of several metal organic frameworks (MOFs) of varying topologies, including the MOFs PCN-14, NU-125, NU-1100 and DUT-49. Diffusion coefficients of the pure components, as well as methane/ethane, methane/ propane and methane/butane binary mixtures, were calculated using molecular dynamics simulations to understand the effect of the longer alkanes on uptake of natural gas in MOB. The calculated self diffusion coefficients of all four components are on the order of 10(-8) m(2)/s. The diffusion coefficients of the pure components decrease as a function of chain length in all of the MOFs studied and show different behaviour as a function of loading in different MOB. The self-diffusivities follow the trend DPCN-14 < DNU-125 approximate to DNU-1100 < DDUT-49, which is exactly the reverse order of the densities of the MOFs: PCN-14 > NU-125 approximate to NU-1100 > DUT-49. By comparing the diffusion of pure methane and methane mixtures vvith the higher alkancs, it is observed that the diffusivity of methane is unaffected by the presence of the higher alkanes in the MOFs considered, indicating that the diffusion path of methane is not blocked by the higher alkanes present in natural gas. (C) 2014 Elsevier Ltd. All rights reserved.

  1. Simple rules help select best hydrocarbon distillation scheme

    SciTech Connect (OSTI)

    Sanchezllanes, M.T.; Perez, A.L.; Martinez, M.P.; Aguilar-Rodriguez, E.; Rosal, R. del )

    1993-12-06

    Separation economics depend mainly on investment for major equipment and energy consumption. This relationship, together with the fact that, in most cases, many alternative schemes will be proposed, make it essential to find an optimum scheme that minimizes overall costs. Practical solutions are found by applying heuristics -- exploratory problem-solving techniques that eliminate alternatives without applying rigorous mathematical procedures. These techniques have been applied to a case study. In the case study, a hydrocarbon mixture will be transported through a pipeline to a fractionation plant, where it will be separated into commercial products for distribution. The fractionation will consist of a simple train of distillation columns, the sequence of which will be defined by applying heuristic rules and determining the required thermal duties for each column. The facility must separate ethane, propane and mixed butanes, natural gasoline (light straight-run, or LSR, gasoline), and condensate (heavy naphtha). The ethane will be delivered to an ethylene plant as a gaseous stream, the propane and butanes will be stored in cryogenic tanks, and the gasoline and heavy naphtha also will be stored.

  2. Oxygenates from light alkanes catalyzed by NO{sub x} in the gas phase

    SciTech Connect (OSTI)

    Otsuka, Kiyoshi; Takahashi, Ryo; Yamanaka, Ichiro

    1999-07-01

    The partial oxidations of light alkanes (methane, ethane, propane, and iso-butane) catalyzed by NO{sub x} in the gas phase have been studied at a pressure of less than 1 bar. For all the alkanes tested, the addition of NO to the mixture of alkanes and O{sub 2} enhanced the selectivities and the yields of oxygenates remarkably. It was suggested that NO{sub 2} generated from NO and O{sub 2} initiated the oxidation of alkanes and would specifically accelerate the C-C bond fission, enhancing the formation of C{sub 1}-oxygenates from ethane, propane, and iso-butane. No{sub 2} and NO would be used as a homogeneous catalyst at >600 C because nitroalkanes formed were decomposed completely, releasing the NO{sub x}. The comparison of the product distributions for the decomposition and oxidation of nitroalkanes and alkylnitrites strongly suggested that the oxygenates (HCHO, CH{sub 3}CHO, and CH{sub 3}COCH{sub 3}) were formed from the corresponding alkylnitrites which must be the reaction intermediates during the oxidation of alkanes with an O{sub 2} and NO mixture.

  3. Thermodynamic properties of liquefied petroleum gases (LPG). Interim report 15 Aug 75-31 Jan 77 (final)

    SciTech Connect (OSTI)

    Sallet, D.W.; Wu, K.F.

    1980-04-01

    The thermodynamic properties of several liquefied petroleum gases (with particular emphasis on propane) are discussed in detail. It is concluded that the widely used propane data by Stearns and George are too inconsistent and too inaccurate to be used for mass flow calculations of propane and propane mixtures through safety valves of rail tank cars. Accordingly, the thermodynamic properties of propane, propylene, n-butane, and a mixture of 65% (by mole) propane, 25% propylene, and 10% n-butane are recalculated using equations of states proposed by Benedict-Webb-Rubin (BWR) and by Starling. It is shown that Starling's equation results in thermodynamic properties which are more consistent and compare better with measured values than the BWR equation. Thermodynamic data for the four liquefied petroleum gases discussed above are calculated and presented in tabular form. In addition, predictions of pure propane mass flow rates (based upon isentropic), homogeneous equilibrium flow) are given. The influence of the thermodynamic data upon the predicted mass flow rates is demonstrated.

  4. Study of autoignition in a premixed charge, internal combustion engine using comprehensive chemical kinetics: experiments and predictions

    SciTech Connect (OSTI)

    Dimpelfeld, P.M.

    1985-01-01

    A model is developed to predict autoignition in a premixed charge engine. Experimental data are obtained with spark ignition and premixed charge compression ignition. Seven fuels are examined: methane, ethane, propane, n-butane, methanol, ethylene, and propylene. Binary fuel mixtures are also examined, as are the effects of engine speed, equivalence ratio, load, and compression ratio. An initial temperature correction must be used to accurately predict the observed time of autoignition. Analysis of spark-ignited data show that the fuels fall into two groups, depending on the temperature correction ranging from 35 K to 80 K: methane, propane, n-butane, and methanol. Three fuels fall into the group with a temperature correction ranging from 110K and 140K: ethane, ethylene, and propylene. The rate of pressure rise during compression ignition is controlled by varying the fuel-air equivalence ratio. The effects of compression ratio and load on the rate and load on the rate of pressure rise are also examined. The predicted rates of temperature rise during compression ignition are compared to the observed rates of temperature rise.

  5. Laser ultrasonic furnace tube coke monitor. Quarterly technical progress report No. 1, May 1--August 1, 1998

    SciTech Connect (OSTI)

    1998-08-15

    The overall aim of the project is to demonstrate the performance and practical use of a laser ultrasonic probe for measuring the thickness of coke deposits located within the high temperature tubes of a thermal cracking furnace. This aim will be met by constructing an optical probe that will be tested using simulated coke deposits that are positioned inside of a bench-scale furnace. Successful development of the optical coke detector will provide industry with the only available method for on-line measurement of coke deposits. The optical coke detector will have numerous uses in the refining and petrochemical sectors including monitoring of visbreakers, hydrotreaters, delayed coking units, vacuum tower heaters, and various other heavy oil heating applications where coke formation is a problem. The coke detector will particularly benefit the olefins industry where high temperature thermal crackers are used to produce ethylene, propylene, butylene and other important olefin intermediates. The ethylene industry requires development of an on-line method for gauging the thickness of coke deposits in cracking furnaces because the current lack of detailed knowledge of coke deposition profiles introduces the single greatest uncertainty in the simulation and control of modern cracking furnaces. The laser ultrasonic coke detector will provide operators with valuable new information allowing them to better optimize the decoking turnaround schedule and therefore maximize production capacity.

  6. Potential for Microbial Stimulation in Deep Vadose Zone Sediments by Gas-Phase Nutrients

    SciTech Connect (OSTI)

    Li, S.W.; Plymale, A. E.; Brockman, F.J.

    2006-04-05

    Viable microbial populations are low, typically 10{sup 4} cells per gram, in deep vadose zones in arid climates. There is evidence that microbial distribution in these environments is patchy. In addition, infiltration or injection of nutrient-laden water has the potential to spread and drive contaminants downward to the saturated zone. For these reasons, there are uncertainties regarding the feasibility of bioremediation of recalcitrant contaminants in deep vadose zones. The objectives of this study were to investigate the occurrence of denitrifying activity and gaseous carbon-utilizing activity in arid-climate deep vadose zone sediments contaminated with, and/or affected by past exposure to, carbon tetrachloride (CT). These metabolisms are known to degrade CT and/or its breakdown product chloroform under anoxic conditions. A second objective was to determine if CT would be degraded in these sediments under unsaturated, bulk-phase aerobic incubation conditions. Both denitrifier population (determined by MPN) and microbial heterotrophic activity (measured by mineralization of 14-C labeled glucose and acetate) were relatively low and the sediments with greater in situ moisture (10-21% versus 2-7%) tended to have higher activities. When sediments were amended with gaseous nutrients (nitrous oxide and triethyl/tributyl phosphate) and gaseous C sources (a mixture of methane, ethane, propylene, propane, and butane) and incubated for 6 months, approximately 50% of the samples showed removal of one or more gaseous C sources, with butane most commonly used (44% of samples), followed by propylene (42%), propane (31%), ethane (22%), and methane (4%). Gaseous N and gaseous P did not stimulate removal of gaseous C substrates compared to no addition of N and P. CT and gaseous C sources were spiked into the sediments that removed gaseous C sources to determine if hydrocarbon-degraders have the potential to degrade CT under unsaturated conditions. In summary, gaseous C sources--particularly butane and propylene--have promise for increasing the numbers and activity of indigenous microbial populations in arid-climate deep vadose zone sediments.

  7. Superacid catalysis of light hydrocarbon conversion. DOE PETC seventh quarterly progress report, April 1, 1995--July 31, 1995

    SciTech Connect (OSTI)

    Gates, B.C.

    1996-02-01

    Iron- and manganese-promoted sulfated zirconia is a catalyst for the conversion of propane, but the rate of conversion of propane is much less than the rate of conversion of butane. Whereas this catalyst appears to be a good candidate for practical, industrial conversion of butane, it appears to lack sufficient activity for practical conversion of propane. The propane conversion data reported here provide excellent insights into the chemistry of the catalytic conversion. Solid and catalysts, namely, sulfated zirconia, iron- and manganese-promoted sulfated zirconia, and USY zeolite, were tested for conversion of propane at 1 atm, 200-450{degrees}C, and propane partial pressures in the range of 0.01-0.05 atm. Both promoted and unpromoted sulfated zirconia were found to be active for conversion of propane into butanes, pentanes, methane, ethane, ethylene, and propylene in the temperature range of 200-350{degrees}C, but catalyst deactivation was rapid. At the higher temperatures, only cracking and dehydrogenation products were observed. In contrast to the zirconia-supported catalysts, USY zeolite was observed to convert propane (into propylene, methane, and ethylene) only at temperatures {ge}400{degrees}C. The initial (5 min on stream) rates of propane conversion in the presence of iron- and manganese-promoted sulfated zirconia, sulfated zirconia, and USY zeolite at 450{degrees}C and 0.01 atm propane partial pressure were 3.3 x 10{sup -8}, 0.3 x 10{sup -8}, and 0.06 x 10{sup -8} mol/(s{center_dot}g), respectively. The product distributions in the temperature range 200-450{degrees}C are those of acid-base catalysis, being similar to what has been observed in superacid solution chemistry at temperatures <0{degrees}C. If propane conversion at 450{degrees}C can be considered as a probe of acid strength of the catalyst, the activity comparison suggests that the promoted sulfated zirconia is a stronger acid than sulfated zirconia, which is a stronger acid than USY zeolite.

  8. Method for forming a chemical microreactor

    DOE Patents [OSTI]

    Morse, Jeffrey D. (Martinez, CA); Jankowski, Alan (Livermore, CA)

    2009-05-19

    Disclosed is a chemical microreactor that provides a means to generate hydrogen fuel from liquid sources such as ammonia, methanol, and butane through steam reforming processes when mixed with an appropriate amount of water. The microreactor contains capillary microchannels with integrated resistive heaters to facilitate the occurrence of catalytic steam reforming reactions. Two distinct embodiment styles are discussed. One embodiment style employs a packed catalyst capillary microchannel and at least one porous membrane. Another embodiment style employs a porous membrane with a large surface area or a porous membrane support structure containing a plurality of porous membranes having a large surface area in the aggregate, i.e., greater than about 1 m.sup.2/cm.sup.3. Various methods to form packed catalyst capillary microchannels, porous membranes and porous membrane support structures are also disclosed.

  9. Anion effects in the extraction of lanthanide 2-thenoyltrifluoroacetone complexes into an ionic liquid

    SciTech Connect (OSTI)

    Jensen, Mark P.; Beitz, James V.; Rickert, Paul G.; Borkowski, Marian; Laszak, Ivan; Dietz, Mark L.

    2012-07-01

    The extraction of trivalent lanthanides from an aqueous phase containing 1 M NaClO{sub 4} into the room temperature ionic liquid 1-butyl-3-methylimidazolium nonafluoro-1-butane sulfonate by the beta-diketone extractant 2-thenoyltrifluoroacetone (Htta) was studied. Radiotracer distribution, absorption spectroscopy, time-resolved laser-induced fluorescence spectroscopy, and X-ray absorption fine structure measurements point to the extraction of multiple lanthanide species. At low extractant concentrations, fully hydrated aqua cations of the lanthanides are present in the ionic liquid phase. As the extractant concentration is increased 1:2 and 1:3 lanthanide:tta species are observed. In contrast, 1:4 Ln:tta complexes were observed in the extraction of lanthanides by Htta into 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. (authors)

  10. Dynamics of CN+alkane reactions by crossed-beam dc slice imaging

    SciTech Connect (OSTI)

    Huang Cunshun; Li Wen; Estillore, Armando D.; Suits, Arthur G.

    2008-08-21

    The hydrogen atom abstraction reactions of CN (X {sup 2}{sigma}{sup +}) with alkanes have been studied using the crossed molecular beam technique with dc slice ion imaging at collision energies of 7.5 and 10.8 kcal/mol. The product alkyl radical images were obtained via single photon ionization at 157 nm for the reactions of CN (X {sup 2}{sigma}{sup +}) with n-butane, n-pentane, n-hexane, and cyclohexane. From analysis of the images, we obtained the center-of-mass frame product angular distributions and translational energy distributions directly. The results indicate that the products are largely backscattered and that most of the available energy ({approx}80%-85%) goes to the internal energy of the products. The reaction dynamics is discussed in light of recent kinetics data, theoretical calculations, and results for related halogen and oxygen atom reactions.

  11. A remarkable shape-catalytic effect of confinement on the rotational isomerization of small hydrocarbons

    SciTech Connect (OSTI)

    Santiso, Erik E; Gubbins, Keith E; Buongiorno Nardelli, Marco

    2008-01-01

    As part of an effort to understand the effect of confinement by porous carbons on chemical reactions, we have carried out density functional theory calculations on the rotational isomerization of three four-membered hydrocarbons: n-butane, 1-butene, and 1,3-butadiene. Our results show that the interactions with the carbon walls cause a dramatic change on the potential energy surface for pore sizes comparable to the molecular dimensions. The porous material enhances or hinders reactions depending on how similar is the shape of the transition state to the shape of the confining material. The structure of the stable states and their equilibrium distributions are also drastically modified by confinement. Our results are consistent with a doubly exponential behavior of the reaction rates as a function of pore size, illustrating how the shape of a catalytic support can dramatically change the efficiency of a catalyst. (51 refs.)

  12. Critical radius for sustained propagation of spark-ignited spherical flames

    SciTech Connect (OSTI)

    Kelley, Andrew P.; Jomaas, Grunde; Law, Chung K.

    2009-05-15

    An experimental study was performed to determine the requirements for sustained propagation of spark-ignited hydrogen-air and butane-air flames at atmospheric and elevated pressures. Results show that sustained propagation is always possible for mixtures whose Lewis number is less than unity, as long as a flame can be initially established. However, for mixtures whose Lewis number is greater than unity, sustained propagation depends on whether the initially ignited flame can attain a minimum radius. This minimum radius was determined for mixtures of different equivalence ratios and pressures, and was found to agree moderately well with the theoretically predicted critical radius beyond which there is no solution for the adiabatic, quasi-steady propagation of the spherical flame. The essential roles of pressure, detailed chemistry, and the need to use local values in the quantitative evaluation of the flame response parameters are emphasized. (author)

  13. The Chemical Composition and Structure of Supported Sulfated Zirconia with Regulated Size Nanoparticles

    SciTech Connect (OSTI)

    Kanazhevskiy, V. V.; Shmachkova, V. P.; Kotsarenko, N. S.; Kochubey, D. I.; Vedrine, J. C.

    2007-02-02

    A set of model skeletal isomerization catalysts - sulfated zirconia nanoparticles of controlled thickness anchored on different supports - was prepared using colloidal solutions of Zr salt on titania as support. The nanoparticles of zirconia (1-5 nm) are epitaxially connected to the support surface, with S/Zr ratio equals to 1.3-1.5. It was shown by EXAFS that nanoparticles of non-stoichiometric zirconium sulfate Zr(SO4)1+x, where x<0.5, are formed on the support surface. Its structure looks like half-period shifted counterdirected chains built-up by zirconium atoms linked by triangle pyramids of sulfate groups. Considering catalytic data of skeletal n-butane isomerisation at 150 deg. C, one can suggest that these species behave as the active component of sulfated zirconia. They are formed in subsurface layers as zirconium hydroxide undergoes sulfation followed by thermal treatment.

  14. Relaxed active space: Fixing tailored-CC with high order coupled cluster. II

    SciTech Connect (OSTI)

    Melnichuk, Ann Bartlett, Rodney J.

    2014-02-14

    Due to the steep increase in computational cost with the inclusion of higher-connected cluster operators in coupled-cluster applications, it is usually not practical to use such methods for larger systems or basis sets without an active space partitioning. This study generates an active space subject to unambiguous statistical criteria to define a space whose size permits treatment at the CCSDT level. The automated scheme makes it unnecessary for the user to judge whether a chosen active space is sufficient to correctly solve the problem. Two demanding applications are presented: twisted ethylene and the transition states for the bicyclo[1,1,0]butane isomerization. As bi-radicals both systems require at least a CCSDT level of theory for quantitative results, for the geometries and energies.

  15. Use of look-ahead modeling in pipeline operations

    SciTech Connect (OSTI)

    Wray, B.; O`Leary, C.

    1995-12-31

    Amoco Canada Petroleum Company, Ltd. operates the Cochin pipeline system. Cochin pumps batched liquid ethane, propane, ethylene, butane, and NGL. Operating and scheduling this pipeline is very complex. There are safety considerations, especially for ethylene, which cannot be allowed to drop below vapor pressure. Amoco Canada needs to know where batches are in the line, what pressure profiles will look like into the future, and when batches arrive at various locations along the line. In addition to traditional instrumentation and SCADA, Amoco Canada uses modeling software to help monitor and operate the Cochin pipeline. Two important components of the modeling system are the Estimated Time of Arrival (ETA) and Predictive Model (PM) modules. These modules perform look ahead modeling to assist in operating the Cochin pipeline. The modeling software was first installed for the Cochin system in February of 1994, and was commissioned on August 1, 1994. This paper will discuss how the look ahead modules are used for the Cochin pipeline.

  16. Chemical microreactor and method thereof

    DOE Patents [OSTI]

    Morse, Jeffrey D.; Jankowski, Alan

    2005-11-01

    A chemical microreactor suitable for generation of hydrogen fuel from liquid sources such as ammonia, methanol, and butane through steam reforming processes when mixed with an appropriate amount of water contains capillary microchannels with integrated resistive heaters to facilitate the occurrence of catalytic steam reforming reactions. One such microreactor employs a packed catalyst capillary microchannel and at least one porous membrane. Another employs a porous membrane with a large surface area or a porous membrane support structure containing a plurality of porous membranes having a large surface area in the aggregate, i.e., greater than about 1 m.sup.2 /cm.sup.3. The packed catalyst capillary microchannels, porous membranes and porous membrane support structures may be formed by a variety of methods.

  17. Crossed-beam DC slice imaging of fluorine atom reactions with linear alkanes

    SciTech Connect (OSTI)

    Shi, Yuanyuan; Kamasah, Alexander; Joalland, Baptiste; Suits, Arthur G.

    2015-05-14

    We report the reaction dynamics of F atom with selected alkanes studied by crossed beam scattering with DC slice ion imaging. The target alkanes are propane, n-butane, and n-pentane. The product alkyl radicals are probed by 157 nm single photon ionization following reaction at a collision energy of ∼10 kcal mol{sup −1}. The analyzed data are compared with the corresponding theoretical studies. Reduced translational energy distributions for each system show similar trends with little of the reaction exoergicity appearing in translation. However, the pentane reaction shows a somewhat smaller fraction of available energy in translation than the other two, suggesting greater energy channeled into pentyl internal degrees of freedom. The center-of-mass angular distributions all show backscattering as well as sharp forward scattering that decreases in relative intensity with the size of the molecule. Possible reasons for these trends are discussed.

  18. Word Pro - Untitled1

    Gasoline and Diesel Fuel Update (EIA)

    9 Table 5.10 Natural Gas Plant Liquids Production, Selected Years, 1949-2011 (Thousand Barrels per Day) Year Finished Petroleum Products 1 Liquefied Petroleum Gases Pentanes Plus 4 Total Ethane 2 Isobutane Normal Butane 3 Propane 2,3 Total 1949 53 8 11 61 74 155 223 430 1950 66 12 13 69 101 195 238 499 1955 68 34 30 120 205 390 313 771 1960 47 51 45 161 291 549 333 929 1965 41 92 67 185 390 734 434 1,210 1970 25 201 84 248 561 1,095 540 1,660 1975 7 337 90 237 552 1,217 409 1,633 1976 6 365 82

  19. Table 5.10 Natural Gas Plant Liquids Production, 1949-2011 (Thousand Barrels)

    U.S. Energy Information Administration (EIA) Indexed Site

    0 Natural Gas Plant Liquids Production, 1949-2011 (Thousand Barrels) Year Finished Petroleum Products 1 Liquefied Petroleum Gases Pentanes Plus 4 Total Ethane 2 Isobutane Normal Butane 3 Propane 2,3 Total 1949 19,210 3,056 4,182 22,283 27,114 56,634 81,241 157,086 1950 23,931 4,253 4,667 25,323 37,018 71,261 86,769 181,961 1951 26,505 5,545 5,509 27,960 45,798 84,812 93,437 204,754 1952 25,488 7,089 6,568 31,349 54,732 99,738 98,289 223,515 1953 25,739 6,151 7,006 35,308 61,544 110,009 102,831

  20. Minutes of the tenth meeting of the centers for the analysis of thermal/mechanical energy conversion concepts

    SciTech Connect (OSTI)

    DiPippo, R.

    1981-03-01

    The agenda, list of participants, and minutes of the meeting are presented. Included in the appendices are figures, data, outlines, etc. from the following presentations: 500 kW Direct-Contact Heat Exchanger Pilot Plant; LBL/EPRI Heat Exchanger Field Test, Critical Temperature and Pressure Comparisons for n-Butane/n-Pentane Mixtures; Second Law Techniques in the Correlation of Cost-Optimized Binary Power Plants; Outline of Chapter on Geothermal Well Logging; Outline and Highlights from Geothermal Drilling and Completion Technology Development Program Annual Progress: October 1979-September 1980; Geothermal Well Stimulation; World Update on Installed Geothermal Power Plants; Baca No. 1 Demonstration Flask Plant: Technical and Cost Data; Heber Binary Project; 45 mw Demonstration Plant; Raft River 5 mw Geothermal Dual-Boiling-Cycle Plant; Materials Considerations in the Design of Geothermal Power Plants; Raft River Brine Treatment for Tower Make-up; and Site Photographs of Raft River Valley.

  1. U.S. Imports of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

    294,833 302,821 280,042 272,798 273,770 301,517 1981-2015 Crude Oil 227,255 236,785 216,669 220,747 221,117 244,915 1920-2015 Natural Gas Plant Liquids and Liquefied Refinery Gases 3,621 4,126 3,046 4,026 4,880 5,580 1981-2015 Pentanes Plus 4 325 2 316 647 318 1981-2015 Liquefied Petroleum Gases 3,617 3,801 3,044 3,710 4,233 5,262 1981-2015 Ethane 1993-2006 Ethylene 1993-2015 Propane 2,284 2,486 1,935 2,476 3,127 3,853 1995-2015 Propylene 668 724 433 344 383 608 1993-2015 Normal Butane 140 76

  2. Beowawe Bottoming Binary Unit - Final Technical Report for EE0002856

    SciTech Connect (OSTI)

    McDonald, Dale Edward

    2013-02-12

    This binary plant is the first high-output refrigeration based waste heat recovery cycle in the industry. Its working fluid is environmentally friendly and as such, the permits that would be required with a butane based cycle are not necessary. The unit is modularized, meaning that the unit’s individual skids were assembled in another location and were shipped via truck to the plant site. This project proves the technical feasibility of using low temperature brine The development of the unit led to the realization of low temperature, high output, and environmentally friendly heat recovery systems through domestic research and engineering. The project generates additional renewable energy for Nevada, resulting in cleaner air and reduced carbon dioxide emissions. Royalty and tax payments to governmental agencies will increase, resulting in reduced financial pressure on local entities. The major components of the unit were sourced from American companies, resulting in increased economic activity throughout the country.

  3. Risk analysis of an LPG facility

    SciTech Connect (OSTI)

    Daley, H.F.; Chapman, P.D.L.

    1986-01-01

    This paper describes methods used to conduct a safety review of an existing LPG loading, processing, and storage facility. An engineering team conducted a Hazard and Operability study of the plant to identify potential problems. A Probabilistic Risk Assessment was also made on the facility where the probability and consequences of worst case accidents were estimated. Stone and Webster recently completed an analysis of an LPG terminal to determine if there were any engineering, design, or operating deficiencies which could jeopardize the operability of the facility or make operation hazardous. The facility includes a dock for off-loading refrigerated propane and butane, transfer piping from the dock to storage, a heating system, pressurized storage, dehydration, product transfer and loading.

  4. Deflagration to detonation transition in mixtures of alkane LNG/LPG constituents with O/sub 2//N/sub 2/

    SciTech Connect (OSTI)

    Lindstedt, R.P.; Michels, H.J.

    1988-04-01

    Deflagration to detonation transitions (DDT) of methane, methane/ethane, ethane, propane, and butane in mixtures with increasing dilution of nitrogen have been studied in a smooth 2'' id detonation tube with a length/diameter ratio of 220. The results obtained demonstrate the presence of two regimes of DDT depending on the reactivity of the mixture. The first regime displays rapid acceleration to a stable detonation, while the second regime contains a quasistable, strong deflagration of rapidly increasing duration with decreasing mixture reactivity. It is established that the order of DDT under the conditions employed follows the order of autoignition temperatures for the fuels considered. The conditional use of transition parameters for estimates of relative detonabilities based on a qualitative similarity between induction times and times to transition is demonstrated to hold only for the first transition regime.

  5. Process boasts 95% selectivity for LPG

    SciTech Connect (OSTI)

    Brinkmeyer, F.M.; Drehman, L.E.; Olbrich, M.E.; Rohr, D.F.

    1983-03-28

    This article describes a new Phillips catalytic process for the dehydrogenation and/or the dehydrocyclization of paraffinic feedstocks, steam active reforming (STAR), which produces no structural isomerization. Light paraffins such as propane, isobutane, and normal butane can be dehydrogenated to their respective mono-olefins with selectivities as high as 95%. The process offers such advantages as: it will accept a wide range of feedstocks; selectivity to desired products is high; there is a minimum of structural isomerization which permits the production of specific products from particular feedstocks with high purity; it works well with paraffinic and olefinic materials which make poor feeds in conventional reforming processes; and the catalyst has moderate tolerance for sulfur and nitrogen compounds.

  6. Conversion of lpg hydrocarbons to distillate fuels or lubes using integration of lpg dehydrogenation and mogdl

    SciTech Connect (OSTI)

    Chang, C. D.; Penick, J. E.; Socha, R. F.

    1985-09-17

    Disclosed is a method and apparatus for producing distillate and/or lubes which employ integrating catalytic (or thermal) dehydrogenation of paraffins with MOGDL. The process feeds the product from a low temperature propane and/or butane dehydrogenation zone into a first catalytic reactor zone, which operates at low pressure and contains zeolite oligomerization catalysts, where the low molecular weight olefins are reacted to primarily gasoline range materials. These gasoline range materials can then be pressurized to the pressure required for reacting to distillate in a second catalytic reactor zone operating at high pressure and containing a zeolite oligomerization catalyst. The distillate is subsequently sent to a hydrotreating unit and product separation zone to form lubes and other finished products.

  7. Carbon adsorption system protects LPG storage sphere

    SciTech Connect (OSTI)

    Gothenquist, C.A.; Rooker, K.M.

    1996-07-01

    Chevron U.S.A. Products Co. installed a carbon adsorption system to protect an LPG storage sphere at its refinery in Richmond, Calif. Vessel damage can result when amine contamination leads to emulsion formation and consequent amine carry-over, thus promoting wet-H{sub 2}S cracking. In Chevron`s No. 5 H{sub 2}S recovery plant, a mixture of butane and propane containing H{sub 2}S is contacted with diethanolamine (DEA) in a liquid-liquid absorber. The absorber is a countercurrent contactor with three packed beds. Because the sweetening system did not include a carbon adsorption unit for amine purification, contaminants were building up in the DEA. The contaminants comprised: treatment chemicals, hydrocarbons, foam inhibitors, and amine degradation products. The paper describes the solution to this problem.

  8. U.S. Natural Gas Plant Field Production

    U.S. Energy Information Administration (EIA) Indexed Site

    2010 2011 2012 2013 2014 2015 View History Natural Gas Liquids 757,019 808,865 881,306 951,057 1,100,298 1,194,630 1981-2015 Pentanes Plus 101,155 106,284 116,002 126,809 143,831 156,568 1981-2015 Liquefied Petroleum Gases 655,864 702,581 765,304 824,248 956,467 1,038,062 1981-2015 Ethane 317,180 337,972 356,592 354,089 398,206 404,287 1981-2015 Propane 213,782 230,227 260,704 300,348 359,430 407,750 1981-2015 Normal Butane 56,655 57,399 65,555 80,045 100,930 118,151 1981-2015 Isobutane 68,247

  9. U.S. Refinery Net Input

    U.S. Energy Information Administration (EIA) Indexed Site

    2010 2011 2012 2013 2014 2015 View History Total 4,178,588 4,091,601 4,007,375 4,037,265 3,954,862 3,894,471 2005-2015 Crude Oil 5,374,094 5,404,347 5,489,516 5,589,006 5,784,637 5,915,532 2005-2015 Natural Gas Plant Liquids 154,941 171,074 175,607 168,808 172,563 171,936 2005-2015 Pentanes Plus 54,697 61,059 59,432 56,153 52,853 50,850 2005-2015 Liquefied Petroleum Gases 100,244 110,015 116,175 112,655 119,710 121,086 2005-2015 Normal Butane 39,253 42,087 45,747 42,461 45,916 47,870 2005-2015

  10. Pentan isomers compound flame front structure

    SciTech Connect (OSTI)

    Mansurov, Z.A.; Mironenko, A.W.; Bodikov, D.U.; Rachmetkaliev, K.N.

    1995-08-13

    The fuels (hexane, pentane, diethyl ether) and conditions investigated in this study are relevant to engine knock in spark- ignition engines. A review is provided of the field of low temperature hydrocarbon oxidation. Studies were made of radical and stable intermediate distribution in the front of cool flames: Maximum concentrations of H atoms and peroxy radicals were observed in the luminous zone of the cool flame front. Peroxy radicals appear before the luminous zone at 430 K due to diffusion. H atoms were found in cool flames of butane and hexane. H atoms diffuses from the luminous zone to the side of the fresh mixture, and they penetrate into the fresh mixture to a small depth. Extension of action sphear of peroxy radicals in the fresh mixture is much greater than that of H atoms due to their small activity and high concentrations.

  11. Synthesis of 3-amino-4-hydroxylaminothiazolidine-2-thiones and 2,3-dimethyl-4. cap alpha. ,5-dihydro-7-thioxothiazolo(3,4-b)-1,2,4-triazines

    SciTech Connect (OSTI)

    Epshtein, S.P.; Orlova, T.I.; Rukasov, A.F.; Tashchi, V.P.; Putsykin, Yu. G.

    1987-10-01

    The reaction of dimeric nitroso chlorides of olefins with potassium dithiocarbazate was used to synthesize 3-amino-4-hydroxylaminothiazolidine-2-thiones, which undergo rearrangement to 2-mercapto-1,3,4-thiadiazines on heating and react with butane-2,3-dione to give 2,3-dimethyl-4..cap alpha..,5-dihydro-7-thioxothiazolo(3,4-b)-1,2,4-triazine 4-oxides. The latter are reduced by sodium borohydride to the corresponding 3,4,4..cap alpha..,5-tetrahydro-7-thioxo derivatives. The IR spectra of KBr pellets of the compounds were recorded with a Perkin-Elmer spectrometer. The UV spectra of solutions in ethanol were obtained with a Specord UV spectrophotometer. The PMR spectra of solutions of the compounds in d/sub 6/-DMSO were obtained with a Varian FT-80A spectrometer with tetramethylsilane (TMS) as the internal standard.

  12. Arabidopsis AtSerpin1, Crystal Structure and in Vivo Interaction with Its Target Protease RESPONSIVE TO DESICCATION-21 (RD21)

    SciTech Connect (OSTI)

    Lampl, Nardy; Budai-Hadrian, Ofra; Davydov, Olga; Joss, Tom V.; Harrop, Stephen J.; Curmi, Paul M.G.; Roberts, Thomas H.; Fluhr, Robert

    2010-05-25

    In animals, protease inhibitors of the serpin family are associated with many physiological processes, including blood coagulation and innate immunity. Serpins feature a reactive center loop (RCL), which displays a protease target sequence as a bait. RCL cleavage results in an irreversible, covalent serpin-protease complex. AtSerpin1 is an Arabidopsis protease inhibitor that is expressed ubiquitously throughout the plant. The x-ray crystal structure of recombinant AtSerpin1 in its native stressed conformation was determined at 2.2 {angstrom}. The electrostatic surface potential below the RCL was found to be highly positive, whereas the breach region critical for RCL insertion is an unusually open structure. AtSerpin1 accumulates in plants as a full-length and a cleaved form. Fractionation of seedling extracts by nonreducing SDS-PAGE revealed the presence of an additional slower migrating complex that was absent when leaves were treated with the specific cysteine protease inhibitor l-trans-epoxysuccinyl-l-leucylamido (4-guanidino)butane. Significantly, RESPONSIVE TO DESICCATION-21 (RD21) was the major protease labeled with the l-trans-epoxysuccinyl-l-leucylamido (4-guanidino)butane derivative DCG-04 in wild type extracts but not in extracts of mutant plants constitutively overexpressing AtSerpin1, indicating competition. Fractionation by nonreducing SDS-PAGE followed by immunoblotting with RD21-specific antibody revealed that the protease accumulated both as a free enzyme and in a complex with AtSerpin1. Importantly, both RD21 and AtSerpin1 knock-out mutants lacked the serpin-protease complex. The results establish that the major Arabidopsis plant serpin interacts with RD21. This is the first report of the structure and in vivo interaction of a plant serpin with its target protease.

  13. Influence of Crystal Expansion/Contraction on Zeolite Membrane Permeation

    SciTech Connect (OSTI)

    Sorenson, Stephanie G; Payzant, E Andrew; Noble, Richard D; Falconer, John L.

    2010-01-01

    X-ray diffraction was used to measure the unit cell parameters of B-ZSM-5, SAPO-34, and NaA zeolite powders as a function of adsorbate loading at 303 K, and in one case, at elevated temperatures. Most adsorbates expanded the zeolite crystals below saturation loading at 303 K: n-hexane and SF6 in B-ZSM-5, methanol and CO2 in SAPO-34, and methanol in NaA zeolite. As the loadings increased, the crystals expanded more. Changes in the unit cell volumes of B-ZSM-5 and SAPO-34 zeolite powders correlated with changes in permeation through zeolite membranes defects. When the zeolite crystals expanded or contracted upon adsorption, the defect sizes decreased or increased. In B-ZSM-5 membranes, the fluxes through defects decreased dramatically when n-hexane or SF6 adsorbed. In contrast, i-butane adsorption at 303 K contracted B-ZSM-5 crystals at low loadings and expanded them at higher loadings. Correspondingly, the flux through B-ZSM-5 membrane defects increased at low i-butane loadings and decreased at high loading because the defects increased in size at low loading and decreased at high loadings. At 398 K and 473 K, n-hexane expanded the B-ZSM-5 unit cell more as the temperature increased from 303 to 473 K. The silicalite-1 and B-ZSM-5 unit cell volumes expanded similarly upon n-hexane adsorption at 303 K; boron substitution had little effect on volume expansion.

  14. Regional analysis of non-methane hydrocarbons and meteorology of the rural southeast United States

    SciTech Connect (OSTI)

    Hagerman, L.M.

    1996-11-01

    Measurements of non-methane hydrocarbons, as well as ozone, meteorological and trace gas data, were made at four rural sites located within the southeastern United States as a part of the Southern Oxidants Study. Fifty-six C2-C10 hydrocarbons were collected from 1200-1300 local time, once every six days from September 1992 through October 1993. The measurements were made in an effort to enhance the understanding of the behavior and trends of ozone and other photochemical oxidants in this region. The light molecular weight alkanes (ethane, propane, n-butane, iso-butane), ethene and acetylene display a seasonal variation with a winter maximum and summer minimum. Isoprene was virtually non-existent during the winter at all sites, and averaged from 9.8 ppbC (Yorkville, GA) to 21.15 ppbC (Centreville, AL) during the summer. The terpene concentration was greatest in the summer with averages ranging between 3.19 ppbC (Centreville, AL) to 6.38 ppbC (Oak Grove, MS), but was also emitted during the winter months, with a range of 1.25 to 1.9 ppbC for all sites. Propylene-equivalent concentrations were calculated to account for differences in reaction rates between the hydroxyl radical and individual hydrocarbons, and to thereby estimate their relative contribution to ozone, especially in regards to the highly reactive biogenic compounds such as isoprene. It was calculated that biogenics represent at least 65% of the total non-methane hydrocarbon sum at these four sites during the summer season when considering propylene-equivalent concentrations. An ozone episode which occurred from July 20 to July 24 1993 was used as an example to show ozone profiles at each of the sites, and to show the effect of synoptic meteorology on high ozone by examining NOAA daily weather maps and climatic data.

  15. Activation of ethane in the presence of solid acids: Sulfated zirconia, iron- and manganese-promoted sulfated zirconia, and zeolites

    SciTech Connect (OSTI)

    Cheung, Tsz-Keung; Gates, B.

    1997-06-01

    Ethane was activated in the presence of solid acids [sulfated zirconia (SZ), iron- and manganese-promoted sulfated zirconia (FMSZ), HZSM-5, and USY zeolite] at 1 atm, 200-450{degrees}C, and ethane partial pressures in the range 0.014.2 atm. The data were measured with a flow reactor at low conversions (<0.005) such that reaction of ethane took place in the near absence of alkenes. Catalysis was demonstrated for ethane conversion in the presence of FMSZ at 450{degrees}C and 0.2 atm ethane partial pressure, but the reactions were not shown to be catalytic for the other solid acids and other conditions. FMSZ was active for converting ethane into methane, ethene, and butane at an ethane partial pressure of 0.2 atm and at temperatures of 200-300{degrees}C; the other solid acids had no detectable activities under these conditions. At higher temperatures, each of the solid acids was active for conversion of ethane into ethene; butane and methane were also formed in the presence of FMSZ, HZSM-5, and USY zeolite, whereas methane was the only other hydrocarbon observed in the presence of SZ. The initial (5 min on stream) selectivities to ethene at approximately 0.1 % conversion, ethane partial pressure of 0.2 atm, and 450{degrees}C were approximately 98, 94, 97, and 99%, for SZ, FMSZ, HZSM-5, and USY zeolite, respectively. Under the same reaction conditions, the initial rates of ethane conversion were 0. 1 5 x 10{sup -8}, 3.5 x 10{sup -8} 3.9 x 10{sup -8}, and 0.56 x 10{sup -8} mol/(s {circ} g) for SZ, FMSZ, HZSM-5, and USY zeolite, respectively. The reactivities are consistent with chemistry analogous to that occurring in superacidic solutions and with the suggestion that FMSZ is a stronger acid than the others investigated here. 25 refs., 13 figs., 1 tab.

  16. X-Ray Absorption Studies of Vanadium-Containing Metal Oxide Nanocrystals

    SciTech Connect (OSTI)

    Hohn, Keith, L.

    2006-01-09

    Metal oxide nanocrystals offer significant potential for use as catalysts or catalyst supports due to their high surface areas and unique chemical properties that result from the high number of exposed corners and edges. However, little is known about the catalytic activity of these materials, especially as oxidation catalysts. This research focused on the preparation, characterization and use of vanadium-containing nanocrystals as selective oxidation catalysts. Three vanadium-containing nanocrystals were prepared using a modified sol-gel procedure: V/MgO, V/SiO2, and vanadium phosphate (VPO). These represent active oxidation catalysts for a number of industrially relevant reactions. The catalysts were characterized by x-ray diffraction and Raman, UV-VIS, infrared and x-ray absorption spectroscopies with the goal of determining the primary structural and chemical differences between nanocrystals and microcrystals. The catalytic activity of these catalysts was also studied in oxidative dehydrogenation of butane and methanol oxidation to formaldehyde. V/MgO nanocrystals were investigated for activity in oxidative dehydrogenation of butane and compared to conventional V/MgO catalysts. Characterization of V/MgO catalysts using Raman spectroscopy and x-ray absorption spectroscopy showed that both types of catalysts contained magnesium orthovanadate at vanadium loadings below 15 weight%, but above that loading, magnesium pyrovanadate may have been present. In general, MgO nanocrystals had roughly half the crystal size and double the surface area of the conventional MgO. In oxidative dehydrogenation of butane, nanocrystalline V/MgO gave higher selectivity to butene than conventional V/MgO at the same conversion. This difference was attributed to differences in vanadium domain size resulting from the higher surface areas of the nanocrystalline support, since characterization suggested that similar vanadium phases were present on both types of catalysts. Experiments in methanol oxidation were used to probe the chemical differences between sol-gel prepared and conventionally prepared metal oxides. Both V/MgO and V/SiO2 were studied. For both catalysts, similar product selectivities were noted for either preparation method, suggesting similar acid/base and redox properties for the catalysts. At lower weight loadings (<5%), activity was also similar, but at higher weight loadings the sol-gel prepared catalysts were more active. This was attributed to the greater dispersion of vanadium on sol-gel prepared catalysts, and it was suggested that small vanadium oxide domains were more active in methanol oxidation than polymeric and bulk domains. A novel sol-gel method was developed for preparation of VPO catalysts, which are used industrially in butane oxidation to maleic anhydride. In this method vanadium (V) triisopropoxide was reacted with orthophosphoric acid in THF to form a gel. Drying this gel under air resulted in an intercalated VOPO4 compound, where solvent molecules were trapped between layers of the vanadium phosphate compound. Higher surface areas could be achieved by drying this gel at high pressure in an autoclave. The amount of solvent (THF) placed in the autoclave was important in this process. Low amounts of solvent led to a lower surface area, as the solvent evaporated before reaching the critical point and collapsed the gel's pores. In addition, vanadium reduction occurred in the autoclave due to reaction of isopropanol with the vanadium phosphate. Higher amounts of THF reduced the concentration of isopropanol, leading to less reduction. Surfaces areas in excess of 100 m2/g were achieved with this method, and the product was confirmed through XPS and IR to be VOHPO4*0.5H2O, the common precursor for industrial VPO catalysts. Furthermore, this product displayed a platelet morphology, which is desirable for butane oxidation. Further work showed that this material could be transformed to (VO)2P2O7 (the industrial catalyst for butane oxidation to maleic anhydride) by heating under nitrogen without losing much surface are

  17. Conversion of LPG hydrocarbons to distillate fuels or lubes using integration of LPG dehydrogenation and mogdl

    SciTech Connect (OSTI)

    Chang, C.D.; Penick, J.E.; Socha, R.F.

    1987-07-07

    This patent describes an apparatus for producing distillates of lubes from paraffins, which comprise: (a) a dehydrogenation reactor including means for passing a paraffinic feedstock stream into a dehydrogenation zone at conditions of pressure and temperature selected to convert the paraffins to an olefin rich effluent stream comprising at least one of the group consisting of propylene and butylene; (b) a low pressure oligomerization catalytic reactor including means for contacting the olefin rich effluent stream in a low pressure oligomerization catalytic reactor zone with a crystalline zeolite oligomerization catalyst at conditions of pressure and temperature selected to convert olefins to a first reactor effluent stream rich in liquid olefinic gasoline range hydrocarbons; (c) a first means for separating the first reactor effluent stream to form a substantially liquid C/sub 5/+ rich stream and a C/sub 4/- rich stream; (d) means for passing the C/sub 5/+ rich stream to a high pressure oligomerization catalytic reactor zone; (e) a high pressure oligomerization catalytic reactor including means for contacting the substantially liquid C/sub 5/+ rich stream in the high pressure oligomerization catalytic reactor zone with a crystalline zeolite oligomerization catalyst at conditions of temperature and pressure selected to produce a second reactor effluent stream which is rich in distillate; (f) second means for separating the second reactor effluent stream to recover an olefinic gasoline stream and a distillate stream; and (g) a hydrotreating reactor including means for contacting the distillate stream with hydrogen in a hydrotreating unit to produce a hydrotreated distillate stream comprising lube range hydrocarbons.

  18. Interpenetrating metal-organic frameworks formed by self-assembly of tetrahedral and octahedral building blocks

    SciTech Connect (OSTI)

    Lu Yongming; Lan Yaqian; Xu Yanhong; Su Zhongmin; Li Shunli; Zang Hongying; Xu Guangjuan

    2009-11-15

    To investigate the relationship between topological types and molecular building blocks (MBBs), we have designed and synthesized a series of three-dimensional (3D) interpenetrating metal-organic frameworks based on different polygons or polyhedra under hydrothermal conditions, namely [Cd(bpib){sub 0.5}(L{sup 1})] (1), [Cd(bpib){sub 0.5}(L{sup 2})].H{sub 2}O (2), [Cd(bpib){sub 0.5}(L{sup 3})] (3) and [Cd(bib){sub 0.5}(L{sup 1})] (4), where bpib=1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane, bib=1,4-bis(1H-imidazol-1-yl)butane, H{sub 2}L{sup 1}=4-(4-carboxybenzyloxy)benzoic acid, H{sub 2}L{sup 2}=4,4'-(ethane-1,2-diylbis(oxy))dibenzoic acid and H{sub 2}L{sup 3}=4,4'-(1,4-phenylenebis(methylene))bis(oxy)dibenzoic acid, respectively. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compounds 1-3 display alpha-Po topological nets with different degrees of interpenetration based on the similar octahedral [Cd{sub 2}(-COO){sub 4}] building blocks. Compound 4 is a six-fold interpenetrating diamondoid net based on tetrahedral MBBs. By careful inspection of these structures, we find that various carboxylic ligands and N-donor ligands with different coordination modes and conformations, and metal centers with different geometries are important for the formation of the different MBBs. It is believed that different topological types lie on different MBBs with various polygons or polyhedra. Such as four- and six-connected topologies are formed by tetrahedral and octahedral building blocks. In addition, with the increase of carboxylic ligands' length, the degrees of interpenetration have been changed in the alpha-Po topological nets. And the luminescent properties of these compounds have been investigated in detail. - Graphical abstract: A series of three-dimensional interpenetrating metal-organic frameworks based on different polygons or polyhedra has been synthesized. The crystal structures and topological analysis of these compounds, along with a systematic investigation of the relationship between topological types and molecular building blocks, will be discussed.

  19. Water-enhanced solvation of organics

    SciTech Connect (OSTI)

    Lee, J.H.

    1993-07-01

    Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log {gamma}{sub s} vs x{sub w}/x{sub s} curve. From graph shape {Delta}(log {gamma}{sub s}) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement {Delta} (log {gamma}{sub acid})/{Delta}(x{sub w}/x{sub acid}) = {minus}0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was {minus}0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

  20. MgO-Supported Cluster Catalysts with Pt-Ru Interactions Prepared from Pt3Ru6(CO)21(u3-H)(u-H)3

    SciTech Connect (OSTI)

    Chotisuwan,S.; Wittapyakun, J.; Lobo-Lapidus, R.; Gates, B.

    2007-01-01

    Bimetallic MgO-supported catalysts were prepared by adsorption of Pt{sub 3}Ru{sub 6}(CO){sub 21}({mu}{sub 3}-H)({mu}-H){sub 3} on porous MgO. Characterization of the supported clusters by infrared (IR) spectroscopy showed that the adsorbed species were still in the form of metal carbonyls. The supported clusters were decarbonylated by treatment in flowing helium at 300 C, as shown by IR and extended X-ray absorption fine structure (EXAFS) data, and the resulting supported PtRu clusters were shown by EXAFS spectroscopy to have metal frames that retained Pt-Ru bonds but were slightly restructured relative to those of the precursor; the average cluster size was almost unchanged as a result of the decarbonylation. These are among the smallest reported bimetallic clusters of group-8 metals. The decarbonylated sample catalyzed ethylene hydrogenation with an activity similar to that reported previously for {gamma}-Al{sub 2}O{sub 3}-supported clusters prepared in nearly the same way and having nearly the same structure. Both samples were also active for n-butane hydrogenolysis, with the MgO-supported catalyst being more active than the {gamma}-Al{sub 2}O{sub 3}-supported catalyst.

  1. Kinetic effects on double hysteresis in spin crossover molecular magnets analyzed with first order reversal curve diagram technique

    SciTech Connect (OSTI)

    Stan, Raluca-Maria; Gaina, Roxana; Enachescu, Cristian E-mail: radu.tanasa@uaic.ro; Stancu, Alexandru; Tanasa, Radu E-mail: radu.tanasa@uaic.ro; Bronisz, Robert

    2015-05-07

    In this paper, we analyze two types of hysteresis in spin crossover molecular magnets compounds in the framework of the First Order Reversal Curve (FORC) method. The switching between the two stable states in these compounds is accompanied by hysteresis phenomena if the intermolecular interactions are higher than a threshold. We have measured the static thermal hysteresis (TH) and the kinetic light induced thermal hysteresis (LITH) major loops and FORCs for the polycrystalline Fe(II) spin crossover compound [Fe{sub 1?x}Zn{sub x}(bbtr){sub 3}](ClO{sub 4}){sub 2} (bbtr?=?1,4-di(1,2,3-triazol-1-yl)butane), either in a pure state (x?=?0) or doped with Zn ions (x?=?0.33) considering different sweeping rates. Here, we use this method not only to infer the domains distribution but also to disentangle between kinetic and static components of the LITH and to estimate the changes in the intermolecular interactions introduced by dopants. We also determined the qualitative relationship between FORC distributions measured for TH and LITH.

  2. Chemistry of Tantalum Clusters in Solution And on SiO(2) Supports: Analogies And Contrasts

    SciTech Connect (OSTI)

    Nemana, S.; Okamoto, N.L.; Browning, N.D.; Gates, B.C.

    2009-06-03

    Tantalum clusters have been synthesized from Ta(CH{sub 2}Ph){sub 5} on the surface of porous fumed SiO{sub 2}. When these clusters are small, incorporating, on average, several Ta atoms, their chemistry is similar to that of molecular tantalum clusters (and other early transition-metal) clusters. For example, The Ta-Ta bonds in these small supported clusters have been characterized by extended X-ray absorption fine structure (EXAFS), IR, and UV-vis spectroscopy, being similar to those in molecular analogues. The redox reactions of the supported clusters, characterized by X-ray absorption near-edge structure, are analogous to those of early transition-metal clusters in solution. In contrast to the largest of these clusters in solution and in the solid state, those supported on SiO{sub 2} are raftlike, facilitating the substantial metal-support-oxygen bonding that is evident in the EXAFS spectra. Samples consisting of tantalum clusters on SiO{sub 2} catalyze alkane disproportionation and the conversion of methane with n-butane to give other alkanes, but catalytic properties of analogous clusters in solution have barely been explored.

  3. An experimental and kinetic modeling study of n-butanol combustion

    SciTech Connect (OSTI)

    Sarathy, S.M.; Thomson, M.J.; Togbe, C.; Dagaut, P.; Halter, F.; Mounaim-Rousselle, C.

    2009-04-15

    n-Butanol is a fuel that has been proposed as an alternative to conventional gasoline and diesel fuels. In order to better understand the combustion characteristics of n-butanol, this study presents new experimental data for n-butanol in three experimental configurations. Species concentration profiles are presented in jet stirred reactor (JSR) at atmospheric conditions and a range of equivalence ratios. The laminar flame speed obtained in an n-butanol premixed laminar flame is also provided. In addition, species concentration profiles for n-butanol and n-butane in an opposed-flow diffusion flame are presented. The oxidation of n-butanol in the aforementioned experimental configurations has been modeled using an improved detailed chemical kinetic mechanism (878 reactions involving 118 species) derived from a previously proposed scheme in the literature. The proposed mechanism shows good qualitative agreement with the various experimental data. Sensitivity analyses and reaction path analyses have been conducted to interpret the results from the JSR and opposed-flow diffusion flame. It is shown that the main reaction pathway in both configurations is via H-atom abstraction from the fuel followed by {beta}-scission of the resulting fuel radicals. Several unimolecular decomposition reactions are important as well. This study gives a better understanding of n-butanol combustion and the product species distribution. (author)

  4. Fundamental Study of the Oxidation Characteristics and Pollutant Emissions of Model Biodiesel Fuels

    SciTech Connect (OSTI)

    Feng, Q.; Wang, Y. L.; Egolfopoulos, Fokion N.; Tsotsis, T. T.

    2010-07-18

    In this study, the oxidation characteristics of biodiesel fuels are investigated with the goal of contributing toward the fundamental understanding of their combustion characteristics and evaluating the effect of using these alternative fuels on engine performance as well as on the environment. The focus of the study is on pure fatty acid methyl-esters (FAME,) that can serve as surrogate compounds for real biodiesels. The experiments are conducted in the stagnation-flow configuration, which allows for the systematic evaluation of fundamental combustion and emission characteristics. In this paper, the focus is primarily on the pollutant emission characteristics of two C{sub 4} FAMEs, namely, methyl-butanoate and methyl-crotonate, whose behavior is compared with that of n-butane and n-pentane. To provide insight into the mechanisms of pollutant formation for these fuels, the experimental data are compared with computed results using a model with consistent C1-C4 oxidation and NOx formation kinetics.

  5. Explosive photodissociation of methane induced by ultrafast intense laser

    SciTech Connect (OSTI)

    Kong Fanao; Luo Qi; Xu Huailiang; Sharifi, Mehdi; Song Di; Chin, See Leang

    2006-10-07

    A new type of molecular fragmentation induced by femtosecond intense laser at the intensity of 2x10{sup 14} W/cm{sup 2} is reported. For the parent molecule of methane, ethylene, n-butane, and 1-butene, fluorescence from H (n=3{yields}2), CH (A {sup 2}{delta}, B {sup 2}{sigma}{sup -}, and C {sup 2}{sigma}{sup +}{yields}X {sup 2}{pi}), or C{sub 2} (d {sup 3}{pi}{sub g}{yields}a {sup 3}{pi}{sub u}) is observed in the spectrum. It shows that the fragmentation is a universal property of neutral molecule in the intense laser field. Unlike breaking only one or two chemical bonds in conventional UV photodissociation, the fragmentation caused by the intense laser undergoes vigorous changes, breaking most of the bonds in the molecule, like an explosion. The fragments are neutral species and cannot be produced through Coulomb explosion of multiply charged ion. The laser power dependence of CH (A{yields}X) emission of methane on a log-log scale has a slope of 10{+-}1. The fragmentation is thus explained as multiple channel dissociation of the superexcited state of parent molecule, which is created by multiphoton excitation.

  6. Thermal Degradation Studies of Polyurethane/POSS Nanohybrid Elastomers

    SciTech Connect (OSTI)

    Lewicki, J P; Pielichowski, K; TremblotDeLaCroix, P; Janowski, B; Todd, D; Liggat, J J

    2010-03-05

    Reported here is the synthesis of a series of Polyurethane/POSS nanohybrid elastomers, the characterization of their thermal stability and degradation behavior at elevated temperatures using a combination of Thermal Gravimetric Analysis (TGA) and Thermal Volatilization Analysis (TVA). A series of PU elastomers systems have been formulated incorporating varying levels of 1,2-propanediol-heptaisobutyl-POSS (PHIPOSS) as a chain extender unit, replacing butane diol. The bulk thermal stability of the nanohybrid systems has been characterized using TGA. Results indicate that covalent incorporation of POSS into the PU elastomer network increase the non-oxidative thermal stability of the systems. TVA analysis of the thermal degradation of the POSS/PU hybrid elastomers have demonstrated that the hybrid systems are indeed more thermally stable when compared to the unmodified PU matrix; evolving significantly reduced levels of volatile degradation products and exhibiting a {approx}30 C increase in onset degradation temperature. Furthermore, characterization of the distribution of degradation products from both unmodified and hybrid systems indicate that the inclusion of POSS in the PU network is directly influencing the degradation pathways of both the soft and hard block components of the elastomers: The POSS/PU hybrid systems show reduced levels of CO, CO2, water and increased levels of THF as products of thermal degradation.

  7. Nonlinear effects in the extraction of laminar flame speeds from expanding spherical flames

    SciTech Connect (OSTI)

    Kelley, A.P.; Law, C.K.

    2009-09-15

    Various factors affecting the determination of laminar flames speeds from outwardly propagating spherical flames in a constant-pressure combustion chamber were considered, with emphasis on the nonlinear variation of the stretched flame speed to the flame stretch rate, and the associated need to nonlinearly extrapolate the stretched flame speed to yield an accurate determination of the laminar flame speed and Markstein length. Experiments were conducted for lean and rich n-butane/air flames at 1atm initial pressure, demonstrating the complex and nonlinear nature of the dynamics of flame evolution, and the strong influences of the ignition transient and chamber confinement during the initial and final periods of the flame propagation, respectively. These experimental data were analyzed using the nonlinear relation between the stretched flame speed and stretch rate, yielding laminar flame speeds that agree well with data determined from alternate flame configurations. It is further suggested that the fidelity in the extraction of the laminar flame speed from expanding spherical flames can be facilitated by using small ignition energy and a large combustion chamber. (author)

  8. HIV-1 entry inhibition by small-molecule CCR5 antagonists: A combined molecular modeling and mutant study using a high-throughput assay

    SciTech Connect (OSTI)

    Labrecque, Jean; Metz, Markus; Lau, Gloria; Darkes, Marilyn C.; Wong, Rebecca S.Y.; Bogucki, David; Carpenter, Bryon; Chen Gang; Li Tongshuang; Nan, Susan; Schols, Dominique; Bridger, Gary J.; Fricker, Simon P.; Skerlj, Renato T.

    2011-05-10

    Based on the attrition rate of CCR5 small molecule antagonists in the clinic the discovery and development of next generation antagonists with an improved pharmacology and safety profile is necessary. Herein, we describe a combined molecular modeling, CCR5-mediated cell fusion, and receptor site-directed mutagenesis approach to study the molecular interactions of six structurally diverse compounds (aplaviroc, maraviroc, vicriviroc, TAK-779, SCH-C and a benzyloxycarbonyl-aminopiperidin-1-yl-butane derivative) with CCR5, a coreceptor for CCR5-tropic HIV-1 strains. This is the first study using an antifusogenic assay, a model of the interaction of the gp120 envelope protein with CCR5. This assay avoids the use of radioactivity and HIV infection assays, and can be used in a high throughput mode. The assay was validated by comparison with other established CCR5 assays. Given the hydrophobic nature of the binding pocket several binding models are suggested which could prove useful in the rational drug design of new lead compounds.

  9. Determination, correlation, and mechanistic interpretation of effects of hydrogen addition on laminar flame speeds of hydrocarbon–air mixtures

    SciTech Connect (OSTI)

    Tang, C. L.; Huang, Z. H.; Law, C. K.

    2010-08-30

    The stretch-affected propagation speeds of expanding spherical flames of n-butane–air mixtures with hydrogen addition were measured at atmospheric pressure and subsequently processed through a nonlinear regression analysis to yield the stretch-free laminar flame speeds. Based on a hydrogen addition parameter (RH) and an effective fuel equivalence ratio (?F), these laminar flame speeds were found to increase almost linearly with RH, for ?F between 0.6 and 1.4 and RHRH from 0 to 0.5, with the slope of the variation assuming a minimum around stoichiometry. These experimental results also agree well with computed values using a detailed reaction mechanism. Furthermore, a mechanistic investigation aided by sensitivity analysis identified that kinetic effects through the global activation energy, followed by thermal effects through the adiabatic flame temperature, have the most influence on the increase in the flame speeds and the associated linear variation with RH due to hydrogen addition. Nonequidiffusion effects due to the high mobility of hydrogen, through the global Lewis number, have the least influence. Further calculations for methane, ethene, and propane as the fuel showed similar behavior, leading to possible generalization of the phenomena and correlation.

  10. A reduced mechanism for methane and one-step rate expressions for fuel-lean catalytic combustion of small alkanes on noble metals

    SciTech Connect (OSTI)

    Deshmukh, S.R.; Vlachos, D.G.

    2007-06-15

    A reduced mechanism and a one-step rate expression for fuel-lean methane/air catalytic combustion on an Rh catalyst are proposed. These are developed from a detailed microkinetic model using a computer-aided model reduction strategy that employs reaction path analysis, sensitivity analysis, partial equilibrium analysis, and simple algebra to deduce the most abundant reaction intermediate and the rate-determining step. The mechanism and the one-step rate expression are then tested on Pt catalyst. It is found that the reaction proceeds effectively via the same mechanistic pathway on both noble metals, but the effective reaction orders differ due to the difference in the adsorption strength of oxygen. Based on the homologous series idea, the rate expression is extended to small alkanes (ethane and propane; butane is also briefly discussed) and is found to reasonably describe experimental data. Estimation of the relevant parameters in the rate expression for various fuels and catalysts using the semiempirical bond-order conservation theory, quantum mechanical density functional theory, and/or simple experiments is discussed. Finally, it is proposed that detailed microkinetic models with coverage-dependent parameters can assist in rationalizing the apparent discrepancies between experimental data from various research groups. (author)

  11. Thermal chemistry of copper(I)-N,N '-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces

    SciTech Connect (OSTI)

    Ma Qiang; Zaera, Francisco; Gordon, Roy G.

    2012-01-15

    The surface chemistry of copper(I)-N,N'-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces has been characterized under ultrahigh vacuum by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy. A series of thermal stepwise conversions were identified, starting with the partial dissociative adsorption of the copper acetamidinate dimers into a mixture of monomers and dimers on the surface. An early dissociation of a C-N bond leads to the production of N-sec-butylacetamidine, which is detected in TPD experiments in three temperature regimes, the last one centered around 480 K. Butene, and a small amount of butane, is also detected above approximately 500 K, and hydrogen production, an indication of dehydrogenation of surface fragments, is observed at 460, 550 and 670 K. In total, only about 10% of the initial copper(I)-N,N'-di-sec-butylacetamidinate adsorbed monolayer decomposes, and only about {approx}3% of carbon is left behind on the surface after heating to high temperatures. The implications of this surface chemistry to the design of chemical film growth processes using copper acetamidinates as precursors are discussed.

  12. Theoretical studies of high-order harmonic generation: Effects of symmetry, degeneracy, and orientation

    SciTech Connect (OSTI)

    Madsen, C. B.; Madsen, L. B.

    2007-10-15

    Using a quantum-mechanical three-step model, we present numerical calculations of the high-order harmonic generation from four polyatomic molecules. Ethylene (C{sub 2}H{sub 4}) serves as an example where orbital symmetry directly affects the harmonic yield. We treat the case of methane (CH{sub 4}) to address the high-order harmonic generation resulting from a molecule with degenerate orbitals. To this end we illustrate how the single-orbital contributions show up in the total high-order harmonic signal. This example illustrates the importance of adding coherently the amplitude contributions from the individual degenerate orbitals. Finally, we study the high-order harmonic generation from propane (C{sub 3}H{sub 8}) and butane (C{sub 4}H{sub 10}). These two molecules, being extended and far from spherical in structure, produce harmonics with nontrivial orientational dependencies. In particular, propane can be oriented so that very high-frequency harmonics are favored, and thus the molecule contains prospects for the generation of uv attosecond pulses.

  13. A model-free temperature-dependent conformational study of n-pentane in nematic liquid crystals

    SciTech Connect (OSTI)

    Burnell, E. Elliott; Weber, Adrian C. J.; Dong, Ronald Y.; Meerts, W. Leo; Lange, Cornelis A. de

    2015-01-14

    The proton NMR spectra of n-pentane orientationally ordered in two nematic liquid-crystal solvents are studied over a wide temperature range and analysed using covariance matrix adaptation evolutionary strategy. Since alkanes possess small electrostatic moments, their anisotropic intermolecular interactions are dominated by short-range size-and-shape effects. As we assumed for n-butane, the anisotropic energy parameters of each n-pentane conformer are taken to be proportional to those of ethane and propane, independent of temperature. The observed temperature dependence of the n-pentane dipolar couplings allows a model-free separation between conformer degrees of order and conformer probabilities, which cannot be achieved at a single temperature. In this way for n-pentane 13 anisotropic energy parameters (two for trans trans, tt, five for trans gauche, tg, and three for each of gauche{sub +} gauche{sub +}, pp, and gauche{sub +} gauche{sub ?}, pm), the isotropic trans-gauche energy difference E{sub tg} and its temperature coefficient E{sub tg}{sup ?} are obtained. The value obtained for the extra energy associated with the proximity of the two methyl groups in the gauche{sub +} gauche{sub ?} conformers (the pentane effect) is sensitive to minute details of other assumptions and is thus fixed in the calculations. Conformer populations are affected by the environment. In particular, anisotropic interactions increase the trans probability in the ordered phase.

  14. Global gas processing will strengthen to meet expanding markets

    SciTech Connect (OSTI)

    Haun, R.R.; Otto, K.W.; Whitley, S.C.; Gist, R.L.

    1996-07-01

    The worldwide LPG industry continues to expand faster than the petroleum industry -- 4%/year for LPG vs. 2%/year for petroleum in 1995 and less than 1%/year in the early 1990s. This rapid expansion of LPG markets is occurring in virtually every region of the world, including such developing countries as China. The Far East is the focus of much of the LPG industry`s attention, but many opportunities exist in other regions such as the Indian subcontinent, Southeast Asia, and Latin America. The investment climate is improving in all phases of downstream LPG marketing, including terminaling, storage, and wholesale and retail distribution. The world LPG supply/demand balance has been relatively tight since the Gulf War and should remain so. Base demand (the portion of demand that is not highly price-sensitive) is expanding more rapidly than supplies. As a result, the proportion of total LPG supplies available for price-sensitive petrochemical feedstock markets is declining, at least in the short term. The paper discusses importers, price patterns, world LPG demand, world LPG supply, US NGL supply, US gas processing, ethane and propane supply, butane, isobutane, and natural gasoline supply, and US NGL demand.

  15. Method and apparatus for controlling fuel/air mixture in a lean burn engine

    DOE Patents [OSTI]

    Kubesh, John Thomas (San Antonio, TX); Dodge, Lee Gene (San Antonio, TX); Podnar, Daniel James (San Antonio, TX)

    1998-04-07

    The system for controlling the fuel/air mixture supplied to a lean burn engine when operating on natural gas, gasoline, hydrogen, alcohol, propane, butane, diesel or any other fuel as desired. As specific humidity of air supplied to the lean burn engine increases, the oxygen concentration of exhaust gas discharged by the engine for a given equivalence ratio will decrease. Closed loop fuel control systems typically attempt to maintain a constant exhaust gas oxygen concentration. Therefore, the decrease in the exhaust gas oxygen concentration resulting from increased specific humidity will often be improperly attributed to an excessive supply of fuel and the control system will incorrectly reduce the amount of fuel supplied to the engine. Also, the minimum fuel/air equivalence ratio for a lean burn engine to avoid misfiring will increase as specific humidity increases. A relative humidity sensor to allow the control system to provide a more enriched fuel/air mixture at high specific humidity levels. The level of specific humidity may be used to compensate an output signal from a universal exhaust gas oxygen sensor for changing oxygen concentrations at a desired equivalence ratio due to variation in specific humidity specific humidity. As a result, the control system will maintain the desired efficiency, low exhaust emissions and power level for the associated lean burn engine regardless of the specific humidity level of intake air supplied to the lean burn engine.

  16. Breckinridge Project, initial effort. Report VII, Volume I. Introduction and background. [Storage losses of 28 products and by-products

    SciTech Connect (OSTI)

    none,

    1982-01-01

    The proposed plant site consists of 1594 acres along the Ohio River in Breckinridge County, Kentucky. An option to purchase the site has been secured on behalf of the Breckinridge Project by the Commonwealth of Kentucky Department of Energy. Figure 1 is an area map locating the site with respect to area cities and towns. The nearest communities to the site are the hamlet of Stephensport, Kentucky, about 3-1/2 miles northeast and Cloverport, Kentucky, which is 6 miles to the southwest. The nearest major cities are Owensboro, Kentucky, 45 road miles to the west and Louisville, Kentucky, 65 miles to the northeast. The Breckinridge facility will convert about 23,000 TPD of run-of-mine (ROM) coal into a nominal 50,000 BPD of hydrocarbon liquids including a significant quantity of transportation fuels. Major products refined for marketing include pipeline gas, propane, butane, 105 RONC gasoline reformate, middle distillate and heavy distillate. By-products include sulfur, anhydrous ammonia, and commercial-grade phenol. Care is being taken to minimize the impact of the facility operations on the environment. Water and wastewater treatment systems have been designed to achieve zero discharge. Waste solids will be disposed of in a carefully designed and well-monitored landfill operation. Also, special design features have been included to minimize air emissions.

  17. U.S. Natural Gas Plant Field Production

    Gasoline and Diesel Fuel Update (EIA)

    Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History Natural Gas Liquids 101,809 102,880 100,283 106,269 103,071 104,629 1981-2015 Pentanes Plus 14,341 14,218 13,829 13,963 12,798 12,666 1981-2015 Liquefied Petroleum Gases 87,468 88,662 86,454 92,306 90,273 91,963 1981-2015 Ethane 32,934 34,146 32,977 35,905 36,534 37,506 1981-2015 Propane 34,853 34,959 34,187 36,192 34,569 35,143 1981-2015 Normal Butane 9,970 10,248 10,103 10,387 10,054 9,735 1981-2015 Isobutane 9,711 9,309 9,187 9,822 9,116

  18. U.S. Refinery Net Input

    Gasoline and Diesel Fuel Update (EIA)

    Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History Total 346,773 340,480 321,878 318,765 321,561 328,213 2005-2015 Crude Oil 523,409 516,507 485,221 479,416 494,682 519,726 2005-2015 Natural Gas Plant Liquids 13,079 13,240 14,690 15,903 17,686 18,057 2005-2015 Pentanes Plus 4,606 4,453 4,693 4,431 3,897 3,932 2005-2015 Liquefied Petroleum Gases 8,473 8,787 9,997 11,472 13,789 14,125 2005-2015 Normal Butane 2,137 1,869 3,144 5,323 7,093 7,560 2005-2015 Isobutane 6,336 6,918 6,853 6,149 6,696

  19. Investigation of pressure drop in capillary tube for mixed refrigerant Joule-Thomson cryocooler

    SciTech Connect (OSTI)

    Ardhapurkar, P. M.; Sridharan, Arunkumar; Atrey, M. D.

    2014-01-29

    A capillary tube is commonly used in small capacity refrigeration and air-conditioning systems. It is also a preferred expansion device in mixed refrigerant Joule-Thomson (MR J-T) cryocoolers, since it is inexpensive and simple in configuration. However, the flow inside a capillary tube is complex, since flashing process that occurs in case of refrigeration and air-conditioning systems is metastable. A mixture of refrigerants such as nitrogen, methane, ethane, propane and iso-butane expands below its inversion temperature in the capillary tube of MR J-T cryocooler and reaches cryogenic temperature. The mass flow rate of refrigerant mixture circulating through capillary tube depends on the pressure difference across it. There are many empirical correlations which predict pressure drop across the capillary tube. However, they have not been tested for refrigerant mixtures and for operating conditions of the cryocooler. The present paper assesses the existing empirical correlations for predicting overall pressure drop across the capillary tube for the MR J-T cryocooler. The empirical correlations refer to homogeneous as well as separated flow models. Experiments are carried out to measure the overall pressure drop across the capillary tube for the cooler. Three different compositions of refrigerant mixture are used to study the pressure drop variations. The predicted overall pressure drop across the capillary tube is compared with the experimentally obtained value. The predictions obtained using homogeneous model show better match with the experimental results compared to separated flow models.

  20. Dehydrocyclodimerization, converting LPG to aromatics

    SciTech Connect (OSTI)

    Johnson, J.A.; Hilder, G.K.

    1984-03-01

    British Petroleum (BP) recognized the potential need for ways of exploiting feedstocks with low opportunity cost and commenced a research program at its Sunbury Research Center to discover and develop a catalyst for the conversion of LPG to a liquid product. The successful outcome of this research program is the Cyclar /SUP SM/ process, a joint development of UOP Process Division and British Petroleum. The Cyclar process offers a single-step conversion of LPG to an aromatic product which has a highvalue, is easily transported and useful both to fuel and petrochemical applications. The LPG producer can invest in a single unit, avoiding the need to identify and develop markets for multiple C/sub 3/ and C/sub 4/ products. This catalytic process, which employs UOP Continuous Catalyst Regeneration (CCR) technology, can also be applied to refinery light ends to produce a high-quality gasoline. Aromatic and hydrogen yields from propane and butane feeds surpass those obtained from catalytic reforming of Light Arabian naphtha. This paper describes the principles of the Cyclar process and illustrates yields and economics for several interesting applications.

  1. Mounded LPG storage - Experience and developments

    SciTech Connect (OSTI)

    Barber, D.

    1988-01-01

    Liquefied petroleum gas (LPG) is stored after production, and for distribution and use, in pressure vessels which vary in size from a few kilogrammes to many thousands of tons. The types of LPG under consideration are commercial butane, commercial propane, or mixtures of the two gases in varying proportions. Mounded storage systems are becoming popular as an alternative to the better-known traditional systems. The most widely used and therefore best-known of the traditional systems are the above-ground pressure-vessel designs. These more commonly comprise factory-made cylinders which are installed horizontally, being supported on saddles at each end of the vessel. When such vessels are installed in an LPG terminal, depot, or filling plant, they are required in multiple units to facilitate the storage of more than one grade of product and to enable regular maintenance and inspection to be carried out. Today's safety regulations require such installations to be divided into sub-groups of six tanks, with all the tanks located at a safe distance from one another, and from other facilities in the immediate area. These safety distances are being increased as a result of experience, which means terminals now require large areas of land.

  2. Rio Grande pipeline introduces LPG to Mexico

    SciTech Connect (OSTI)

    1997-06-01

    Rio Grande Pipeline, a joint venture between Mid-America Pipeline Co., Amoco Pipeline Co. and Navajo Pipeline Co., has broken new ground in the energy industry as the first LPG pipeline to cross the US-Mexico border. Plans for the project were announced in November 1995 and first deliveries started three months ago on March 21, 1997. The 8-inch, 265-mile pipeline originates near Odessa, TX, where it receives an 85-15 propane-butane mix via a connection to Mid-America Pipeline. From Odessa, product moves west through the Texas desert and crosses the Rio Grande River about 15 miles south of El Paso near Clint, TX and extends 20 miles into Mexico. Capacity of the line is 24,000 bpd and it has been averaging about 22,000 bpd since line-fill. All in all, it sounded like a reasonably feasible, routine project. But perceptions can be deceiving, or at least misleading. In other words, the project can be summarized as follows: one river, two cultures and a world of difference. The official border crossing for pipeline construction took place on Dec. 2, 1996, with a directional drill under the Rio Grande River, but in actuality, the joint venture partners were continually bridging differences in language, laws, customs and norms with Pemex and contracted workers from Mexico.

  3. Computational study of hydrocarbon adsorption in metal-organic framework Ni2(dhtp)

    SciTech Connect (OSTI)

    Sun, Xiuquan; Wick, Collin D.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2011-03-31

    Molecular dynamic simulations were carried out to study the sorption, structural properties, and diffusivities of n-hexane and cyclohexane adsorbed in Ni2(dhtp). The results indicated strong interactions between the alkanes and the host material. The free energy perturbation method was employed to investigate the adsorption free energies of methane, ethane, n-butane, n-hexane and cyclohexane. For linear alkanes, the free energy lowered as the length of the carbon chain increased. Also, the adsorption of n-hexane was preferred over cyclohexane, due to its ability to rearrange its structure to maximize contacts with the host. Furthermore, due to the large pore size of Ni2(dhtp), higher loadings of alkanes did not significantly affect the alkane structure, and enhanced the free energy of adsorption for subsequent alkanes being loaded. According to our studies, Ni2(dhtp) has a very promising potential for adsorption and storage of alkanes. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  4. Interstaple Dithiol Cross-Linking in Au(25)(SR)(18) Nanomolecules: A Combined Mass Spectrometric and Computational Study

    SciTech Connect (OSTI)

    Jiang, Deen; Dass, Amala; Tschumper, Gregory; Mattern, Daniell; Van Dornshuld, Eric; Kota, Rajesh; Jupally, Vijay

    2011-01-01

    A systematic study of cross-linking chemistry of the Au{sub 25}(SR){sub 18} nanomolecule by dithiols of varying chain length, HS-(CH2)n-SH where n = 2, 3, 4, 5, and 6, is presented here. Monothiolated Au{sub 25} has six [RSAuSRAuSR] staple motifs on its surface, and MALDI mass spectrometry data of the ligand exchanged clusters show that propane (C3) and butane (C4) dithiols have ideal chain lengths for interstaple cross-linking and that up to six C3 or C4 dithiols can be facilely exchanged onto the cluster surface. Propanedithiol predominately exchanges with two monothiols at a time, making cross-linking bridges, while butanedithiol can exchange with either one or two monothiols at a time. The extent of cross-linking can be controlled by the Au{sub 25}(SR){sub 18} to dithiol ratio, the reaction time of ligand exchange, or the addition of a hydrophobic tail to the dithiol. MALDI MS suggests that during ethane (C2) dithiol exchange, two ethanedithiols become connected by a disulfide bond; this result is supported by density functional theory (DFT) prediction of the optimal chain length for the intrastaple coupling. Both optical absorption spectroscopy and DFT computations show that the electronic structure of the Au{sub 25} nanomolecule retains its main features after exchange of up to eight monothiol ligands.

  5. AN ESTIMATE OF THE CHEMICAL COMPOSITION OF TITAN's LAKES

    SciTech Connect (OSTI)

    Cordier, Daniel; Mousis, Olivier; Lunine, Jonathan I.; Lavvas, Panayotis; Vuitton, Veronique

    2009-12-20

    Hundreds of radar-dark patches interpreted as lakes have been discovered in the north and south polar regions of Titan. We have estimated the composition of these lakes by using the direct abundance measurements from the Gas Chromatograph Mass Spectrometer aboard the Huygens probe and recent photochemical models based on the vertical temperature profile derived by the Huygens Atmospheric Structure Instrument. Thermodynamic equilibrium is assumed between the atmosphere and the lakes, which are also considered nonideal solutions. We find that the main constituents of the lakes are ethane (C{sub 2}H{sub 6}) (approx76%-79%), propane (C{sub 3}H{sub 8}) (approx7%-8%), methane (CH{sub 4}) (approx5%-10%), hydrogen cyanide (HCN) (approx2%-3%), butene (C{sub 4}H{sub 8}) (approx1%), butane (C{sub 4}H{sub 10}) (approx1%), and acetylene (C{sub 2}H{sub 2}) (approx1%). The calculated composition of lakes is then substantially different from what has been expected from models elaborated prior to the exploration of Titan by the Cassini-Huygens spacecraft.

  6. Inter-staple Dithiol Crosslinking in Au25(SR)18 Nanomolecules: A Combined Mass Spectrometric and Computational Study

    SciTech Connect (OSTI)

    Dass, Amala; Jiang, Deen; Jupally, Vijay; Kota, Rajesh; Mattern, Daniell; Tschumper, Gregory; Van Dornshuld, Eric

    2011-01-01

    A systematic study of cross-linking chemistry of the Au{sub 25}(SR){sub 18} nanomolecule by dithiols of varying chain length, HS-(CH{sub 2}){sub n}-SH where n = 2, 3, 4, 5, and 6, is presented here. Monothiolated Au{sub 25} has six [RSAuSRAuSR] staple motifs on its surface, and MALDI mass spectrometry data of the ligand exchanged clusters show that propane (C3) and butane (C4) dithiols have ideal chain lengths for interstaple cross-linking and that up to six C3 or C4 dithiols can be facilely exchanged onto the cluster surface. Propanedithiol predominately exchanges with two monothiols at a time, making cross-linking bridges, while butanedithiol can exchange with either one or two monothiols at a time. The extent of cross-linking can be controlled by the Au{sub 25}(SR){sub 18} to dithiol ratio, the reaction time of ligand exchange, or the addition of a hydrophobic tail to the dithiol. MALDI MS suggests that during ethane (C2) dithiol exchange, two ethanedithiols become connected by a disulfide bond; this result is supported by density functional theory (DFT) prediction of the optimal chain length for the intrastaple coupling. Both optical absorption spectroscopy and DFT computations show that the electronic structure of the Au{sub 25} nanomolecule retains its main features after exchange of up to eight monothiol ligands.

  7. Molecular mechanism of hydrocarbons binding to the metal–organic framework

    SciTech Connect (OSTI)

    Sun, Xiuquan; Wick, Collin D.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2011-01-07

    The adsorption and diffusivity of methane, ethane, n-butane, n-hexane and cyclohexane in a metal organic framework (MOF) with the organic linker tetrakis[4-(carboxyphenyl)oxamethyl]methane, the metal salt, Zn2+, and organic pillar, 4,4’-bipyridin was studied using molecular dynamics simulations. For the n-alkanes, the longer the chain, the lower the free energy of adsorption, which was attributed to a greater number of contacts between the alkane and MOF. Cyclohexane had a slightly higher adsorption free energy than n-hexane. Furthermore, for cyclo- and n-hexane, there were no significant differences in adsorption free energies between systems with low to moderate loadings. The diffusivity of the n-alkanes was found to strongly depend on chain length with slower diffusion for longer chains. Cyclohexane had no effective diffusion, suggesting that the selectivity the MOF has towards n-hexane over cyclohexane is the result of kinetics instead of energetics. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  8. A comparative experimental and computational study of methanol, ethanol, and n-butanol flames

    SciTech Connect (OSTI)

    Veloo, Peter S.; Wang, Yang L.; Egolfopoulos, Fokion N.; Westbrook, Charles K.

    2010-10-15

    Laminar flame speeds and extinction strain rates of premixed methanol, ethanol, and n-butanol flames were determined experimentally in the counterflow configuration at atmospheric pressure and elevated unburned mixture temperatures. Additional measurements were conducted also to determine the laminar flame speeds of their n-alkane/air counterparts, namely methane, ethane, and n-butane in order to compare the effect of alkane and alcohol molecular structures on high-temperature flame kinetics. For both propagation and extinction experiments the flow velocities were determined using the digital particle image velocimetry method. Laminar flame speeds were derived through a non-linear extrapolation approach based on direct numerical simulations of the experiments. Two recently developed detailed kinetics models of n-butanol oxidation were used to simulate the experiments. The experimental results revealed that laminar flame speeds of ethanol/air and n-butanol/air flames are similar to those of their n-alkane/air counterparts, and that methane/air flames have consistently lower laminar flame speeds than methanol/air flames. The laminar flame speeds of methanol/air flames are considerably higher compared to both ethanol/air and n-butanol/air flames under fuel-rich conditions. Numerical simulations of n-butanol/air freely propagating flames, revealed discrepancies between the two kinetic models regarding the consumption pathways of n-butanol and its intermediates. (author)

  9. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    SciTech Connect (OSTI)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  10. Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

    SciTech Connect (OSTI)

    Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

    2012-03-14

    Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X? = Cl?, Br?) generates ethyl halides via halogen atom abstraction from FeXn3?n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ?0.05 M X?. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 ± 0.5) × 106 M?1 s?1) and with FeBr2+ (k = (3.0 ± 0.5) × 107 M?1 s?1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

  11. Methane-derived hydrocarbons produced under upper-mantle conditions

    SciTech Connect (OSTI)

    Kolesnikov, Anton; Kutcherov, Vladimir G.; Goncharov, Alexander F.

    2009-08-13

    There is widespread evidence that petroleum originates from biological processes. Whether hydrocarbons can also be produced from abiogenic precursor molecules under the high-pressure, high-temperature conditions characteristic of the upper mantle remains an open question. It has been proposed that hydrocarbons generated in the upper mantle could be transported through deep faults to shallower regions in the Earth's crust, and contribute to petroleum reserves. Here we use in situ Raman spectroscopy in laser-heated diamond anvil cells to monitor the chemical reactivity of methane and ethane under upper-mantle conditions. We show that when methane is exposed to pressures higher than 2 GPa, and to temperatures in the range of 1,000-1,500 K, it partially reacts to form saturated hydrocarbons containing 2-4 carbons (ethane, propane and butane) and molecular hydrogen and graphite. Conversely, exposure of ethane to similar conditions results in the production of methane, suggesting that the synthesis of saturated hydrocarbons is reversible. Our results support the suggestion that hydrocarbons heavier than methane can be produced by abiogenic processes in the upper mantle.

  12. End use energy consumption data base: transportation sector

    SciTech Connect (OSTI)

    Hooker, J.N.; Rose, A.B.; Greene, D.L.

    1980-02-01

    The transportation fuel and energy use estimates developed a Oak Ridge National Laboratory (ORNL) for the End Use Energy Consumption Data Base are documented. The total data base contains estimates of energy use in the United States broken down into many categories within all sectors of the economy: agriculture, mining, construction, manufacturing, commerce, the household, electric utilities, and transportation. The transportation data provided by ORNL generally cover each of the 10 years from 1967 through 1976 (occasionally 1977 and 1978), with omissions in some models. The estimtes are broken down by mode of transport, fuel, region and State, sector of the economy providing transportation, and by the use to which it is put, and, in the case of automobile and bus travel, by the income of the traveler. Fuel types include natural gas, motor and aviation gasoline, residual and diesel oil, liuqefied propane, liquefied butane, and naphtha- and kerosene-type jet engine fuels. Electricity use is also estimated. The mode, fuel, sector, and use categories themselves subsume one, two, or three levels of subcategories, resulting in a very detailed categorization and definitive accounting.

  13. Portable thermo-photovoltaic power source

    DOE Patents [OSTI]

    Zuppero, Anthony C. (Idaho Falls, ID); Krawetz, Barton (Idaho Falls, ID); Barklund, C. Rodger (Idaho Falls, ID); Seifert, Gary D. (Idaho Falls, ID)

    1997-01-14

    A miniature thermo-photovoltaic (TPV) device for generation of electrical power for use in portable electronic devices. A TPV power source is constructed to provide a heat source chemical reactor capable of using various fuels, such as liquid hydrocarbons, including but not limited to propane, LPG, butane, alcohols, oils and diesel fuels to generate a source of photons. A reflector dish guides misdirected photon energy from the photon source toward a photovoltaic array. A thin transparent protector sheet is disposed between the photon source and the array to reflect back thermal energy that cannot be converted to electricity, and protect the array from thermal damage. A microlens disposed between the protector sheet and the array further focuses the tailored band of photon energy from the photon source onto an array of photovoltaic cells, whereby the photon energy is converted to electrical power. A heat recuperator removes thermal energy from reactor chamber exhaust gases, preferably using mini- or micro-bellows to force air and fuel past the exhaust gases, and uses the energy to preheat the fuel and oxidant before it reaches the reactor, increasing system efficiency. Mini- or micro-bellows force ambient air through the system both to supply oxidant and to provide cooling. Finally, an insulator, which is preferably a super insulator, is disposed around the TPV power source to reduce fuel consumption, and to keep the TPV power source cool to the touch so it can be used in hand-held devices.

  14. Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C–H bond activation

    SciTech Connect (OSTI)

    Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R.

    2013-11-21

    Both ceria (CeO{sub 2}) and alumina (Al{sub 2}O{sub 3}) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), Ce{sub x}Al{sub y}O{sub z}, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C{sub 4}H{sub 10}) is studied. The very active species CeAlO{sub 4}{sup •} can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other Ce{sub x}Al{sub y}O{sub z} NBONCs do not show reactivities toward CO and C{sub 4}H{sub 10}. The structures, as well as the reactivities, of Ce{sub x}Al{sub y}O{sub z} NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO{sub 4}{sup •} NBONC possesses a kite-shaped structure with an O{sub t}CeO{sub b}O{sub b}AlO{sub t} configuration (O{sub t}, terminal oxygen; O{sub b}, bridging oxygen). An unpaired electron is localized on the O{sub t} atom of the AlO{sub t} moiety rather than the CeO{sub t} moiety: this O{sub t} centered radical moiety plays a very important role for the reactivity of the CeAlO{sub 4}{sup •} NBONC. The reactivities of Ce{sub 2}O{sub 4}, CeAlO{sub 4}{sup •}, and Al{sub 2}O{sub 4} toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO{sub 4}{sup •} with C{sub 4}H{sub 10} to form the CeAlO{sub 4}H•C{sub 4}H{sub 9}{sup •} encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of Al{sub x}O{sub y}/M{sub m}O{sub n} or M{sub m}O{sub n}/Al{sub x}O{sub y} materials are proposed consistent with the presented experimental and theoretical results.

  15. Computational Capabilities for Predictions of Interactions at the Grain Boundary of Refractory Alloys

    SciTech Connect (OSTI)

    Sengupta, Debasis; Kwak, Shaun; Vasenkov, Alex; Shin, Yun Kyung; Duin, Adri van

    2014-09-30

    New high performance refractory alloys are critically required for improving efficiency and decreasing CO2 emissions of fossil energy systems. The development of these materials remains slow because it is driven by a trial-and-error experimental approach and lacks a rational design approach. Atomistic Molecular Dynamic (MD) design has the potential to accelerate this development through the prediction of mechanical properties and corrosion resistance of new materials. The success of MD simulations depends critically on the fidelity of interatomic potentials. This project, in collaboration with Penn State, has focused on developing and validating high quality quantum mechanics based reactive potentials, ReaxFF, for Ni-Fe-Al-Cr-O-S system. A larger number of accurate density functional theory (DFT) calculations were performed to generate data for parameterizing the ReaxFF potentials. These potentials were then used in molecular dynamics (MD) and molecular dynamics-Monte Carlo (MD-MC) for much larger system to study for which DFT calculation would be prohibitively expensive, and to understand a number of chemical phenomena Ni-Fe-Al-Cr-O-S based alloy systems . These include catalytic oxidation of butane on clean Cr2O3 and pyrite/Cr2O3, interfacial reaction between Cr2O3 (refractory material) and Al2O3 (slag), cohesive strength of at the grain boundary of S-enriched Cr compared to bulk Cr and Ssegregation study in Al, Al2O3, Cr and Cr2O3 with a grain structure. The developed quantum based ReaxFF potential are available from the authors upon request. During this project, a number of papers were published in peer-reviewed journals. In addition, several conference presentations were made.

  16. Fundamental and semi-global kinetic mechanisms for hydrocarbon combustion. Final report, March 1977-October 1980

    SciTech Connect (OSTI)

    Dryer, F L; Glassman, I; Brezinsky, K

    1981-03-01

    Over the past three and one half years, substantial research efforts of the Princeton Fuels Research Group have been directed towards the development of simplified mechanisms which would accurately describe the oxidation of hydrocarbons fuels. The objectives of this combustion research included the study of semi-empirical modeling (that is an overall description) of the chemical kinetic mechanisms of simple hydrocarbon fuels. Such fuels include the alkanes: ethane, propane, butane, hexane and octane as well as the critically important alkenes: ethene, propene and butene. As an extension to this work, the study of the detailed radical species characteristics of combustion systems was initiated as another major aspect of the program, with emphasis on the role of the OH and HO/sub 2/ radicals. Finally, the studies of important alternative fuel problems linked the program to longer range approaches to the energy supply question. Studies of alternative fuels composed the major elements of this area of the program. The efforts on methanol research were completed, and while the aromatics aspects of the DOE work have been a direct extension of efforts supported by the Air Force Office of Scientific Research, they represented a significant part of the overall research effort. The emphasis in the proposed program is to provide further fundamental understanding of the oxidation of hydrocarbon fuels which will be useful in guiding engineering approaches. Although the scope of program ranges from the fundamentals of chemical kinetics to that of alternative fuel combustion, the objective in mind is to provide insight and guidance to the understanding of practical combustion environments. The key to our approach has been our understanding of the fundamental combustion chemistry and its relation to the important practical combustion problems which exist in implementing energy efficient, alternate fuels technologies.

  17. Toxicity Data to Determine Refrigerant Concentration Limits

    SciTech Connect (OSTI)

    Calm, James M.

    2000-09-30

    This report reviews toxicity data, identifies sources for them, and presents resulting exposure limits for refrigerants for consideration by qualified parties in developing safety guides, standards, codes, and regulations. It outlines a method to calculate an acute toxicity exposure limit (ATEL) and from it a recommended refrigerant concentration limit (RCL) for emergency exposures. The report focuses on acute toxicity with particular attention to lethality, cardiac sensitization, anesthetic and central nervous system effects, and other escape-impairing effects. It addresses R-11, R-12, R-22, R-23, R-113, R-114, R-116, R-123, R-124, R-125, R-134, R-134a, R-E134, R-141b, R-142b, R-143a, R-152a, R-218, R-227ea, R-236fa, R-245ca, R-245fa, R-290, R-500, R-502, R-600a, R-717, and R-744. It summarizes additional data for R-14, R-115, R-170 (ethane), R-C318, R-600 (n-butane), and R-1270 (propylene) to enable calculation of limits for blends incorporating them. The report summarizes the data a nd related safety information, including classifications and flammability data. It also presents a series of tables with proposed ATEL and RCL concentrations-in dimensionless form and the latter also in both metric (SI) and inch-pound (IP) units of measure-for both the cited refrigerants and 66 zerotropic and azeotropic blends. They include common refrigerants, such as R-404A, R-407C, R-410A, and R-507A, as well as others in commercial or developmental status. Appendices provide profiles for the cited single-compound refrigerants and for R-500 and R-502 as well as narrative toxicity summaries for common refrigerants. The report includes an extensive set of references.

  18. Investigating the validity of the Knudsen prescription for diffusivities in a mesoporous covalent organic framework

    SciTech Connect (OSTI)

    Krishna, Rajamani; van Baten, Jasper M.

    2011-04-27

    Molecular dynamics (MD) simulations were performed to determine the self-diffusivity (Di,self) and the Maxwell–Stefan diffusivity (ÐI) of hydrogen, argon, carbon dioxide, methane, ethane, propane, n-butane, n-pentane, and n-hexane in BTP-COF, which is a covalent organic framework (COF) that has one-dimensional 3.4-nm-sized channels. The MD simulations show that the zero-loading diffusivity (ÐI(0)) is consistently lower, by up to a factor of 10, than the Knudsen diffusivity (Di,Kn) values. The ratio ÐI(0)/Di,Kn is found to correlate with the isosteric heat of adsorption, which, in turn, is a reflection of the binding energy for adsorption on the pore walls: the stronger the binding energy, the lower the ratio ÐI(0)/Di,Kn. The diffusion selectivity, which is defined by the ratio D1,self/D2,self for binary mixtures, was determined to be significantly different from the Knudsen selectivity (M2/M1)1/2, where MI is the molar mass of species i. For mixtures in which component 2 is more strongly adsorbed than component 1, the expression (D1,self/D2,self)/(M2/M1)1/2 has values in the range of 1–10; the departures from the Knudsen selectivity increased with increasing differences in adsorption strengths of the constituent species. The results of this study have implications in the modeling of diffusion within mesoporous structures, such as MCM-41 and SBA-15.

  19. Soil Iodine Determination in Deccan Syneclise, India: Implications for Near Surface Geochemical Hydrocarbon Prospecting

    SciTech Connect (OSTI)

    Mani, Devleena; Kumar, T. Satish; Rasheed, M. A.; Patil, D. J.; Dayal, A. M.; Rao, T. Gnaneshwar; Balaram, V.

    2011-03-15

    The association of iodine with organic matter in sedimentary basins is well documented. High iodine concentration in soils overlying oil and gas fields and areas with hydrocarbon microseepage has been observed and used as a geochemical exploratory tool for hydrocarbons in a few studies. In this study, we measure iodine concentration in soil samples collected from parts of Deccan Syneclise in the west central India to investigate its potential application as a geochemical indicator for hydrocarbons. The Deccan Syneclise consists of rifted depositional sites with Gondwana-Mesozoic sediments up to 3.5 km concealed under the Deccan Traps and is considered prospective for hydrocarbons. The concentration of iodine in soil samples is determined using ICP-MS and the values range between 1.1 and 19.3 ppm. High iodine values are characteristic of the northern part of the sampled region. The total organic carbon (TOC) content of the soil samples range between 0.1 and 1.3%. The TOC correlates poorly with the soil iodine (r{sup 2} < 1), indicating a lack of association of iodine with the surficial organic matter and the possibility of interaction between the seeping hydrocarbons and soil iodine. Further, the distribution pattern of iodine compares well with two surface geochemical indicators: the adsorbed light gaseous hydrocarbons (methane through butane) and the propane-oxidizing bacterial populations in the soil. The integration of geochemical observations show the occurrence of elevated values in the northern part of the study area, which is also coincident with the presence of exposed dyke swarms that probably serve as conduits for hydrocarbon microseepage. The corroboration of iodine with existing geological, geophysical, and geochemical data suggests its efficacy as one of the potential tool in surface geochemical exploration of hydrocarbons. Our study supports Deccan Syneclise to be promising in terms of its hydrocarbon prospects.

  20. Investigating the Synthesis of Ligated Metal Clusters in Solution Using a Flow Reactor and Electrospray Ionization Mass Spectrometry

    SciTech Connect (OSTI)

    Olivares, Astrid M.; Laskin, Julia; Johnson, Grant E.

    2014-09-18

    The scalable synthesis of subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth and post-reduction etching are still not well understood. Herein, we demonstrate a temperature-controlled flow reactor for studying cluster formation in solution at well-defined conditions. Employing this technique methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with an adjustable length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates and products synthesized in real time was characterized using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged metal-ligand complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged metal-ligand complexes while hindering the growth of triply charged clusters. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of reduction synthesis in solution.

  1. Modeling of 1,3-hexadiene, 2,4-hexadiene and 1,4-hexadiene-doped methane flames: Flame modeling, benzene and styrene formation

    SciTech Connect (OSTI)

    Sharma, Sandeep; Harper, Michael R.; Green, William H.

    2010-07-15

    In this work, we have developed a detailed chemical kinetic model and reacting flow simulation for the hexadiene-doped 2-d methane diffusion flames studied experimentally by McEnally and Pfefferle. The GRI-Mech 2.11 methane oxidation and Lawrence Livermore butane oxidation mechanisms were used as the base mechanism to which hexadiene chemistry generated by Reaction Mechanism Generator (RMG) was added. Some important chemically activated pathways leading to aromatic species formation, including the reactions on C{sub 5}H{sub 7}, C{sub 6}H{sub 10}, C{sub 6}H{sub 9}, C{sub 6}H{sub 7}, C{sub 8}H{sub 8} and C{sub 8}H{sub 9} potential energy surfaces, are examined in great detail using quantum chemistry (CBS-QB3) and master equation analysis as implemented in Variflex. An efficient program to solve the doped methane diffusion flame was developed. The solver uses the method of lines to solve the species mass balance equation arising in the diffusion flame. It assumes that the temperature and velocity profiles of the doped flame are the same as those of the undoped flame. The mole fractions of various species as predicted by our model are compared to the experimentally measured mole fractions. The agreement between theory and experiments is quite good for most molecules. The added hexadiene dopants to the flame decompose to produce significant amount of cyclopentadienyl radical, which combines with methyl radical to produce benzene. We also show that styrene is formed primarily by recombination of cyclopentadienyl and propargyl radicals, a pathway which to our knowledge, has not been included in prior flame simulations. (author)

  2. New Design Methods And Algorithms For High Energy-Efficient And Low-cost Distillation Processes

    SciTech Connect (OSTI)

    Agrawal, Rakesh

    2013-11-21

    This project sought and successfully answered two big challenges facing the creation of low-energy, cost-effective, zeotropic multi-component distillation processes: first, identification of an efficient search space that includes all the useful distillation configurations and no undesired configurations; second, development of an algorithm to search the space efficiently and generate an array of low-energy options for industrial multi-component mixtures. Such mixtures are found in large-scale chemical and petroleum plants. Commercialization of our results was addressed by building a user interface allowing practical application of our methods for industrial problems by anyone with basic knowledge of distillation for a given problem. We also provided our algorithm to a major U.S. Chemical Company for use by the practitioners. The successful execution of this program has provided methods and algorithms at the disposal of process engineers to readily generate low-energy solutions for a large class of multicomponent distillation problems in a typical chemical and petrochemical plant. In a petrochemical complex, the distillation trains within crude oil processing, hydrotreating units containing alkylation, isomerization, reformer, LPG (liquefied petroleum gas) and NGL (natural gas liquids) processing units can benefit from our results. Effluents from naphtha crackers and ethane-propane crackers typically contain mixtures of methane, ethylene, ethane, propylene, propane, butane and heavier hydrocarbons. We have shown that our systematic search method with a more complete search space, along with the optimization algorithm, has a potential to yield low-energy distillation configurations for all such applications with energy savings up to 50%.

  3. Cu{sup II} coordination polymers based on 5-methoxyisophthalate and flexible N-donor ligands: Structures and magnetic properties

    SciTech Connect (OSTI)

    Chang, Xin-Hong; Qin, Jian-Hua; Ma, Lu-Fang; Wang, Li-Ya

    2014-04-01

    Three Cu{sup II} coordination polymers, ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib)]){sub n} (1), ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib){sub 2}]){sub n} (2) and ([Cu(CH{sub 3}O-ip)(bbip)]?2H{sub 2}O){sub n} (3) (CH{sub 3}O-H{sub 2}ip is 5-methoxyisophthalic acid, bmib is 1,4-bis(2-methylimidazol-1-yl)butane and bbip is 1,3-bis(1H-benzimidazolyl)propane), have been synthesized by hydrothermal methods. Complexes 1–3 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 shows a 3D six-connected self-penetrating network based on paddlewheel secondary building units. Complex 2 has a 3-fold interpenetrating 3D diamond framework. Complex 3 possesses a 1D tube-like chain. Thermo-gravimetric and magnetic properties of 1–3 were also investigated. - Graphical abstract: Structures and magnetic properties of copper(II) coordination polymers constructed from 5-methoxyisophthalate linker and two flexible N-donor ancillary ligands. Three copper(II) coordination polymers with 5-methoxyisophthalate and two related flexible N-donor ancillary ligands have been synthesized and structurally characterized. Moreover, thermal behaviors and magnetic properties of these complexes have also been investigated. - Highlights: • Three Cu(II) coordination polymers were synthesized. • The conformations of N-donor ligands and pH value have an effect on the final structures. • The magnetic properties of 1–3 have been investigated.

  4. Kinetic inhibition of natural gas hydrates in offshore drilling, production, and processing operations. Annual report, January 1--December 31, 1992

    SciTech Connect (OSTI)

    1992-12-31

    Natural gas hydrates are solid crystalline compounds which form when molecules smaller than n-butane contact molecules of water at elevated pressures and reduced temperatures, both above and below the ice point. Because these crystalline compounds plug flow channels, they are undesirable. In this project the authors proposed an alternate approach of controlling hydrate formation by preventing hydrate growth into a sizeable mass which could block a flow channel. The authors call this new technique kinetic inhibition, because while it allows the system to exist in the hydrate domain, it prevents the kinetic agglomeration of small hydrate crystals to the point of pluggage of a flow channel. In order to investigate the kinetic means of inhibiting hydrate formation, they held two consortium meetings, on June 1, 1990 and on August 31, 1990. At subsequent meetings, the authors determined the following four stages of the project, necessary to reach the goal of determining a new hydrate field inhibitor: (1) a rapid screening method was to be determined for testing the hydrate kinetic formation period of many surfactants and polymer candidates (both individually and combined), the present report presents the success of two screening apparatuses: a multi-reactor apparatus which is capable of rapid, high volume screening, and the backup screening method--a viscometer for testing with gas at high pressure; (2) the construction of two high, constant pressure cells were to experimentally confirm the success of the chemicals in the rapid screening apparatus; (3) in the third phase of the work, Exxon volunteered to evaluate the performance of the best chemicals from the previous two stages in their 4 inch I.D. Multiphase flow loop in Houston; (4) in the final phase of the work, the intention was to take the successful kinetic inhibition chemicals from the previous three stages and then test them in the field in gathering lines and wells from member companies.

  5. Conversion of LPG hydrocarbons into distillate fuels using an integral LPG dehydrogenation-MOGD process

    SciTech Connect (OSTI)

    Owen, H.; Zahner, J.C.

    1987-06-23

    This patent describes a process for converting lower paraffinic hydrocarbon feedstock comprising propane and/or butane into heavier hydrocarbons comprising gasoline and distillate, comprising the steps of: feeding the paraffinic feedstock to a dehydrogenation zone under conversion conditions for dehydrogenating at least a portion of the feedstock; recovering a first dehydrogenation gaseous effluent stream comprising propene and/or butene; contacting the first gaseous effluent steam with a liquid lean oil sorbent stream comprising C/sub 5//sup +/ hydrocarbons under sorption conditions to produce a C/sub 3//sup +/ rich liquid absorber stream and a light gas stream; sequentially pressurizing, heating and passing the C/sub 3//sup +/ rich liquid absorber stream to an oligomerization reactor zone at elevated temperature and pressure; contacting the C/sub 3//sup +/ rich stream with oligomerization catalyst in the oligomerization reactor zone for conversion of at least a portion of lower olefins to heavier hydrocarbons under oligomerization reaction conditions to provide a second reactor effluent stream comprising gasoline and distillate boiling range hydrocarbons; flash separating the second reactor effluent stream into a separator vapor stream comprising a major portion of the hydrocarbons which later form the lean oil stream, and a major portion of the C/sub 4//sup -/ hydrocarbons and a separator liquid stream comprising the gasoline and distillate boiling range materials produced in the oligomerization reactor zone; fractionating the separator liquid stream in a first product debutanizer tower into a first debutanizer overhead vapor stream comprising C/sub 4//sup -/ hydrocarbons and a product debutanizer liquid bottoms stream comprising C/sub 5//sup +/ gasoline and distillate boiling range hydrocarbons.

  6. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

    SciTech Connect (OSTI)

    Adams, MM; Hoarfrost, AL; Bose, A; Joye, SB; Girguis, PR

    2013-05-14

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C-2), propane (C-3), and butane (C-4) in anoxic sediments in contrast to methane (C-1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C-1-C-4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C-1-C-4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75 degrees C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C-1-C-4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C-2-C-4 alkanes. Maximum C-1-C-4 alkane oxidation rates occurred at 55 degrees C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C-3 was oxidized at the highest rate over time, then C-4, C-2, and C-1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C-2-C(4)alkanes with AOM for available oxidants and the influence on the fate of C-1 derived from these hydrothermal systems.

  7. On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

    SciTech Connect (OSTI)

    Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

    2014-07-20

    The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) and n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

  8. Hydrogen production from the steam reforming of Dinethyl Ether and Methanol

    SciTech Connect (OSTI)

    Semelsberger, T. A.; Borup, R. L.

    2004-01-01

    This study investigates dimethyl ether (DME) steam reforming for the generation of hydrogen rich fuel cell feeds for fuel cell applications. Methanol has long been considered as a fuel for the generation of hydrogen rich fuel cell feeds due to its high energy density, low reforming temperature, and zero impurity content. However, it has not been accepted as the fuel of choice due its current limited availability, toxicity and corrosiveness. While methanol steam reforming for the generation of hydrogen rich fuel cell feeds has been extensively studied, the steam reforming of DME, CH{sub 3}OCH{sub 3} + 3H{sub 2}O = 2CO{sub 2} + 6H{sub 2}, has had limited research effort. DME is the simplest ether (CH{sub 3}OCH{sub 3}) and is a gas at ambient conditions. DME has physical properties similar to those of LPG fuels (i.e. propane and butane), resulting in similar storage and handling considerations. DME is currently used as an aerosol propellant and has been considercd as a diesel substitute due to the reduced NOx, SOx and particulate emissions. DME is also being considered as a substitute for LPG fuels, which is used extensively in Asia as a fuel for heating and cooking, and naptha, which is used for power generation. The potential advantages of both methanol and DME include low reforming temperature, decreased fuel proccssor startup energy, environmentally benign, visible flame, high heating value, and ease of storage and transportation. In addition, DME has the added advantages of low toxicity and being non-corrosive. Consequently, DME may be an ideal candidate for the generation of hydrogen rich fuel cell feeds for both automotive and portable power applications. The steam reforming of DME has been demonstrated to occur through a pair of reactions in series, where the first reaction is DME hydration followed by MeOH steam reforming to produce a hydrogen rich stream.

  9. Appearance, temperature, and NO{sub x} emission of two inverse diffusion flames with different port design

    SciTech Connect (OSTI)

    Sze, L.K.; Cheung, C.S.; Leung, C.W.

    2006-01-01

    Experiments were carried out to investigate the appearance, temperature distribution, and NO{sub x} emission index of two inverse diffusion flames, one with circumferentially arranged ports (CAPs) and the other with co-axial (CoA) jets, both burning LPG with 70% butane and 30% propane. Flame appearances were investigated first with a fixed fueling rate at different airflow rates equivalent to air jet Reynolds numbers (Re) of 1000 to 4500; and then at a fixed airflow rate with different fueling rates equivalent to overall equivalence ratios (F) of 1.0 to 2.0. The CAP flame is found to consist of two zones: a lower entrainment zone and an upper mixing and combustion zone. The CoA flame in most cases is similar to a diffusion flame. The two-zone structure can be observed only at Re larger than 2500. The temperature distributions of the flames are similar at overall equivalence ratios of 1.0 and 1.2 for Re=2500, except that the corresponding CoA flame is longer. The flame temperature is higher in the CAP flame than the CoA flame at higher overall equivalence ratios. A measurement of centerline oxygen concentrations shows that the oxygen concentration reaches a minimum value at a flame height of 50 mm in the CAP flame but decreases more gradually in the CoA flame. It can be concluded that there is more intense air-fuel mixing in a CAP flame than the CoA flame. Investigation of the emission index of NO{sub x} (EINO{sub x}) for both flames at Re=2500 and overall equivalence ratios of 1.0 to 6.0 reveals that the EINO{sub x} curve of each flame is bell-shaped, with a maximum value of 3.2 g/kg at F=1.2 for the CAP flame and 3 g/kg at F=2.2 for the CoA flame.

  10. Quantum cascade laser investigations of CH{sub 4} and C{sub 2}H{sub 2} interconversion in hydrocarbon/H{sub 2} gas mixtures during microwave plasma enhanced chemical vapor deposition of diamond

    SciTech Connect (OSTI)

    Ma Jie; Cheesman, Andrew; Ashfold, Michael N. R.; Hay, Kenneth G.; Wright, Stephen; Langford, Nigel; Duxbury, Geoffrey; Mankelevich, Yuri A.

    2009-08-01

    CH{sub 4} and C{sub 2}H{sub 2} molecules (and their interconversion) in hydrocarbon/rare gas/H{sub 2} gas mixtures in a microwave reactor used for plasma enhanced diamond chemical vapor deposition (CVD) have been investigated by line-of-sight infrared absorption spectroscopy in the wavenumber range of 1276.5-1273.1 cm{sup -1} using a quantum cascade laser spectrometer. Parameters explored include process conditions [pressure, input power, source hydrocarbon, rare gas (Ar or Ne), input gas mixing ratio], height (z) above the substrate, and time (t) after addition of hydrocarbon to a pre-existing Ar/H{sub 2} plasma. The line integrated absorptions so obtained have been converted to species number densities by reference to the companion two-dimensional (r,z) modeling of the CVD reactor described in Mankelevich et al. [J. Appl. Phys. 104, 113304 (2008)]. The gas temperature distribution within the reactor ensures that the measured absorptions are dominated by CH{sub 4} and C{sub 2}H{sub 2} molecules in the cool periphery of the reactor. Nonetheless, the measurements prove to be of enormous value in testing, tensioning, and confirming the model predictions. Under standard process conditions, the study confirms that all hydrocarbon source gases investigated (methane, acetylene, ethane, propyne, propane, and butane) are converted into a mixture dominated by CH{sub 4} and C{sub 2}H{sub 2}. The interconversion between these two species is highly dependent on the local gas temperature and the H atom number density, and thus on position within the reactor. CH{sub 4}->C{sub 2}H{sub 2} conversion occurs most efficiently in an annular shell around the central plasma (characterized by 1400CH{sub 4} is favored in the more distant regions where T{sub gas}<1400 K. Analysis of the multistep interconversion mechanism reveals substantial net consumption of H atoms accompanying the CH{sub 4}->C{sub 2}H{sub 2} conversion, whereas the reverse C{sub 2}H{sub 2}->CH{sub 4} process only requires H atoms to drive the reactions; H atoms are not consumed by the overall conversion.

  11. Three 3D hybrid networks based on octamolybdates and different Cu{sup I}/Cu{sup II}-bis(triazole) motifs

    SciTech Connect (OSTI)

    Zhang, Chun-Jing; Pang, Hai-Jun; Tang, Qun; Wang, Hui-Yuan; Chen, Ya-Guang

    2010-12-15

    Three 3D compounds based on octamolybdate clusters and various Cu{sup I}/Cu{sup II}-bis(triazole) motifs, [Cu{sup I}{sub 2}btb][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (1), [Cu{sup I}{sub 2}btpe][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (2), and [Cu{sup II}(btpe){sub 2}][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (3) [btb=1,4-bis(1,2,4-triazol-1-yl)butane, btpe=1,5-bis(1,2,4-triazol-1-yl)pentane], were isolated via tuning flexible ligand spacer length and metal coordination preferences. In 1, the copper(I)-btb motif is a one-dimensional (1D) chain which is further linked by hexadentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters via coordinating to Cu{sup I} cations giving a 3D structure. In 2, the copper(I)-btpe motif exhibits a 'stairs'-like [Cu{sup I}{sub 2}btpe]{sup 2+} sheet, and the tetradentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters interact with two neighboring [Cu{sup I}{sub 2}btpe]{sup 2+} sheets constructing a 3D framework. In 3, the copper(II)-btpe motif possesses a novel (2D{yields}3D) interdigitated structure, which is further connected by the tetradentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters forming a 3D framework. The thermal stability and luminescent properties of 1-3 are investigated in the solid state. -- Graphical abstract: Three 3D compounds based on {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters with different Cu{sup I}/Cu{sup II}-bis(triazole) motifs were synthesized by regularly tuning flexible ligand spacer length and metal coordination preferences. Display Omitted

  12. The magnetic and electronic structure of vanadyl pyrophosphate from density functional theory

    SciTech Connect (OSTI)

    Cheng, Mu-Jeng; Nielsen, Robert J.; Tahir-Kheli, Jamil; Goddard III, William A.

    2011-01-01

    We have studied the magnetic structure of the high symmetry vanadyl pyrophosphate ((VO)?P?O?, VOPO), focusing on the spin exchange couplings, using density functional theory (B3LYP) with the full three-dimensional periodicity. VOPO involves four distinct spin couplings: two larger couplings exist along the chain direction (a-axis), which we predict to be antiferromagnetic, JOPO = ?156.8 K and JO = ?68.6 K, and two weaker couplings appear along the c (between two layers) and b directions (between two chains in the same layer), which we calculate to be ferromagnetic, Jlayer = 19.2 K and Jchain = 2.8 K. Based on the local density of states and the response of spin couplings to varying the cell parameter a, we found that JOPO originates from a super-exchange interaction through the bridging –O–P–O– unit. In contrast, JO results from a direct overlap of 3dx²?y² orbitals on two vanadium atoms in the same V2O8 motif, making it very sensitive to structural fluctuations. Based on the variations in V–O bond length as a function of strain along a, we found that the V–O bonds of V–(OPO)2–V are covalent and rigid, whereas the bonds of V–(O)2–V are fragile and dative. These distinctions suggest that compression along the a-axis would have a dramatic impact on JO, changing the magnetic structure and spin gap of VOPO. This result also suggests that assuming JO to be a constant over the range of 2–300 K whilst fitting couplings to the experimental magnetic susceptibility is an invalid method. Regarding its role as a catalyst, the bonding pattern suggests that O2 can penetrate beyond the top layers of the VOPO surface, converting multiple V atoms from the +4 to +5 oxidation state, which seems crucial to explain the deep oxidation of n-butane to maleic anhydride.

  13. Incorporating a completely renormalized coupled cluster approach into a composite method for thermodynamic properties and reaction paths

    SciTech Connect (OSTI)

    Nedd, Sean; DeYonker, Nathan; Wilson, Angela; Piecuch, Piotr; Gordon, Mark

    2012-04-12

    The correlation consistent composite approach (ccCA), using the S4 complete basis set two-point extrapolation scheme (ccCA-S4), has been modified to incorporate the left-eigenstate completely renormalized coupled cluster method, including singles, doubles, and non-iterative triples (CR-CC(2,3)) as the highest level component. The new ccCA-CC(2,3) method predicts thermodynamic properties with an accuracy that is similar to that of the original ccCA-S4 method. At the same time, the inclusion of the single-reference CR-CC(2,3) approach provides a ccCA scheme that can correctly treat reaction pathways that contain certain classes of multi-reference species such as diradicals, which would normally need to be treated by more computationally demanding multi-reference methods. The new ccCA-CC(2,3) method produces a mean absolute deviation of 1.7 kcal/mol for predicted heats of formation at 298 K, based on calibration with the G2/97 set of 148 molecules, which is comparable to that of 1.0 kcal/mol obtained using the ccCA-S4 method, while significantly improving the performance of the ccCA-S4 approach in calculations involving more demanding radical and diradical species. Both the ccCA-CC(2,3) and ccCA-S4 composite methods are used to characterize the conrotatory and disrotatory isomerization pathways of bicyclo[1.1.0]butane to trans-1,3-butadiene, for which conventional coupled cluster methods, such as the CCSD(T) approach used in the ccCA-S4 model and, in consequence, the ccCA-S4 method itself might fail by incorrectly placing the disrotatory pathway below the conrotatory one. The ccCA-CC(2,3) scheme provides correct pathway ordering while providing an accurate description of the activation and reaction energies characterizing the lowest-energy conrotatory pathway. The ccCA-CC(2,3) method is thus a viable method for the analyses of reaction mechanisms that have significant multi-reference character, and presents a generally less computationally intensive alternative to true multi-reference methods, with computer costs and ease of use that are similar to those that characterize the more established, CCSD(T)-based, ccCA-S4 methodology.

  14. First-principles binary diffusion coefficients for H, H{sub 2}, and four normal alkanes + N{sub 2}

    SciTech Connect (OSTI)

    Jasper, Ahren W. Kamarchik, Eugene; Miller, James A.; Klippenstein, Stephen J.

    2014-09-28

    Collision integrals related to binary (dilute gas) diffusion are calculated classically for six species colliding with N{sub 2}. The most detailed calculations make no assumptions regarding the complexity of the potential energy surface, and the resulting classical collision integrals are in excellent agreement with previous semiclassical results for H + N{sub 2} and H{sub 2} + N{sub 2} and with recent experimental results for C{sub n}H{sub 2n+2} + N{sub 2}, n = 2–4. The detailed classical results are used to test the accuracy of three simplifying assumptions typically made when calculating collision integrals: (1) approximating the intermolecular potential as isotropic, (2) neglecting the internal structure of the colliders (i.e., neglecting inelasticity), and (3) employing unphysical R{sup ?12} repulsive interactions. The effect of anisotropy is found to be negligible for H + N{sub 2} and H{sub 2} + N{sub 2} (in agreement with previous quantum mechanical and semiclassical results for systems involving atomic and diatomic species) but is more significant for larger species at low temperatures. For example, the neglect of anisotropy decreases the diffusion coefficient for butane + N{sub 2} by 15% at 300 K. The neglect of inelasticity, in contrast, introduces only very small errors. Approximating the repulsive wall as an unphysical R{sup ?12} interaction is a significant source of error at all temperatures for the weakly interacting systems H + N{sub 2} and H{sub 2} + N{sub 2}, with errors as large as 40%. For the normal alkanes in N{sub 2}, which feature stronger interactions, the 12/6 Lennard–Jones approximation is found to be accurate, particularly at temperatures above ?700 K where it predicts the full-dimensional result to within 5% (although with somewhat different temperature dependence). Overall, the typical practical approach of assuming isotropic 12/6 Lennard–Jones interactions is confirmed to be suitable for combustion applications except for weakly interacting systems, such as H + N{sub 2}. For these systems, anisotropy and inelasticity can safely be neglected but a more detailed description of the repulsive wall is required for quantitative predictions. A straightforward approach for calculating effective isotropic potentials with realistic repulsive walls is described. An analytic expression for the calculated diffusion coefficient for H + N{sub 2} is presented and is estimated to have a 2-sigma error bar of only 0.7%.

  15. Commercial potential of natural gas storage in lined rock caverns (LRC)

    SciTech Connect (OSTI)

    1999-11-01

    The geologic conditions in many regions of the United States will not permit the development of economical high-deliverability gas storage in salt caverns. These regions include the entire Eastern Seaboard; several northern states, notably Minnesota and Wisconsin; many of the Rocky Mountain States; and most of the Pacific Northwest. In late 1997, the United States Department of Energy (USDOE) Federal Energy Technology Center engaged Sofregaz US to investigate the commercialization potential of natural gas storage in Lined Rock Caverns (LRC). Sofregaz US teamed with Gaz de France and Sydkraft, who had formed a consortium, called LRC, to perform the study for the USDOE. Underground storage of natural gas is generally achieved in depleted oil and gas fields, aquifers, and solution-mined salt caverns. These storage technologies require specific geologic conditions. Unlined rock caverns have been used for decades to store hydrocarbons - mostly liquids such as crude oil, butane, and propane. The maximum operating pressure in unlined rock caverns is limited, since the host rock is never entirely impervious. The LRC technology allows a significant increase in the maximum operating pressure over the unlined storage cavern concept, since the gas in storage is completely contained with an impervious liner. The LRC technology has been under development in Sweden by Sydkraft since 1987. The development process has included extensive technical studies, laboratory testing, field tests, and most recently includes a storage facility being constructed in southern Sweden (Skallen). The LRC development effort has shown that the concept is technically and economically viable. The Skallen storage facility will have a rock cover of 115 meters (375 feet), a storage volume of 40,000 cubic meters (250,000 petroleum barrels), and a maximum operating pressure of 20 MPa (2,900 psi). There is a potential for commercialization of the LRC technology in the United States. Two regions were studied in some detail - the Northeast and the Southeast. The investment cost for an LRC facility in the Northeast is approximately $182 million and $343 million for a 2.6-billion cubic foot (bcf) working gas facility and a 5.2-bcf working gas storage facility, respectively. The relatively high investment cost is a strong function of the cost of labor in the Northeast. The labor union-related rules and requirements in the Northeast result in much higher underground construction costs than might result in Sweden, for example. The LRC technology gas storage service is compared to other alternative technologies. The LRC technology gas storage service was found to be competitive with other alternative technologies for a variety of market scenarios.

  16. Synthesis, structures and properties of a family of four two-dimensional coordination polymers constructed from 5-hydroxyisophthalate

    SciTech Connect (OSTI)

    Zhang, Kou-Lin; Zhang, Jing-Bo; Jing, Chu-Yue; Zhang, Lei; Walton, Richard I.; Zhu, Peizhi; Ng, Seik Weng

    2014-03-15

    Four 2D coordination polymers (CPs) with different structures containing the multifunctional ligand 5-hydroxyisophthalate (5-OH-BDC{sup 2?}), [Zn(5-OH-BDC)(btb)]·2H{sub 2}O (1), [Cd(5-OH-BDC)(btp)(H{sub 2}O)]·3H{sub 2}O (2), [Cd(5-OH-BDC)(bth){sub 2}(H{sub 2}O)]·H{sub 2}O (3) and [Pb(5-OH-BDC)]·H{sub 2}O (4) [btp=1, 3-bis(1,2,4-triazol-1-yl)propane, btb=1,4-bis(1,2,4-triazol-1-yl)butane, bth=1, 6-bis(1,2,4-triazol-1-yl)hexane] were obtained. 1–3 were synthesised hydrothermally, while 4 was obtained under ambient condition. The adjacent (2D?2D) polycatenated 2D layers of 1 polythread in a parallel manner to form an unusual 2D?3D polythreaded framework. 2 contains an undulated 2D (4, 4) network and further extends into an “embracing” double-layer structure through the C–H···? and ?···? stacking interactions. 3 exhibits a non-interpenetrating 2D (4, 4)-network. 4 exhibits a 2D double-layered binodal (4, 4)-net containing oblong nanochannels with symbol (4{sup 3}6{sup 3}){sub 2}. Reversible dehydration–rehydration is observed in 1, 2 and 4, which fall within the category of “recoverable collapsing” and “guest-induced re-formation” frameworks, while 3 exhibits irreversible dehydration–rehydration behaviour. The solid state fluorescent properties of 1–4 have been investigated. -- Graphical abstract: Among four 2D CPs reported, 1 is an unusual 2D?3D polythreaded framework. 4 exhibits 2D double-layered binodal (4, 4)-net containing nanochannels. Reversible dehydration–rehydration is observed in 1, 2 and 4. Highlights: • Four 2D CPs based on 5-hydroxyisophthalate with d{sup 10} and Pb(II) ions were reported. • 1 is an unusual 2D?3D polythreaded framework. • 4 shows a binodal (4, 4)-connected 2D double-layer network with nanochannels. • The materials 1, 2 and 4 show reversible dehydration–rehydration behaviours. • Solid state fluorescent properties were investigated.

  17. Water-Soluble 2-Hydroxyisophthalamides for Sensitization of Lanthanide Luminescence

    SciTech Connect (OSTI)

    Samuel, Amanda P. S.; Moore, Evan G.; Melchior, Marco; Xu, Jide; Raymond, Kenneth N.

    2008-02-20

    A series of octadentate ligands featuring the 2-hydroxyisophthalamide (IAM) antenna chromophore (to sensitize Tb(III) and Eu(III) luminescence) has been prepared and characterized. The length of the alkyl amine scaffold that links the four IAM moieties has been varied in order to investigate the effect of the ligand backbone on the stability and photophysical properties of the Ln(III) complexes. The amine backbones utilized in this study are N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-ethane-1,2-diamine [H(2,2)-], N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-propane-1,3-diamine [H(3,2)-] and N,N,N{prime},N{prime}-tetrakis-(2-aminoethyl)-butane-1,4-diamine [H(4,2)-]. These ligands also incorporate methoxyethylene [MOE] groups on each of the IAM chromophores to increase their water solubility. The aqueous ligand protonation constants and Tb(III) and Eu(III) formation constants were determined from solution thermodynamic studies. The resulting values indicate that at physiological pH, the Eu(III) and Tb(III) complexes of H(2,2)-IAM-MOE and H(4,2)-IAM-MOE are sufficiently stable to prevent dissociation at nanomolar concentrations. The photophysical measurements for the Tb(III) complexes gave overall quantum yield values of 0.56, 0.39, and 0.52 respectively for the complexes with H(2,2)-IAM-MOE, H(3,2)-IAM-MOE and H(4,2)-IAM-MOE, while the corresponding Eu(III) complexes displayed significantly weaker luminescence, with quantum yield values of 0.0014, 0.0015, and 0.0058, respectively. Analysis of the steady state Eu(III) emission spectra provides insight into the solution symmetries of the complexes. The combined solubility, stability and photophysical performance of the Tb(III) complexes in particular make them well suited to serve as the luminescent reporter group in high sensitivity time-resolved fluoroimmunoassays.

  18. First-principles binary diffusion coefficients for H, H2 and four normal alkanes + N2

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Jasper, Ahren W.; Kamarchik, Eugene; Miller, James A.; Klippenstein, Stephen J.

    2014-09-30

    Collision integrals related to binary (dilute gas) diffusion are calculated classically for six species colliding with N2. The most detailed calculations make no assumptions regarding the complexity of the potential energy surface, and the resulting classical collision integrals are in excellent agreement with previous semiclassical results for H + N2 and H2 + N2 and with recent experimental results for C n H2n+2 + N2, n = 2–4. The detailed classical results are used to test the accuracy of three simplifying assumptions typically made when calculating collision integrals: (1) approximating the intermolecular potential as isotropic, (2) neglecting the internal structuremore » of the colliders (i.e., neglecting inelasticity), and (3) employing unphysical R–12 repulsive interactions. The effect of anisotropy is found to be negligible for H + N2 and H2 + N2 (in agreement with previous quantum mechanical and semiclassical results for systems involving atomic and diatomic species) but is more significant for larger species at low temperatures. For example, the neglect of anisotropy decreases the diffusion coefficient for butane + N2 by 15% at 300 K. The neglect of inelasticity, in contrast, introduces only very small errors. Approximating the repulsive wall as an unphysical R–12 interaction is a significant source of error at all temperatures for the weakly interacting systems H + N2 and H2 + N2, with errors as large as 40%. For the normal alkanes in N2, which feature stronger interactions, the 12/6 Lennard–Jones approximation is found to be accurate, particularly at temperatures above –700 K where it predicts the full-dimensional result to within 5% (although with somewhat different temperature dependence). Overall, the typical practical approach of assuming isotropic 12/6 Lennard–Jones interactions is confirmed to be suitable for combustion applications except for weakly interacting systems, such as H + N2. For these systems, anisotropy and inelasticity can safely be neglected but a more detailed description of the repulsive wall is required for quantitative predictions. Moreover, a straightforward approach for calculating effective isotropic potentials with realistic repulsive walls is described. An analytic expression for the calculated diffusion coefficient for H + N2 is presented and is estimated to have a 2-sigma error bar of only 0.7%.« less

  19. Spectroelectrochemical Sensor for Pertechnetate Applicable to Hanford and Other DOE Sites

    SciTech Connect (OSTI)

    Heineman, William R; Seliskar, Carl J; Bryan, Samuel A

    2012-09-18

    The general aim of our work funded by DOE is the design and implementation of a new sensor technology that offers unprecedented levels of specificity needed for analysis of the complex chemical mixtures found at DOE sites nationwide. The specific goal of this project was the development of a sensor for technetium (Tc) that is applicable to characterizing and monitoring the vadose zone and associated subsurface water at the Hanford Site and other DOE sites. The concept for the spectroelectrochemical sensor is innovative and represents a breakthrough in sensor technology. The sensor combines three modes of selectivity (electrochemistry, spectroscopy, and selective partitioning) into a single sensor to substantially improve selectivity. The sensor consists of a basic spectroelectrochemical configuration that we have developed under our previous DOE grants: a waveguide with an optically transparent electrode (OTE) that is coated with a thin chemically-selective film that preconcnetrates the analyte. The key to adapting this generic sensor to detect TcO4- and Tc complexes lies in the development of chemically-selective films that preconcentrate the analyte and, when necessary, chemically convert it into a complex with electrochemical and spectroscopic properties appropriate for sensing. Significant accomplishments were made in the general areas of synthesis and characterization of polymer films that efficiently preconcentrate the analyte, development and characterization of sensors and associated instrumentation, and synthesis and characterization of relevant Re and Tc complexes. Two new polymer films for the preconcentration step in the sensor were developed: partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SSEBS) and phosphine containing polymer films. The latter was a directed polymer film synthesis that combined the proper electrostatic properties to attract TcO4- and also incorporated a suitable ligand for covalently trapping a lower oxidation state Tc complex within the film for spectroelectrochemical detection. Spectroelectrochemical sensors were developed and demonstrated, first using [Re(dmpe)3]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) as a model compound with the non-radioactive Re surrogate for radioactive Tc. A fluorescence based spectroelectrochemical sensor for [Tc(dmpe)3]+/2+was then developed using SSEBS as the preconcentrating film. Portable instrumentation for the fluorescence spectroelectrochemical sensor was fabricated and tested. The effects of components in Hanford subsurface water on sensor performance with a detailed evaluation of the effect of total ionic strength on sensitivity demonstrated the ability to use the spectroelectrochemical sensor on representative water samples. A variety Re and Tc complexes were synthesized and characterized to explore the best ligands to use for detection of Tc. A lower oxidation-state Tc-complex [Tc(dmpe)3]+ (dmpe = 1,2-bis(dimethylphosphino)ethane) was synthesized to use as a model compound for developing Tc sensors. [Tc(dmpe)3]+/2+ exhibited the important properties of solution fluorescence at ambient temperatures and reversible electrochemistry. A range of low oxidation state dioxo Re- and Tc-complexes of formulae [ReO2(py)4]+, [ReO2(CN)4]-, [ReO2(P-P)2]+ and [ReO2(S-S)2]+ (py = pyridine) were synthesized. An exhaustive study of the spectroscopy and electrochemistry of Re(diimine)(CO)3(halide) complexes was performed. These complexes served as models for the Tc(diimine)(CO)3(halide) complexes that were readily formed from Tc(CO)x(halides)6-x complexes which are themselves constituents of tank waste samples from Hanford. Of particular interest were new Tc complexes with the +5 and +6 oxidation states. Tetrabutylammonium salt of tetrachlorooxotechnetate(V), (nBu4N)[TcOCl4] (I) was synthesized and the structure determined. [TcO2(CN)4]3- , [TcO2(en)2]2+ , [TcO2(im)4]+, and [TcO2(py)4]+ (en = ethylenediamine; im = imidazole; py = pyridine) complexes were synthesized and solution and solid state 99Tc NMR spectra were acquired giving

  20. Development of Modified Pag (Polyalkylene Glycol) High VI High Fuel Efficient Lubricant for LDV Applications

    SciTech Connect (OSTI)

    Gangopadhyay, Arup; McWatt, D. G.; Zdrodowski, R. J.; Liu, Zak; Elie, Larry; Simko, S. J.; Erdemir, Ali; Ramirez, Giovanni; Cuthbert, J.; Hock, E. D.

    2015-09-30

    Engine oils play a critical role in friction reduction. Improvements in engine oil technology steadily improved fuel economy as the industry moved through ILSAC GF-1 to GF-5 specifications. These improvements were influenced by changes in base oil chemistry, development of new friction modifiers and their treat levels, and the total additive package consisting of various other components. However, the improvements are incremental and further fuel consumption reduction opportunities are becoming more challenging. Polyalkylene glycol (PAG) based engine oils are being explored as a step forward for significant fuel consumption reduction. Although PAG fluids are used in many industrial applications, its application as an engine oil has been explored in a limited way. The objective of this project is to deep dive in exploring the applicability of PAG technology in engine oil, understanding the benefits, and limitations, elucidating the mechanism(s) for friction benefits, if any, and finally recommending how to address any limitations. The project was designed in four steps, starting with selection of lubricant technology, followed by friction and wear evaluations in laboratory bench tests which are relatively simple and inexpensive and also served as a screener for further evaluation. Selected formulations were chosen for more complex engine component level tests i.e., motored valvetrain friction and wear, piston ring friction using a motored single cylinder, and motored engine tests. A couple of formulations were further selected based on component level tests for engine dyno tests i.e., Sequence VID (ASTM D6709) for fuel economy, Sequence IVA (ASTM D6891) for valvetrain wear, and Sequence VG (ASTM D6593) for sludge and varnish protection. These are some of the industry standard tests required for qualifying engine oils. Out of these tests, a single PAG oil was selected for chassis roll dynamometer tests for fuel economy and emission measurements using FTP (Federal Test Procedure) metro/highway cycles. Five different PAG chemistries were selected by varying the starting alcohol, the oxide monomers (ethylene oxide, propylene oxide, or butylene oxide), capped or uncapped, homopolymer or random copolymer. All formulations contained a proprietary additive package and one which contained additional antiwear and friction modifier additives. Laboratory bench tests (Pin-on-Disk, High Frequency Reciprocating Rig (HFRR), Block-on-Ring, Mini-Traction Machine (MTM) identified formulations having friction, wear, and load carrying characteristics similar to or better than baseline GF-5 SAE 5W-20 oil. Motored valvetrain and motored piston ring friction tests showed nearly 50% friction reduction for some of the PAG formulations compared to GF-5 SAE 5W-20 oil. Motored engine tests showed up to 15% friction benefit over GF-5 SAE 5W-20 oil. It was observed that friction benefits are more related to PAG base oil chemistry than their lower viscosity compared to GF-5 SAE 5W-20 oil. Analysis of wear surfaces from laboratory bench tests and bucket tappets from motored valvetrain tests confirmed the presence of PAG molecules. The adsorption of these polar molecules is believed to be reason for friction reduction. However, the wear surfaces also had thin tribo-film derived from additive components. The tribo-film consisting of phosphates, sulfides, and molybdenum disulfide (when molybdenum additive was present) were observed for both GF-5 SAE 5W-20 and PAG fluids. However, when using PAG fluids, motored valvetrain tests showed high initial wear, which is believed to be due to delay in protective tribo-film formation. After the initial wear, the wear rate of PAG fluids was comparable to GF-5 SAE 5W-20 oil. The PAG oil containing additional antiwear and friction reducing additives showed low initial wear as expected. However, when this oil was evaluated in Sequence IVA test, it showed initially low wear comparable to GF-5 oil but wear accelerated with oil aging indicating rapid deterioration of additive components. ASTM Sequence VG test showed good sludge protection capability but failed to meet varnish rating for GF-5 requirement. Chassis roll dynamometer tests with PAG oil 15-1 showed about 1% fuel economy benefit over GF-5 SAE 5W-20 oil in EPA city cycles only and when the oil was slightly aged (500 miles). No fuel economy benefits could be observed in combined EPA metro/highway cycles. Also, no fuel economy benefit could be observed with continued (500- 10000 miles) oil aging. However, the emission level was comparable to the reference oil and was within EPA limits. Analysis of the PAG oil following tests showed low iron content although additive components were significantly degraded. The results indicate that PAG fluids have significant friction reduction potential but there are challenges with wear and varnish protection capabilities. These limitations are primarily because the selected additive components were chosen to provide a fluid with no metal content that forms little or no sulphated ash. Significant development work is needed to identify additive components compatible with PAG chemistry including their solubility in PAG oil. Miscibility of PAG fluids with mineral base oil is another challenge for oil change service. There is PAG chemistry (oil soluble PAG, OSP) which is soluble in mineral oils but the formulation explored in this investigation did not show significant friction reduction in motored engine tests. Again, highlighting the need for additive development for specific PAG chemistry. The thermal oxidation behavior of these oils has not been explored in this investigation and needs attention.

  1. Five new Zn(II) and Cd(II) coordination polymers constructed by 3,5-bis-oxyacetate-benzoic acid: Syntheses, crystal structures, network topologies and luminescent properties

    SciTech Connect (OSTI)

    Jiang Xianrong; Yuan Hongyan; Feng Yunlong

    2012-07-15

    Five Zn(II) and Cd(II) coordination polymers, [Zn{sub 2}(BOABA)(bpp)(OH)]{center_dot}0.5H{sub 2}O (1), [Cd{sub 3}(BOABA){sub 2}(bpp){sub 2}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O (2), [Cd{sub 3}(BOABA){sub 2}(2,2 Prime -bipy){sub 3}(H{sub 2}O){sub 4}]{center_dot}5.5H{sub 2}O (3), [CdNa(BOABA)(H{sub 2}O)]{sub 2}{center_dot}H{sub 2}O (4) and [Cd{sub 2}(BOABA)(bimb)Cl(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O (5) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid, bpp=1,3-bi(4-pyridyl)propane, 2,2 Prime -bipy=2,2 Prime -bipyridine, bimb=1,4-bis(imidazol-1 Prime -yl)butane), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and TG analyses. 1 is an uninodal 4-connected 2D square grid network based on binuclear zinc clusters. 2 is 2D wavelike layer structure and further linked by hydrogen bonds into the final 3D (5,6,6)-connected topology network. 3 is 3-connected 2D topology network and the 2,2 Prime -bipy ligands decorate in two different types. 4 is a (4,8)-connected 2D topology network with heterocaryotic {l_brace}Cd{sub 2}Na{sub 2}{r_brace} clusters and BOABA{sup 3-} ligands. 5 can be rationalized as a (3,10)-connected 3D topology network with tetranuclear {l_brace}Cd{sub 4}Cl{sub 2}{r_brace} clusters and BOABA{sup 3-} ligands. Meanwhile, photoluminescence studies revealed that these five coordination polymers display strong fluorescent emission bands in the solid state at room temperature. - Graphical abstract: Five new d{sup 10} metal(II) coordination polymers based on H{sub 3}BOABA ligand were obtained and characterized. They display different topological structures and luminescent properties. Highlights: Black-Right-Pointing-Pointer Five d{sup 10} metal(II) polymers based on 3,5-bis-oxyacetate-benzoic acid were obtained. Black-Right-Pointing-Pointer The polymers were structurally characterized by single-crystal X-ray diffraction. Black-Right-Pointing-Pointer Polymers 1-5 display different topological structures. Black-Right-Pointing-Pointer They show strong fluorescent emission bands in the solid state.