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Title: Interactive chemistry of coal-petroleum processing: Quarterly progress report for March 15, 1987-June 15, 1987. [Effect of coal or resid on reaction]

Abstract

The thermal reactions of model compounds NAPH, DMC, PN, BZT, and QN with Maya TLR (topped long resid) showed no reactions. The presence of Maya TLR blocked the intermediate hydrogenation pathway from QN to THQ compared to the reaction without Maya TLR where 13% THQ was formed. Maya TLR served as a strong inhibitor in the catalytic hydrogenations of model compounds, being more detrimental to the hydrogenation and heteroatom removal reactions than coal. The severe inhibition of Maya TLR is caused by the chemical composition of the resid. The resid contains large refractory hydrocarbon species and substantial amounts of metals. Maya TLR was most likely deactivating the NiMo/Al/sub 2/O/sub 3/ catalyst as well as possibly interacting with model species present. Catalyst deactivation due to pore-plugging by petroleum crude and residua reaction products from hydrotreating, i.e., metal sulfides and coke has been studied by Newson. In crude oils and residua, vanadium and nickel compounds are the most abundant organometallic constituents and cause major problems in hydrotreating of residuum oils. At hydroprocessing conditions, these metal compounds deposit on and deactivate the catalyst. Pore mouth plugging in the catalyst by the metal deposit has been known as the major cause in the catalystmore » deactivation. Tamm and co-workers studied two mechanisms of catalyst deactivation by petroleum feed metals: (1) poisoning of the active surface and (2) physical obstruction of the pore structure. Thus, two possible reasons for the severe deactivation observed in the Maya TLR are metal deposition and carbon laydown on the catalyst surface. Another reason why the Maya TLR had a stronger inhibiting effect than coal is that these reactions are at 350/sup 0/C, where the coal was only partially dissolved; therefore, all the bad actors from coal were not available in the system, while those from the resid were. 3 refs., 4 figs., 36 tabs.« less

Authors:
; ;
Publication Date:
Research Org.:
Auburn Univ., AL (USA). Dept. of Chemical Engineering
OSTI Identifier:
6141465
Report Number(s):
DOE/PC/80502-T6
ON: DE87013440
DOE Contract Number:
FG22-85PC80502
Resource Type:
Technical Report
Resource Relation:
Other Information: Portions of this document are illegible in microfiche products
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; CATALYSTS; DEACTIVATION; HYDROGENATION; STRUCTURAL MODELS; CATALYTIC EFFECTS; COAL; DENITRIFICATION; DESULFURIZATION; HETEROCYCLIC COMPOUNDS; MOLYBDENUM; NAPHTHALENE; NICKEL; PETROLEUM RESIDUES; PHENOL; PROCESSING; QUINOLINES; REMOVAL; THIONAPHTHENES; AROMATICS; AZAARENES; AZINES; CARBONACEOUS MATERIALS; CHEMICAL REACTIONS; CONDENSED AROMATICS; ELEMENTS; ENERGY SOURCES; FOSSIL FUELS; FUELS; HYDROCARBONS; HYDROXY COMPOUNDS; MATERIALS; METALS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PETROLEUM; PETROLEUM FRACTIONS; PHENOLS; PYRIDINES; TRANSITION ELEMENTS; 010405* - Coal, Lignite, & Peat- Hydrogenation & Liquefaction

Citation Formats

Curtis, C.W., Guin, J.A., and Tarrer, A.R. Interactive chemistry of coal-petroleum processing: Quarterly progress report for March 15, 1987-June 15, 1987. [Effect of coal or resid on reaction]. United States: N. p., 1987. Web.
Curtis, C.W., Guin, J.A., & Tarrer, A.R. Interactive chemistry of coal-petroleum processing: Quarterly progress report for March 15, 1987-June 15, 1987. [Effect of coal or resid on reaction]. United States.
Curtis, C.W., Guin, J.A., and Tarrer, A.R. 1987. "Interactive chemistry of coal-petroleum processing: Quarterly progress report for March 15, 1987-June 15, 1987. [Effect of coal or resid on reaction]". United States. doi:.
@article{osti_6141465,
title = {Interactive chemistry of coal-petroleum processing: Quarterly progress report for March 15, 1987-June 15, 1987. [Effect of coal or resid on reaction]},
author = {Curtis, C.W. and Guin, J.A. and Tarrer, A.R.},
abstractNote = {The thermal reactions of model compounds NAPH, DMC, PN, BZT, and QN with Maya TLR (topped long resid) showed no reactions. The presence of Maya TLR blocked the intermediate hydrogenation pathway from QN to THQ compared to the reaction without Maya TLR where 13% THQ was formed. Maya TLR served as a strong inhibitor in the catalytic hydrogenations of model compounds, being more detrimental to the hydrogenation and heteroatom removal reactions than coal. The severe inhibition of Maya TLR is caused by the chemical composition of the resid. The resid contains large refractory hydrocarbon species and substantial amounts of metals. Maya TLR was most likely deactivating the NiMo/Al/sub 2/O/sub 3/ catalyst as well as possibly interacting with model species present. Catalyst deactivation due to pore-plugging by petroleum crude and residua reaction products from hydrotreating, i.e., metal sulfides and coke has been studied by Newson. In crude oils and residua, vanadium and nickel compounds are the most abundant organometallic constituents and cause major problems in hydrotreating of residuum oils. At hydroprocessing conditions, these metal compounds deposit on and deactivate the catalyst. Pore mouth plugging in the catalyst by the metal deposit has been known as the major cause in the catalyst deactivation. Tamm and co-workers studied two mechanisms of catalyst deactivation by petroleum feed metals: (1) poisoning of the active surface and (2) physical obstruction of the pore structure. Thus, two possible reasons for the severe deactivation observed in the Maya TLR are metal deposition and carbon laydown on the catalyst surface. Another reason why the Maya TLR had a stronger inhibiting effect than coal is that these reactions are at 350/sup 0/C, where the coal was only partially dissolved; therefore, all the bad actors from coal were not available in the system, while those from the resid were. 3 refs., 4 figs., 36 tabs.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 1987,
month = 1
}

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  • The thermal and catalytic chemistry of napthalene, indan, indene, benzothiophene, o-cresol, benzofuran and quinoline has been investigated to help elucidate the reactions occurring during the coprocessing of coal and petroleum. Hydrogenation reactions were conducted. Three sets of reactions were performed: thermal, thermal with sulfur and catalytic with Mo naphthenate as an oil-soluble catalyst precursor and added sulfur to generate the catalyst in situ. A reaction temperature of 380/sup 0/C and a hydrogen atmosphere of 1250 psig (cold) were used. Analysis of the solids generated from Mo naphthenate and sulfur amorphous and poorly crystalline molybdenum sulfide, most probably MoS/sub 2/; however,more » the exact stoichiometry is inknown. The thermal reaction was performed as a baseline and to evaluate the thermal interactions among the various hydrocarbon and heteroatomic species; the thermal reaction with sulfur was performed to ascertain the effect of excess sulfur on the system since the catalytic system required excess sulfur to form the in situ generated catalyst; and the catalytic reaction was performed to determine the interactive chemistry of the hydrocarbons and heteroatomic species under catalytic coprocessing conditions. 13 refs., 14 figs., 10 tabs.« less
  • Some conversion and hydrogenation reactivity of benzofuran was observed in the thermal reaction with sulfur. However, catalytic reaction with Mo naphthenate was required for substantial, nearly 50%, hydrogenation, complete hydrogenolysis and high levels, approx.80%, deoxygenation. The introduction of benzothiophene and o-cresol lowered both hydrogenation and deoxygenation while the addition of quinoline markedly reduced hydrogenation, virtually eliminated deoxygenation and slightly reduced hydrogenolysis. Quinoline, by contrast to all of the other compounds studied, produced substantial thermal hydrogenation to THQ; however, the introduction of both hydrocarbons and heteroatomics reduced the conversion of quinoline to THQ. The presence of the oxygen containing compounds nearlymore » eliminated the conversion of quinoline to THQ. Similar results were observed in the thermal reactions with sulfur. Catalytically, quinoline was readily hydrogenated and denitrogenated. The addition of both hydrocarbons and heteroatomics had little influence on the quinoline reaction except for the introduction of benzothiophene at higher reactant levels. When added to a catalytic reaction of naphthalene and quinoline, the addition of benzothiophene reduced the catalyst poisoning effects of quinoline. The hydrogenation of naphthalene double while the hydrogenation, hydrogenolysis and denitrogenation of quinoline were all improved. 15 refs.« less
  • The key findings are summarized. In the experiments with added elemental sulfur or sulfur containing organic compounds, the reactor walls appeared to be sulfided. The sulfided walls showed catalytic activity for promoting hydrogenation reactions of the model systems. Additional sulfur added to the model systems had different effects depending upon the reaction occurring. Hydrogenation of naphthalene and quinoline were enhanced; deoxygenation of o-cresol was inhibited; and hydrogenation of benzothiophene was not affected. However, the product which required further hydrogenation was ethylbenzene whose hydrogenation was not readily promoted by molybdenum sulfide. Adding excess amounts of sulfur to model systems containing nitrogenmore » bases which poison the MoS/sub 2/ catalyst may alleviate the effect of the poison to some extent. Two strong nitrogen bases, quinoline and pyridine severely poisoned the catalytic hydrogenation activity and the denitrogenation selectivity of the in situ generated MoS/sub 2/. 22 refs., 2 figs., 28 tabs.« less
  • The introduction of quinoline to the naphthalene/DMC system had a dramatic effect on the products produced during catalytic reactions. The amount of naphthalene hydrogenated to both tetralin and decalin was substantially reduced. Of the three heteroatomic species introduced the catalytic naphthalene/DMC system, quinoline had the greatest inhibiting effect on naphthalene hydrogenation. Benzothiophene had a greater effect than phenol which had the least. The presence of naphthalene and DMC appeared to enhance the amount of hydrodenitrogenation and hydrogenolysis occurring in the catalytic hydrogenation of quinoline. Binary systems of naphthalene/quinoline, tetralin/quinoline and DMC/quinoline did not show any such enhancement. In fact, themore » presence of DMC inhibited the denitrogenation and hydrogenolysis of quinoline. The presence of tetralin either introduced directly or produced from the hydrogenation of naphthalene in the system did not appear to affect the quinoline reaction pathway. Therefore, the promoting effect obtained by the combination of naphthalene/DMC and quinoline is not easily explained by hydrogen donor chemistry but involves complex interactions among the chemical components and the catalyst. Under themal conditions at 350/sup 0/C, quinoline underwent hydrogenation unlike the other species used in this study. Even though a large excess of hydrogen was present, the introduction of naphthalene and DMC reduced by half the amount of quinoline hydrogenation occurring thermally. 10 refs., 1 fig., 19 tabs.« less
  • The objective is to investigate the thermal and catalytic chemistry of coal-petroleum processing using model compounds and actual petroleum-coal materials. The work performed has focused upon: (1) an experimental investigation of the interactive chemistry of coal-petroleum hydrocarbon systems and coal-petroleum hydrocarbon and heteroatom systems: (2) experimental work using an oil-soluble catalyst, Mo naphthenate as a model organometallic for the investigation of the effect of organometallics and petroporphyrins on the interactive chemistry of coal petroleum processing; and (3) a literature review investigating the catalytic effect of vanadium in upgrading heavy ends. 22 refs., 28 tabs.