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Title: Heterogeneous catalytic process for alcohol fuels from syngas. Fourteenth quarterly technical progress report, April--June 1995

Abstract

The project objectives are: (1) To discover, study, and evaluate novel heterogeneous catalytic systems for the production of oxygenated fuel enhancers from synthesis gas. In particular, novel heterogeneous catalysts will be studied and optimized for the production of: (a) C{sub 1}-C{sub 5} alcohols using conventional methanol synthesis conditions, and (b) methanol and isobutanol mixtures which may be used for the downstream synthesis of MTBE or related oxygenates. (2) To explore, analytically and on the bench scale, novel reactor and process concepts for use in converting syngas to liquid fuel products. (3) To develop on the bench scale the best combination of chemistry, catalyst, reactor, and total process configuration to achieve the minimum product cost for the conversion of syngas to liquid products. The authors have prepared a comparative Zn/Cr spinel oxide support that contains excess ZnO and have looked at the catalytic performance of (a) the bare support, (b) a potassium traverse on the bare support to determine the effect of alkali addition in the absence of Pd and (c) a potassium traverse on the support impregnated with 6 wt% Pd. The bare support is an inefficient methanol catalyst. Alkali addition results in an increase in selectivity to total alcoholsmore » vs. the bare support and a dramatic increase higher alcohol synthesis. Pd addition results in further improvements in performance. Selectivities increase with K loading. The 5 wt% K, 5.9 wt% Pd catalyst produces > 100 g/kg-hr of isobutanol at 440 C and 1,000 psi, with 85% selectivity to total alcohols and with a methanol/isobutanol mole ratio of <2. The authors intend to continue formulation screening using K/Pd formulations on ZnO and ZnCr{sub 2}O{sub 4} prepared conventionally and via controlled pH precipitation. They will also examine the effect of Cs in place of K as the alkali promoter and the use of Rh instead of Pd as a promoter.« less

Publication Date:
Research Org.:
Union Carbide Corp., South Charleston, WV (United States)
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
257319
Report Number(s):
DOE/PC/90046-T16
ON: DE96012593; TRN: AHC29615%%15
DOE Contract Number:
AC22-91PC90046
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: [1995]
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; FUEL ADDITIVES; SYNTHESIS; ETHERS; METHANOL; CATALYSTS; MATERIALS TESTING; BUTANOLS; PROGRESS REPORT; HETEROGENEOUS CATALYSIS; CARBON MONOXIDE; HYDROGEN; CHEMICAL REACTORS; ZINC OXIDES; CHROMIUM OXIDES; CATALYST SUPPORTS; POTASSIUM; PALLADIUM; CESIUM; CATALYTIC EFFECTS; RHODIUM; PROPANOLS; EXPERIMENTAL DATA

Citation Formats

NONE. Heterogeneous catalytic process for alcohol fuels from syngas. Fourteenth quarterly technical progress report, April--June 1995. United States: N. p., 1995. Web. doi:10.2172/257319.
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NONE. Heterogeneous catalytic process for alcohol fuels from syngas. Fourteenth quarterly technical progress report, April--June 1995. United States. doi:10.2172/257319.
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NONE. Sun . "Heterogeneous catalytic process for alcohol fuels from syngas. Fourteenth quarterly technical progress report, April--June 1995". United States. doi:10.2172/257319. https://www.osti.gov/servlets/purl/257319.
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@article{osti_257319,
title = {Heterogeneous catalytic process for alcohol fuels from syngas. Fourteenth quarterly technical progress report, April--June 1995},
author = {NONE},
abstractNote = {The project objectives are: (1) To discover, study, and evaluate novel heterogeneous catalytic systems for the production of oxygenated fuel enhancers from synthesis gas. In particular, novel heterogeneous catalysts will be studied and optimized for the production of: (a) C{sub 1}-C{sub 5} alcohols using conventional methanol synthesis conditions, and (b) methanol and isobutanol mixtures which may be used for the downstream synthesis of MTBE or related oxygenates. (2) To explore, analytically and on the bench scale, novel reactor and process concepts for use in converting syngas to liquid fuel products. (3) To develop on the bench scale the best combination of chemistry, catalyst, reactor, and total process configuration to achieve the minimum product cost for the conversion of syngas to liquid products. The authors have prepared a comparative Zn/Cr spinel oxide support that contains excess ZnO and have looked at the catalytic performance of (a) the bare support, (b) a potassium traverse on the bare support to determine the effect of alkali addition in the absence of Pd and (c) a potassium traverse on the support impregnated with 6 wt% Pd. The bare support is an inefficient methanol catalyst. Alkali addition results in an increase in selectivity to total alcohols vs. the bare support and a dramatic increase higher alcohol synthesis. Pd addition results in further improvements in performance. Selectivities increase with K loading. The 5 wt% K, 5.9 wt% Pd catalyst produces > 100 g/kg-hr of isobutanol at 440 C and 1,000 psi, with 85% selectivity to total alcohols and with a methanol/isobutanol mole ratio of <2. The authors intend to continue formulation screening using K/Pd formulations on ZnO and ZnCr{sub 2}O{sub 4} prepared conventionally and via controlled pH precipitation. They will also examine the effect of Cs in place of K as the alkali promoter and the use of Rh instead of Pd as a promoter.},
doi = {10.2172/257319},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Dec 31 00:00:00 EST 1995},
month = {Sun Dec 31 00:00:00 EST 1995}
}
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Technical Report:
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DOI:  10.2172/257319
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  • The principal objectives of this project are to discover and evaluate novel heterogeneous catalysts for conversion of syngas to oxygenates having use as fuel enhancers, to explore novel reactor and process concepts applicable in this process, and to develop the best total process for converting syngas to liquid fuels. The current targets for isobutanol-producing catalysts are to produce an equimolar mixture of methanol and isobutanol with a productivity for isobutanol of > 50 g/Kg-hr. The authors have tested one of our most promising isoalcohol catalysts (10-DAN-55, Pd on ZnCr{sub 2}O{sub 4}) at pressures up to 1500 psi and temperatures frommore » 400{degrees}C to 450{degrees}C at GHSV=6000 and syngas ratio = 1:2.« less

  • The principal objectives of this project are to discover and evaluate novel heterogeneous catalysts for conversion of syngas to oxygenates having use as fuel enhancers, to explore novel reactor and process concepts applicable in this process, and to develop the best total process for converting syngas to liquid fuels. The project is being pursued as two concurrent tasks. Task I involves catalyst research and development and is being largely conducted by catalyst chemists and analytical specialists. Task 2 is largely an engineering activity, and includes process conceptualization and economics and bench-scale process evaluation of systems developed in Task 1. Themore » current goal of the catalyst development program is to increase selectivities to oxygenates to greater than 90% with methanol making up less than 70% of the oxygenates, increase rates to 20 lb/ft{sup 3}/hr, and have conversions of greater than 20%. Earlier work in this organization has shown that a potassium-modified Zn-Or-Mn-0 based catalyst system had alcohol selectivities as high as 70-80 wt %, but the overall alcohol yield was only 11 lb/ft{sup 3}/hr. The effects of the precipitation pH on surface area, porosity, and thermal characteristics of the mixed metal oxide component were examined. A designed experiment showed that the precipitation pH was an important factor influencing the BET surface area, and the calcination temperature had a negative effect on the surface area as expected. The optimal surface area for a given calcination temperature would be achieved at a pH of around 10.2. Other interesting results from the models were that calcination time did not affect any of the physical properties measured and only calcination temperature affected the mean pore diameter of the solid.« less

  • The principal objectives of this project are to discover and evaluate novel heterogeneous catalysts for conversion of syngas to oxygenates having use as fuel enhancers, to explore novel reactor and process concepts applicable in this process, and to develop the best total process for converting syngas to liquid fuels. The project is being pursued as two concurrent tasks. Task 1 involves catalyst research and development and is being largely conducted by catalyst chemists and analytical specialists. Task 2 is largely an engineering activity, and includes process conceptualization and economics and bench-scale process evaluation of systems developed in Task 1. Ourmore » current targets for isobutanol-producing catalysts are to produce a 50/50 split in selectivity between methanol and iso-butanol, a productivity for isobutanol of >50 g/Kg-hr and an overall process conversion of 40%. We have continued to study how preparation variables affect the catalysts` chemical and physical properties.« less

  • The principal objectives of this project are to discover and evaluate novel heterogeneous catalysts for conversion of syngas to oxygenates having use as fuel enhancers, to explore novel reactor and process concepts applicable in this process, and to develop the best total process for converting syngas to liquid fuels. Among our previous best catalysts was the family consisting of potassium-promoted Pd on a Zn/Cr spinel oxide prepared via controlled pH precipitation. We have now examined the effect of potassium promotion on (1) a Zn/Cr/O spinel and (2) on ZnO; these two individual components are used together to make our bestmore » support. The presence of excess zinc oxide has a beneficial effect on the performance of Zn/Cr spinel oxide catalysts (1) promoted with cesium and (2) promoted with both cesium and palladium. The presence of the excess zinc oxide results in a more active and selective catalyst to total alcohols and increased isobutanol rates, demonstrating the effectiveness of zinc oxide addition to the spinel support. Potassium addition promotes higher alcohol synthesis on a commercial Zn/Cr spinel oxide methanol synthesis catalyst. Incremental potassium levels (1, 3 and 5 wt%) result in an increase in total alcohol selectivity, while isobutanol. rates are maximized at 1 wt% potassium. The commercial catalyst promoted with potassium is slightly less active for isobutanol synthesis and less selective to total alcohols when compared with our spinel formulation promoted with potassium and containing excess ZnO. Surface science studies have shown that the surface of these catalysts is predominately ZnO and alkali. With use, the ZnO is reduced to Zn metal, and Cr migrates to the surface giving increased surface acidity. In addition tends to lower the overall acidity. Hydrogen can be observed on the catalyst surface by surface science studies. Hydrogen on the active catalyst is associated with the palladium.« less

  • The principal objectives of this project are to discover and evaluate novel heterogeneous catalysts for conversion of syngas to oxygenates having use as fuel enhancers, to explore novel reactor and process concepts applicable in this process, and to develop the best total process for converting syngas to liquid fuels. The previous best catalysts consisted of potassium-promoted Pd on a Zn/Cr spinel oxide prepared via controlled pH precipitation. The authors have now examined the effect of cesium addition to the Zn/Cr spinel oxide support. Surprisingly, cesium levels required for optimum performance are similar to those for potassium on a wt% basis.more » The addition of 3 wt% cesium gives isobutanol rates > 170 g/kg-hr at 440 C and 1,500 psi with selectivity to total alcohols of 77% and with a methanol/isobutanol mole ratio of 1.4: this performance is as good as their best Pd/K catalyst. The addition of both cesium and palladium to a Zn/Cr spinel oxide support gives further performance improvements. The 5 wt% cesium, 5.9 wt% Pd formulation gives isobutanol rates > 150 g/kg-hr at 440 C and only 1,000 psi with a selectivity to total alcohols of 88% and with a methanol/isobutanol mole ratio of 0.58: this is their best overall performance to date. The addition of both cesium and palladium to a Zn/Cr/Mn spinel oxide support that contains excess Zn has also been examined. This spinel was the support used in the synthesis of 10-DAN-54, the benchmark catalyst. Formulations made on this support show a lower overall total alcohol rate than those using the spinel without Mn present, and require less cesium for optimal performance.« less