Status and future opportunities for conversion of synthesis gas to liquid energy fuels: Final report

Mills, Gregory

doi:10.2172/6546429

Cited by 6 publications

(5 citation statements)

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“…In the CO hydrogenation reaction, varying the operating conditions (temperature ( T ), pressure ( P ), and gas hourly space velocity (GHSV)) has a direct impact on the product selectivity and yields. Typical process parameters monitored for temperature and pressure spans the ranges of 250–350 °C and 5–10 MPa, respectively, , and the reactions are quite dependent on the catalyst employed. ,, For instance, although the best temperature range for Cu-based catalysts is 250–300 °C, that for alkali-doped MoS 2 -based catalyst is 270–330 °C. , That notwithstanding, significant problems associated with higher temperatures include the instability of some oxygenates and excessive formation of CO 2 and methane, as well as catalyst deactivation due to sintering . At constant temperatures, the formation of higher alcohols is thermodynamically favored with increasing pressures. , The general observed trend is that, as P increases, the productivity of higher alcohols increases; however, the effect of P on the reaction kinetics is also catalyst specific, to some extent .…”

Section: Introductionmentioning

confidence: 99%

“…Typical process parameters monitored for temperature and pressure spans the ranges of 250−350 °C and 5− 10 MPa, respectively, 19,25 and the reactions are quite dependent on the catalyst employed. 17,26,27 For instance, although the best temperature range for Cu-based catalysts is 250−300 °C, that for alkali-doped MoS 2 -based catalyst is 270−330 °C. 19,27 That notwithstanding, significant problems associated with higher temperatures include the instability of some oxygenates and excessive formation of CO 2 and methane, as well as catalyst deactivation due to sintering.…”

Section: Introductionmentioning

confidence: 99%

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Higher Alcohols Synthesis: Experimental and Process Parameters Study over a CNH-Supported KCoRhMo Catalyst

Boahene

Dalai

2017

Ind. Eng. Chem. Res.

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The present work investigated the effects of operating conditions (temperature (T), pressure (P), and gas hourly space velocity (GHSV)) on the higher-alcohols synthesis reaction, using a downward-flow fixed-bed reactor. The carbon nanohorn (CNH)-supported KCoRhMo catalysts with compositions of 9% K, 4.5% Co, 1.5% Rh, and 15 wt % Mo were used for this study. The Design Expert software was used to analyze the interaction effects of T (290−370 °C), P (800−1400 psig), and GHSV (2.4−4.8 m 3 (STP)/kg cat /h) on CO conversion, alcohols, and hydrocarbon product selectivities, as well as their respective yields. The validity of the models was assessed by statistical tests: test of significance and coefficient of determination (R 2 ) values. The recorded R 2 values suggested that the quadratic models generated could sufficiently depict the experimental data. Increasing temperature and pressure in the ranges of 290−350 °C and 800−1400 psig, respectively, resulted in corresponding increases in CO conversions; however, with increasing GHSV, the CO conversion decreased monotonically. Numerical optimization assessments of the models selected the optimum operating conditions to be 325 °C, 1320 psig, and 2.4 m 3 (STP)/kg cat /h to give the maximum ethanol and higher alcohols space time yields of 0.126 and 0.177 g/g cat /h, respectively.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Higher Alcohols Synthesis: Experimental and Process Parameters Study over a CNH-Supported KCoRhMo Catalyst

Boahene

Dalai

2017

Ind. Eng. Chem. Res.

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“…This site has collected a bibliography of the large body of documents from the 1920's through the 1970s, which are important for researching the history and development of FTS and related processes as well as an up-to-date listing of the latest publications in this field. Many excellent reviews of FTS have been drawn upon for this report (Mills, 1993;Dry, 2002; in an attempt to summarize, the chemistry (Frohning, et al, 1982), catalyst development (Bartholemew, 1991;Oukaci, et al, 1999;and Raje, et al, 1997), commercial processes (Dry, 2002(Dry, , 1999(Dry, , 1982Senden, et al, 1992;Haid, et al, 2002, Van Nierop et al, 2000, reactor development (Adesini, 1986;Dry, 1988;and Dry and Hoogendoorm, 1981), and economics of FTS.…”

Section: Introductionmentioning

confidence: 99%

Integrated Process Configuration for High-Temperature Sulfur Mitigation during Biomass Conversion via Indirect Gasification

Dutta

Cheah

Bain

et al. 2012

Ind. Eng. Chem. Res.

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amount of design data, more analysis should be performed for mixed alcohols synthesis to examine biomass-optimized configurations including recycle for maximum conversion and the resulting economics. All biomass fuels have potential to significantly reduce the import of petroleum products. Additionally, economies of scale can play a large factor in lowering the product cost. Therefore, opportunities to co-feed with coal or natural gas systems may be one way to get renewable fuels into the marketplace, just as co-firing biomass with coal is being done in the power generation industry. The impetus for this extensive literature review is the recent reorganization of the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (EERE) into eleven new Program Offices. EERE's mission is to strengthen US energy security, environmental quality, and economic health. The Office of Biomass Program is one of these newly created offices. Its goal is developing technologies to transform our abundant biomass resources into clean, affordable, and domestically-produced biofuels, biopower, and high-value bioproducts resulting in economic development, energy supply options, and energy security. In this context, commercially available and nearcommercial syngas conversion processes were evaluated on technological, environmental, and economic bases. This report serves as a first step. Additional, more detailed analyses are required to identify promising, cost-effective fuel synthesis technologies where biomass thermochemical conversion could make an impact. iii Table 1: Summary of Product Information-Facts, Advantages, & Disadvantages Product Facts Advantages Disadvantages H 2 Largest use of syngas Predominately made via SMR Appears to be the most cost competitive option for biomass Automakers working on H 2 fueled vehicles Table of Contents Executive Summary/Conclusions .

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“…Various catalyst systems for the synthesis of higher alcohols from CO/H2 have been developed and widely studied. They can be generally divided into three groups: (1) modified methanol synthesis catalysts (Cu/ZnO-based), (2) group Vm metal based catalysts (Rh, Pd-based; modified Fe, Co and Ni), and…”

Section: Introductionmentioning

confidence: 99%

“…There is still a lack of mechanistic knowledge required for the rational design and preparation of catalysts with high activity and satisfactory selectivity as well as for kinetic modeling and process design. To achieve an understanding of observed activity and selectivity patterns, researchers have attempted to study: (1) the nature of the catalytic sites which are active in the formation of the desired alcohol products; (2) the nature of the surface intermediates or precursors which lead the reaction towards the desired alcohol products; Many other characterization techniques, such as XRD, TEM, adsorption measurements, X-Ray photoelectron spectroscopy, UV spectroscopy, have been applied to generate information about the nature of the surface@-13).…”

Section: Introductionmentioning

confidence: 99%

Probe molecule studies: Active species in alcohol synthesis. Final report, July 1993--July 1994

Blackmond¹,

Wender²,

Oukaci³

et al. 1994

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To develop a better understanding of the mechanism of C2+ alcohol formation from CO/H2 over Co-Cu based catalysts, investigations were carried out by several physical and chemical catalyst characterization techniques, alteration of catalyst reduction condition, CO hydrogenation reaction and in-situ addition of nitromethane as a probe molecule to C0/H2 at steady state. It was demonstrated that the presence of cobalt in a Cu/ZnO based catalyst drastically reduced the activity of Cu for methanol synthesis and significantly suppressed the promotional effect of C 0 2 on methanol formation by blocking or deactivating the copper metal sites, and the copresence of cobalt metal and copper metal did not necessarily promote the formation rates of C2+ alcohols. The reduction treatments using high H2 partial pressure (2 1 atm) at high temperature (> 300OC) were found possible to improve extent of reduction of cobalt without causing sintering of copper metal particles, which consequently increased the local atomic ratio of Coo/Cuo and resulted in dramatic enhancement in the catalyst activity and selectivity for the synthesis of C2-C6 alcohols. A reasonable particle size of cobalt.meta1 in contact with copper metal was suggested to be a key factor in constructing the active sites for the formation of C2+ alcohols. The interaction of CH3N02 with the reaction network of CO hydrogenation over the Cu and Co-Cu based catalysts provided evidence suggesting that the aldehydic methanol intermediate formed from CO and H2 was also involved in the chain growth of C2+ alcohol formation.

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Status and future opportunities for conversion of synthesis gas to liquid energy fuels: Final report

Cited by 6 publications

References 41 publications

Higher Alcohols Synthesis: Experimental and Process Parameters Study over a CNH-Supported KCoRhMo Catalyst

Higher Alcohols Synthesis: Experimental and Process Parameters Study over a CNH-Supported KCoRhMo Catalyst

Integrated Process Configuration for High-Temperature Sulfur Mitigation during Biomass Conversion via Indirect Gasification

Probe molecule studies: Active species in alcohol synthesis. Final report, July 1993--July 1994

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