Conversion of the CO and CO<sub>2</sub> mixture to alcohols and hydrocarbons by hydrogenation under the influence of the water-gas shift reaction, a thermodynamic consideration

GUO Shu-jia; WANG Han; QIN Zhang-feng; LI Zhi-kai; WANG Guo-fu; DONG Mei; FAN Wei-bin; WANG Jian-guo

doi:10.1016/S1872-5813(23)60346-9

Volume 51 Issue 4

Apr. 2023

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Article Navigation > Journal of Fuel Chemistry and Technology > 2023 > 51(4): 482-491

GUO Shu-jia, WANG Han, QIN Zhang-feng, LI Zhi-kai, WANG Guo-fu, DONG Mei, FAN Wei-bin, WANG Jian-guo. Conversion of the CO and CO2 mixture to alcohols and hydrocarbons by hydrogenation under the influence of the water-gas shift reaction, a thermodynamic consideration[J]. Journal of Fuel Chemistry and Technology, 2023, 51(4): 482-491. doi: 10.1016/S1872-5813(23)60346-9

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GUO Shu-jia, WANG Han, QIN Zhang-feng, LI Zhi-kai, WANG Guo-fu, DONG Mei, FAN Wei-bin, WANG Jian-guo. Conversion of the CO and CO₂ mixture to alcohols and hydrocarbons by hydrogenation under the influence of the water-gas shift reaction, a thermodynamic consideration[J]. Journal of Fuel Chemistry and Technology, 2023, 51(4): 482-491. doi: 10.1016/S1872-5813(23)60346-9

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Conversion of the CO and CO₂ mixture to alcohols and hydrocarbons by hydrogenation under the influence of the water-gas shift reaction, a thermodynamic consideration

doi: 10.1016/S1872-5813(23)60346-9

GUO Shu-jia^{1, 2, #
,},
WANG Han^{1, 2, #
,},
QIN Zhang-feng^{1
,
,},
LI Zhi-kai^{1
,
,},
WANG Guo-fu^1
,,
DONG Mei^1
,,
FAN Wei-bin^1
,,
WANG Jian-guo^{1, 2
,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Key Research and Development Program of China (2020YFB0606404) and National Natural Science Foundation of China (21991092, 22272195, U2003123, U1910203).

More Information

Corresponding author: E-mail: qzhf@sxicc.ac.cn; lizhikai@sxicc.ac.cn
Received Date: 2023-02-16
Accepted Date: 2023-03-06
Rev Recd Date: 2023-03-05

Available Online: 2023-03-09

Publish Date: 2023-04-15

Abstract

Abstract

Due to the intervention from the water-gas shift (WGS) reaction (or the reverse one (RWGS)), the hydrogenation of CO (or CO₂) into alcohols and hydrocarbons often displays rather high selectivity to CO₂ (or CO), which makes it rather puzzling to evaluate such conversion processes by using the relatively low selectivity to the target products. Herein, a thermodynamic consideration is made to elaborately evaluate the effect of the WGS/RWGS reaction on the hydrogenation of CO, CO₂, and their mixture to typical alcohols (e.g. methanol) and hydrocarbons (e.g. ethene). The results indicate that for the hydrogenation of CO (or CO₂), although the WGS (or RWGS) reaction, acting as a communicating vessel connecting CO and CO₂, may have a severe influence on the equilibrium conversion of CO (or CO₂), forming a large amount of CO₂ (or CO), it only has a relatively minor impact on the C-based equilibrium yield of the target alcohol/hydrocarbon product. The hydrogenation of CO shows a higher C-based equilibrium yield for the target product than the hydrogenation of CO₂, while the overall C-based equilibrium yield of target product for the hydrogenation of the CO and CO₂ mixture just lies in between. For the hydrogenation of the CO and CO₂ mixture, although the equilibrium conversion of CO and CO₂ may vary greatly with the change in the feed composition, the relation between the overall C-based equilibrium yield of the target product and the feed composition is rather simple; that is, the overall C-based equilibrium yield of alcohol/hydrocarbon product decreases almost lineally with the increase of the CO₂/(CO + CO₂) molar ratio in the feed. These results strongly suggest that the mixture of CO and CO₂ is credible in practice for the production of alcohols and hydrocarbons through hydrogenation, where the overall C-based yield should be used as the major index for the hydrogenation of CO, CO₂, and their mixture.
- thermodynamic consideration,
- CO₂ hydrogenation,
- CO hydrogenation,
- water-gas shift reaction,
- overall C-based yield,
- methanol,
- ethene,
- CO and CO₂ mixture

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References(20)

References

[1]	ZHOU W, CHENG K, KANG J C, ZHOU C, SUBRAMANIAN V, ZHANG Q H, WANG Y. New horizon in C1 chemistry: Breaking the selectivity limitation in transformation of syngas and hydrogenation of CO₂ into hydrocarbon chemicals and fuels[J]. Chem Soc Rev,2019,48(12):3193−3228. doi: 10.1039/C8CS00502H
[2]	ZHAO S Q, LI H W, WANG B, YANG X L, PENG Y H, DU H, ZHANG Y, HAN D Z, LI Z. Recent advances on syngas conversion targeting light olefins[J]. Fuel,2022,321:124124. doi: 10.1016/j.fuel.2022.124124
[3]	JIAO F, LI J J, PAN X L, XIAO J P, LI H B, MA H, WEI M M, PAN Y, ZHOU Z Y, LI M R, MIAO S, LI J, ZHU Y F, XIAO D, HE T, YANG J H, QI F, FU Q, BAO X H. Selective conversion of syngas to light olefins[J]. Science,2016,351(6277):1065−1068. doi: 10.1126/science.aaf1835
[4]	WANG H, FAN S, WANG S, DONG M, QIN Z F, FAN W B, WANG J G. Research progresses in the hydrogenation of carbon dioxide to certain hydrocarbon products[J]. J Fuel Chem Technol,2021,49(11):1609−1619. doi: 10.1016/S1872-5813(21)60122-6
[5]	BUSHUYEV O S, DE LUNA P, DINH C T, TAO L, SAUR G, VAN DE LAGEMAAT J, KELLEY S O, SARGENT E H. What should we make with CO₂ and how can we make it?[J]. Joule,2018,2(5):825−832. doi: 10.1016/j.joule.2017.09.003
[6]	POROSOFF M D, YAN B, CHEN J G. Catalytic reduction of CO₂ by H₂ for synthesis of CO, methanol and hydrocarbons: Challenges and opportunities[J]. Energy Environ Sci,2016,9(1):62−73. doi: 10.1039/C5EE02657A
[7]	ZHONG J W, YANG X F, WU Z L, LIANG B L, HUANG Y Q, ZHANG T. State of the art and perspectives in heterogeneous catalysis of CO₂ hydrogenation to methanol[J]. Chem Soc Rev,2020,49(5):1385−1413. doi: 10.1039/C9CS00614A
[8]	FAYISA B A, YANG Y, ZHEN Z, WANG M Y, LV J, WANG Y, MA X. Engineered chemical utilization of CO₂ to methanol via direct and indirect hydrogenation pathways: A review[J]. Ind Eng Chem Res,2022,61(29):10319−10335. doi: 10.1021/acs.iecr.2c00402
[9]	ALVAREZ A, BANSODE A, URAKAWA A, BAVYKINA A V, WEZENDONK T A, MAKKEE M, GASCON J, KAPTEIJN F. Challenges in the greener production of formates/formic acid, methanol, and DME by heterogeneously catalyzed CO₂ hydrogenation processes[J]. Chem Rev,2017,117(14):9804−9838. doi: 10.1021/acs.chemrev.6b00816
[10]	XIAO F S, AZEVEDO D, NICHOLAS C P, PETIT C. Preface for special issue on engineered methodologies for CO₂ utilization[J]. Ind Eng Chem Res,2022,61(29):10295−10297. doi: 10.1021/acs.iecr.2c02297
[11]	RA E C, KIM K Y, KIM E H, LEE H, AN K, LEE J S. Recycling carbon dioxide through catalytic hydrogenation: Recent key developments and perspectives[J]. ACS Catal,2020,10(19):11318−11345. doi: 10.1021/acscatal.0c02930
[12]	PORTILLO A, ATEKA A, EREÑA J, BILBAO J, AGUAYO A T. Role of Zr loading into In₂O₃ catalysts for the direct conversion of CO₂/CO mixtures into light olefins[J]. J Environ Manage,2022,316:115329. doi: 10.1016/j.jenvman.2022.115329
[13]	VO C H, PÉREZ-RAMÍREZ J, FAROOQ S, KARIMI I A. Prospects of producing higher alcohols from carbon dioxide: A process system engineering perspective[J]. ACS Sustainable Chem Eng,2022,10(36):11875−11884. doi: 10.1021/acssuschemeng.2c02810
[14]	AHMAD K, UPADHYAYULA S. Greenhouse gas CO₂ hydrogenation to fuels: A thermodynamic analysis[J]. Environ Prog Sustainable Energy,2019,38(1):98−111. doi: 10.1002/ep.13028
[15]	GUO S J, WANG H, QIN Z F, LI Z K, WANG G F, DONG M, FAN W B, WANG J G. Feasibility, limit, and suitable reaction conditions for the production of alcohols and hydrocarbons from CO and CO₂ through hydrogenation, a thermodynamic consideration[J]. Ind Eng Chem Res,2022,61(46):17027−17038. doi: 10.1021/acs.iecr.2c02898
[16]	LIU J G, QIN Z F, WANG J G. Methanol synthesis under supercritical conditions: calculations of equilibrium conversions by using the Soave-Redlich-Kwong equation of state[J]. Ind Eng Chem Res,2001,40(17):3801−3805. doi: 10.1021/ie0100479
[17]	QIN Z F, LIU J G, WANG J G. Solvent effects on higher alcohols synthesis under supercritical conditions: A thermodynamic consideration[J]. Fuel Process Technol,2004,85(8/10):1175−1192.
[18]	SOAVE G. Equilibrium constants from a modified Redlich-Kwong equation of state[J]. Chem Eng Sci,1972,27(6):1197−1203. doi: 10.1016/0009-2509(72)80096-4
[19]	GRAAF G H, SIJTSEMA P J J M, STAMHUIS E J, JOOSTEN G E H. Chemical equilibria in methanol synthesis[J]. Chem Eng Sci,1986,41(11):2883−2890. doi: 10.1016/0009-2509(86)80019-7
[20]	ZHANG W Y, WANG S, GUO S J, QIN Z F, DONG M, FAN W B, WANG J G. Ga_mCrO_x/H-SAPO-34(F), a highly efficient bifunctional catalyst for the direct conversion of CO₂ into ethene and propene[J]. Fuel,2022,329:125475. doi: 10.1016/j.fuel.2022.125475