Highly selective synthesis of LPG from CO2 hydrogenation over In2O3/SSZ-13 binfunctional catalyst

LU Si-yu; YANG Hai-yan; YANG Cheng-guang; GAO Peng; SUN Yu-han

doi:10.1016/S1872-5813(21)60057-9

Volume 49 Issue 8

Aug. 2021

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Article Navigation > Journal of Fuel Chemistry and Technology > 2021 > 49(8): 1132-1139

LU Si-yu, YANG Hai-yan, YANG Cheng-guang, GAO Peng, SUN Yu-han. Highly selective synthesis of LPG from CO2 hydrogenation over In2O3/SSZ-13 binfunctional catalyst[J]. Journal of Fuel Chemistry and Technology, 2021, 49(8): 1132-1139. doi: 10.1016/S1872-5813(21)60057-9

Citation:

LU Si-yu, YANG Hai-yan, YANG Cheng-guang, GAO Peng, SUN Yu-han. Highly selective synthesis of LPG from CO₂ hydrogenation over In₂O₃/SSZ-13 binfunctional catalyst[J]. Journal of Fuel Chemistry and Technology, 2021, 49(8): 1132-1139. doi: 10.1016/S1872-5813(21)60057-9

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Highly selective synthesis of LPG from CO₂ hydrogenation over In₂O₃/SSZ-13 binfunctional catalyst

doi: 10.1016/S1872-5813(21)60057-9

LU Si-yu^{1, 2
,},
YANG Hai-yan¹,
YANG Cheng-guang¹,
GAO Peng^{1, 2
,
,},
SUN Yu-han^{1, 3, 4
,
,}

1.
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
2.
University of the Chinese Academy of Sciences, Beijing 100049, China
3.
School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China
4.
Shanghai Institute of Clean Technology, Shanghai 201620, China

Funds: The projected was supported by the National Natural Science Foundation of China (21773286, U1832162), Youth Innovation Promotion Association CAS (2018330), “Transformational Technologies for Clean Energy and Demonstration,” Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21090204), the Shanghai Rising-Star Program, China (19QA1409900)

Received Date: 2021-02-05
Rev Recd Date: 2021-02-22

Available Online: 2021-03-09

Publish Date: 2021-08-31

Abstract

Abstract

Highly selective synthesis of liquefied petroleum gas (LPG, ${\rm{C}}_3^0 $ and ${\rm{C}}_4^0 $) from CO₂ hydrogenation have realized over the In₂O₃/SSZ-13 bifunctional catalyst. The physicochemical properties of the bifunctional catalyst were characterized by X-ray diffraction spectroscopy (XRD), N₂ physical adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NH₃ temperature-programmed desorption (NH₃-TPD). The particle size effect of In₂O₃ and reaction conditions were investigated for CO₂ hydrogenation to LPG over the In₂O₃/SSZ-13 bifunctional catalyst. Results indicate that CO₂ conversion and CO selectivity are related to the particle size of In₂O₃, and fresh 5 nm In₂O₃ shows the highest CO₂ conversion (11.7%) and the highest CO selectivity (61.0%), since it is more prone to reverse water gas reaction (RWGS). However, the hydrocarbon distribution does not exhibit a dependence of In₂O₃ size changes, and the selectivity of LPG maintains at 90% and the selectivity of propane reaches up to 76.8% due to the 8-MR micropores and strong acid sites of SSZ-13 zeolite. Additionally, the yield of LPG shows a volcano type with increasing reaction temperature, and the optimal reaction temperature is 370 ℃. Low space velocity is more favorable to the CO₂ conversion, and LPG selectivity in hydrocarbon products still maintains about 90%. High reaction pressure is beneficial to improving the yield of LPG via promoting the secondary hydrogenation reaction over the SSZ-13 zeolite and inhibiting CO formation. Furthermore, no obvious deactivation is observed after a time on stream (TOS) of 100 h over the In₂O₃/SSZ-13 bifunctional catalyst at 350 ℃, 3 MPa and 9000 mL/(g_cat·h). The research provides a new strategy for highly selective synthesis of LPG from CO₂ hydrogenation.
- CO₂ hydrogenation,
- LPG synthesis,
- In₂O₃/SSZ-13 composite catalyst,
- size effect,
- reaction condition

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References(30)

References

[1]	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
[2]	LIU X L, WANG M H, ZHOU C, ZHOU W, CHENG K, KANG J C, ZHANG Q H, DENG W P, WANG Y. Selective transformation of carbon dioxide into lower olefins with a bifunctional catalyst composed of ZnGa₂O₄ and SAPO-34[J]. ChemComm,2018,54:140−143.
[3]	JIANG X, NIE X, GUO X, SONG C, CHEN J G. Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis[J]. Chem Rev,2020,120(15):7984−8034. doi: 10.1021/acs.chemrev.9b00723
[4]	DAS S, PEREZ RAMIREZ J, GONG J, DEWANGAN N, HIDAJAT K, GATES B. C, KAWI S. Core-shell structured catalysts for thermocatalytic, photocatalytic, and electrocatalytic conversion of CO₂[J]. Chem Soc Rev,2000,49:2937−3004.
[5]	GOEPPERT A, CZAUN M, JONES J P, SURYA PRAKASH G K, OLAH G A. Recycling of carbon dioxide to methanol and derived products - closing the loop[J]. Chem Soc Rev,2014,43(23):7995−8048. doi: 10.1039/C4CS00122B
[6]	LI C, YUAN X, FUJIMOTO K. Direct synthesis of LPG from carbon dioxide over hybrid catalysts comprising modified methanol synthesis catalyst and β-type zeolite[J]. Appl Catal A: Gen,2014,475:155−160. doi: 10.1016/j.apcata.2014.01.025
[7]	LI H, ZHANG P, GUO L, HE Y, ZENG Y, THONGKAM M, NATAKARANAKUL J, KOJIMA T, REUBROYCHAROEN P, VITIDSANT T, YANG G, TSUBAKI N. A well-defined core-shell-structured capsule catalyst for direct conversion of CO₂ into liquefied petroleum gas[J]. Chem Sus Chem,2020,13(8):2060−2065. doi: 10.1002/cssc.201903576
[8]	GAO P, DANG S, LI S, BU X, LIU Z, QIU M, YANG C, WANG H, ZHONG L, HAN Y, LIU Q, WEI W, SUN Y. Direct production of lower olefins from CO₂ conversion via bifunctional catalysis[J]. ACS Catal,2017,8:571−578.
[9]	LI Z L, WANG J J, QU Y Z, LIU H L, TANG C Z, MIAO S, FENG Z C, AN H Y, LI C. Highly selective conversion of carbon dioxide to lower olefins[J]. ACS Catal,2017,7(12):8544−8548. doi: 10.1021/acscatal.7b03251
[10]	LIU X, WANG M, YIN H, HU J, CHENG K, KANG J, ZHANG Q, WANG Y. Tandem catalysis for hydrogenation of CO and CO₂ to lower olefins with bifunctional catalysts composed of spinel oxide and SAPO-34[J]. ACS Catal,2020,10:8303−8314.
[11]	MA Z, POROSOFF M D. Development of tandem catalysts for CO₂ hydrogenation to olefins[J]. ACS Catal,2019,9(3):2639−2656. doi: 10.1021/acscatal.8b05060
[12]	SONG G, LI M, YAN P, NAWAZ M A, LIU D. High conversion to aromatics via CO2-FT over a CO-reduced Cu-Fe₂O₃ catalyst integrated with HZSM-5[J]. ACS Catal,2020,10(19):11268−11279. doi: 10.1021/acscatal.0c02722
[13]	WANG Y, TAN L, TAN M H, ZHANG P P, FANG Y, YONEYAMA Y, YANG G H, TSUBAKI N. Rationally designing bifunctional catalysts as an efficient strategy to boost CO₂ hydrogenation producing value-added aromatics[J]. ACS Catal,2019,9(2):895−901. doi: 10.1021/acscatal.8b01344
[14]	ZHOU C, SHI J, ZHOU W, CHENG K, ZHANG Q, KANG J, WANG Y. Highly active ZnO-ZrO₂ aerogels integrated with H-ZSM-5 for aromatics synthesis from carbon dioxide[J]. ACS Catal,2019,10:302−310.
[15]	GAO P, ZHANG L, LI S, ZHOU Z, SUN Y. Novel heterogeneous catalysts for CO₂ hydrogenation to liquid fuels[J]. ACS Cent Sci,2020,6(10):1657−1670. doi: 10.1021/acscentsci.0c00976
[16]	GAO P, LI S, BU X, DANG S, LIU Z, WANG H, ZHONG L, QIU M, YANG C, CAI J, WEI W, SUN Y. Direct conversion of CO₂ into liquid fuels with high selectivity over a bifunctional catalyst[J]. Nat Chem,2017,9(10):1019−1024. doi: 10.1038/nchem.2794
[17]	WEI J, YAO R, GE Q, XU D, FANG C, ZHANG J, XU H, SUN J. Precisely regulating Brønsted acid sites to promote the synthesis of light aromatics via CO₂ hydrogenation[J]. Appl Catal B: Environ,2021,283:119648.
[18]	LIU Z, NI Y, SUN T, ZHU W, LIU Z. Conversion of CO₂ and H₂ into propane over InZrO and SSZ-13 composite catalyst[J]. J. Energy Chem,2021,54:111−117. doi: 10.1016/j.jechem.2020.04.069
[19]	XU Z, MA H, HUANG Y, QIAN W, ZHANG H, YING W. Synthesis of submicron SSZ-13 with tunable acidity by the seed-assisted method and its performance and coking behavior in the MTO reaction[J]. ACS Omega,2020,5(38):24574−24583. doi: 10.1021/acsomega.0c03075
[20]	YU H F, ZHANG G P, HAN LN, CHANG L P, BAO W R, WANG J C. Cu-SSZ-13 catalyst synthesized under microwave irradiation and its performance in catalytic removal of NO_x from vehicle exhaust[J]. Acta Phys-Chim Sin,2015,31(11):2165−2173. doi: 10.3866/PKU.WHXB201509184
[21]	XU Z, LI J, HUANG Y, MA H, QIAN W, ZHANG H, YING W. Size control of SSZ-13 crystals with APAM and its influence on the coking behaviour during MTO reaction[J]. Catal Sci Technol,2019,9(11):2888−2897. doi: 10.1039/C9CY00412B
[22]	WU L, HENSEN E J M. Comparison of mesoporous SSZ-13 and SAPO-34 zeolite catalysts for the methanol-to-olefins reaction[J]. Catalysis Today,2014,235:160−168. doi: 10.1016/j.cattod.2014.02.057
[23]	DANG S S, GAO P, LIU Z Y, CHEN X Q, YANG C G, WANG H, ZHONG L S, LI S G, SUN Y H. Role of zirconium in direct CO₂ hydrogenation to lower olefins on oxide/zeolite bifunctional catalysts[J]. J Catal,2018,364:382−393. doi: 10.1016/j.jcat.2018.06.010
[24]	JIA X, SUN K, WANG J, SHEN C, LIU C J. Selective hydrogenation of CO₂ to methanol over Ni/In₂O₃ catalyst[J]. J. Energy Chem,2020,50:409−415. doi: 10.1016/j.jechem.2020.03.083
[25]	YU Z, HONG N W, RUO YU C. In situ synthesis of Cu-SSZ-13/cordierite monolithic catalyst for the selective catalytic reduction of NO with NH₃[J]. Acta Phys-Chim Sin,2015,31(2):329−336. doi: 10.3866/PKU.WHXB201412082
[26]	LI Z, QU Y, WANG J, LIU H, LI M, MIAO S, LI C. Highly selective conversion of carbon dioxide to aromatics over tandem catalysts[J]. Joule,2019,3(2):570−583. doi: 10.1016/j.joule.2018.10.027
[27]	YE J, LIU C, M EI, D, G E, Q. Active oxygen vacancy site for methanol synthesis from CO₂ hydrogenation on In₂O₃(110): A DFT study[J]. ACS Catal,2013,3(6):1296−1306. doi: 10.1021/cs400132a
[28]	MARTIN O, MARTIN A J, MONDELLI C, MITCHELL S, SEGAWA T F, HAUERT R, DROUILLY C, CURULLA-FERRE D, PEREZ-RAMIREZ J. Indium oxide as a superior catalyst for methanol synthesis by CO₂ hydrogenation[J]. Angew Chem Int Ed Eng,2016,55(21):6261−6265. doi: 10.1002/anie.201600943
[29]	LI Y, Wang W T, ZHAO F, XU Y T. H - SSZ - 13 molecular sieve synthesized by introducing accelerant and its effect on reactivity of MTO[J]. J Tiangong Univ,2015,34(6):35−40.
[30]	NUMPILAI T, WATTANAKIT C, CHAREONPANICH M, LIMTRAKUL J, WITOON T. Optimization of synthesis condition for CO₂ hydrogenation to light olefins over In₂O₃ admixed with SAPO-34[J]. Energy Convers Manage,2019,180:511−523. doi: 10.1016/j.enconman.2018.11.011