Effect of CaO on the performance of Cu-ZnO-ZrO2 catalyst for methanol synthesis from CO2 and H2

CHEN Jun-jun; GAO Wen-gui; WANG Hua; NA Wei

Volume 44 Issue 4

Apr. 2016

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2016 > 44(4): 437-448

CHEN Jun-jun, GAO Wen-gui, WANG Hua, NA Wei. Effect of CaO on the performance of Cu-ZnO-ZrO2 catalyst for methanol synthesis from CO2 and H2[J]. Journal of Fuel Chemistry and Technology, 2016, 44(4): 437-448.

Citation:

CHEN Jun-jun, GAO Wen-gui, WANG Hua, NA Wei. Effect of CaO on the performance of Cu-ZnO-ZrO₂ catalyst for methanol synthesis from CO₂ and H₂[J]. Journal of Fuel Chemistry and Technology, 2016, 44(4): 437-448.

Citation:

PDF( 7312 KB)

Effect of CaO on the performance of Cu-ZnO-ZrO₂ catalyst for methanol synthesis from CO₂ and H₂

CHEN Jun-jun^{1, 2},
GAO Wen-gui^{1, 3
,
,},
WANG Hua^{1, 3},
NA Wei^{1, 3}

1.
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China
2.
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650093, China
3.
Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China

More Information

Corresponding author: E-mail: gao_wengui@126.com.
Received Date: 2015-10-28
Rev Recd Date: 2016-01-25

Available Online: 2021-01-23

Publish Date: 2016-04-30

Abstract

Abstract

CuO:ZnO:ZrO₂=5:4:1 (molar ratio) catalysts were prepared with CaO doping of 0,1%, 2%, 4%, 8%, 16% (molar fraction) by cocurrent-flow co-precipitation. X-ray diffraction (XRD), thermal analysis(TG-DTG), Fourier infrared (FT-IR), N₂ adsorption desorption (BET), X-ray photoelectron spectroscopy (XPS), hydrogen temperature programmed reduction (H₂-TPR), CO₂ temperature programmed desorption (CO₂-TPD) and NH₃ temperature programmed desorption (NH₃-TPD) were used to characterize the catalysts. The catalyst activity was evaluated with a lab-made fixed bed reactor. Results show that CaO doping enhances Lewis acid and surface alkaline of the catalyst, increases the amount of high temperature carbonate in the catalysts, improves the thermal stability, reduces the CuO particle size, enhances the synergistic effect of Cu-Zn, increases the Cu specific surface area and the Cu dispersion. The catalyst activity is influenced by the surface acidity, the specific surface area of copper, the synergistic effect of Cu-Zn and the dispersion of copper. When the doping amount of CaO is 2%, the copper specific surface area is 79.3 m²/g, the dispersion degree of copper is 34.8%, the CO₂ conversion is 19.01%, the selectivity of methanol is 24.55% and the yield of methanol is 0.044 g/(g_cat·h), catalyst activity is the highest. With the amount of CaO increasing, the excessive CaO occupies the catalyst pore and covers the surface active sites, the Lewis acid and the surface alkaline of the catalysts become so strong that the effective contact of CuO and H₂ is reduced, CO₂ is difficult to desorb, resulting in decrease of catalytic activity. Therefore, the proper doping amount of CaO (2%) can promote the synthesis of methanol through CO₂ hydrogenation.
- cocurrent-flow co-precipitation,
- CaO,
- Cu-ZnO-ZrO₂,
- CO₂ and H₂,
- methanol

FullText(HTML)

References(36)

References

[1]	STEWART C, HESSAMI M. A study of methods of carbon dioxide capture and sequestration-the sustainability of a photosynthetic bioreactor approach[J]. Energy Convers Manage, 2005, 46(3): 403-420. doi: 10.1016/j.enconman.2004.03.009
[2]	LI L, ZHAO N, WEI W, SUN Y H. A review of research progress on CO₂ capture, storage, and utilization in Chinese academy of sciences[J]. Fuel, 2013, 108: 112-130. doi: 10.1016/j.fuel.2011.08.022
[3]	ARESTA M, DIBENEDETTO A. Utilization of CO₂ as a chemical feedstock: Opportunities and challenges[J]. Dalton Trans, 2007, 28: 2975-2992. https://www.researchgate.net/publication/6216482_Utilisation_of_CO2_as_a_chemical_feedstock_opportunities_and_challenges
[4]	SHAMSUL N S, KAMARUDIN S K, RAHMAN N A, KOFLI N T. An overview on the production of bio-methanol as potential renewable energy[J]. Renew Sust Energy Rev, 2014, 33(2): 578-588. https://www.researchgate.net/publication/260758801_An_overview_on_the_production_of_bio-methanol_as_potential_renewable_energy
[5]	BAIKER A. Utilization of carbon dioxide in heterogeneous catalytic synthesis[J]. Appl Organomet Chem, 2000, 14(12): 751-762. doi: 10.1002/(ISSN)1099-0739
[6]	NATESAKHAWAT S, LEKSE J W, BALTRUS J P, OHODNICKI JR P R, HOWARD B H, DENG X Y, MATRANGA C. Active sites and structure-activity relationships of copper-based catalysts for carbon dioxide hydrogenation to methanol[J]. ACS Catal, 2012, 2(8): 1667-1676. doi: 10.1021/cs300008g
[7]	LI C M, YUAN X D, FUJIMOTO K. Development of highly stable catalyst for methanol synthesis from carbon dioxide[J]. Appl Catal A: Gen, 2014, 469: 306-311. https://www.researchgate.net/publication/270924206_Development_of_highly_stable_catalyst_for_methanol_synthesis_from_carbon_dioxide
[8]	MA Y, SUN Q, WU D, FAN W H, ZHANG Y L, DENG J F. A practical approach for the preparation of high activity Cu/ZnO/ZrO₂ catalyst for methanol synthesis from CO₂ hydrogenation[J]. Appl Catal A: Gen, 1998, 171(1): 45-55. doi: 10.1016/S0926-860X(98)00079-9
[9]	SLOCZYNSKI J, GRABOWSKI R, OLSZEWSKI P, KOZLOWSKA A, STOCH J, LACHOWSKA M, SKRZYPEK J. Effect of metal oxide additives on the activity and stability of Cu/ZnO/ZrO₂ catalysts in the synthesis of methanol from CO₂ and H₂[J]. Appl Catal A: Gen, 2006, 310(8): 127-137. https://www.researchgate.net/publication/272071371_The_Influence_of_ZnZr_Ratios_on_CuO-ZnO-ZrO2_Catalysts_for_Methanol_Synthesis_from_CO2_Hydrogenation
[10]	SLOCZYNSKI J, GRABOWSKI R, KOZLOWSKA A, OLSZEWSKI P, LACHOWSKA M, SKRZYPEK J, STOCH J. Effect of Mg and Mn oxide additions on structural and adsorptive properties of Cu/ZnO/ZrO₂ catalysts for the methanol synthesis from CO₂[J]. Appl Catal A: Gen, 2003, 249(1): 129-138. doi: 10.1016/S0926-860X(03)00191-1
[11]	BAN H Y, LI C M, ASAMI K J, FUJIMOTO K. Influence of rare-earth elements (La, Ce, Nd and Pr) on the performance of Cu/Zn/Zr catalyst for CH₃OH synthesis from CO₂[J]. Catal Commun, 2014, 54: 50-54. doi: 10.1016/j.catcom.2014.05.014
[12]	TAN L, YANG G H, YONEYAMA Y, KOU Y L, TAN Y H, VITIDSANT T, TSUBAKI N. Iso-butanol direct synthesis from syngas over the alkali metals modified Cr/ZnO catalysts[J]. Appl Catal A: Gen, 2015, 505: 141-149. doi: 10.1016/j.apcata.2015.08.002
[13]	ZHONG C L, GUO X M, MAO D S, WANG S, WU G S, LU G Z. Effects of alkaline-earth oxides on the performance of a CuO-ZrO₂ catalyst for methanol synthesis via CO₂ hydrogenation[J]. RSC Adv, 2015, 5(65): 52958-52965. doi: 10.1039/C5RA06508A
[14]	ELIAS K F M, LUCREDIO A F, ASSAF E M. Effect of CaO addition on acid properties of Ni-Ca/Al₂O₃ catalysts applied to ethanol steam reforming[J]. Int J Hydrogen Energy, 2013, 38(11): 4407-4417. doi: 10.1016/j.ijhydene.2013.01.162
[15]	MILLAR G J, HOLM I H, UWINS P J R, DRENNAN J. Characterization of precursors to methanol synthesis catalysts Cu/ZnO system[J]. J Chem Soc Faraday, 1998, 94(4): 593-600. doi: 10.1039/a703954i
[16]	BEHRENS M, SCHLÖGL R. How to prepare a good Cu/ZnO catalyst or the role of solid state chemistry for the synthesis of nanostructured catalysts[J]. Z Anorg Allg Chem, 2013, 639(15): 2683-2695. doi: 10.1002/zaac.v639.15
[17]	LI J L, INUI T. Characterization of precursors of methanol synthesis catalysts, copper/zinc/aluminum oxides, precipitated at different pHs and temperatures[J]. Appl Catal A: Gen, 1996, 137(1): 105-117. doi: 10.1016/0926-860X(95)00284-7
[18]	BEHRENS M, GIRGSDIES F, TRUNSCHKE A, SCHLÖGL R. Minerals as model compounds for Cu/ZnO catalyst precursors: Structural and thermal properties and IR spectra of mineral and synthetic Zincian malachite,rosasite and aurichalcite and a catalyst precursor mixture[J]. Eur J Inorg Chem, 2009, 2009(10): 1347-1357. https://www.researchgate.net/publication/228012859_Minerals_as_Model_Compounds_for_CuZnO_Catalyst_Precursors_Structural_and_Thermal_Properties_and_IR_Spectra_of_Mineral_and_Synthetic_Zincian_Malachite_Rosasite_and_Aurichalcite_and_a_Catalyst_Precursor
[19]	BEMS B, SCHUR M, DASSENOY A, JUNKES H, HEREIN D, SCHLÖGL R. relations between synthesis and microstructural properties of copper/zinc hydroxycarbonates[J]. Chem Eur J, 2003, 9(9): 2039-2052. doi: 10.1002/chem.200204122
[20]	BALTES C, VUKOJEVI S, SCHUTH F. Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al₂O₃ catalysts for methanol synthesis[J]. J Catal, 2008, 258(2): 334-344. doi: 10.1016/j.jcat.2008.07.004
[21]	ELIAS F, ACHIM S, THILO L, HARALD H, INGO K. The influence of the precipitation/ageing temperature on a Cu/ZnO/ZrO₂ catalyst for methanol synthesis from H₂ and CO₂[J]. ChemCatChem, 2014, 6(6): 1721-1730. doi: 10.1002/cctc.v6.6
[22]	夏王琼, 唐浩东, 林胜达, 岑亚青, 刘化章. 甲醇合成Cu/ZnO催化剂前驱体的物相转变[J]. 催化学报, 2009, 30(9): 879-884. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200909007.htm XIA Wang-qiong, TANG Hao-dong, LIN Sheng-da, CEN Ya-qing, LIU Hua-zhang. Precursor phase transition of Cu/ZnO catalyst for methanol synthesis[J]. Chin J Catal, 2009, 30(9): 879-884. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200909007.htm
[23]	STOILOVA D, KOLEVA V, VASSILEVA V. Infrared study of some synthetic phases of malachite (Cu₂(OH)₂CO₃)-hydrozincite (Zn₅(OH)₆(CO₃)₂) series[J]. Spectrochi Acta A, 2002, 58(9): 2051-2059. doi: 10.1016/S1386-1425(01)00677-1
[24]	SONG F E, TAN Y S, XIE H J, ZHANG Q D, HAN Y Z. Direct synthesis of dimethylether from biomass-derived syngas over Cu-ZnO-Al₂O₃-ZrO₂(x)/γ-Al₂O₃ bifunctional catalysts: Effect of Zr-loading[J]. Fuel Process Technol, 2014, 126: 88-94.
[25]	张强, 徐征, 千载虎. 在CuO-ZnO及CuO-ZnO-ZrO₂催化剂上CO₂/H₂低压合成甲醇的研究[J]. 催化学报, 1989, 10(1): 22-28. ZHANG Qiang, XU Zheng, QIAN Zai-hu. The study of low pressure synthesis for methanol from CO₂/H₂ on CuO-ZnO and CuO-ZnO-ZrO₂ catalyst[J]. Chin J Catal, 1989, 10(1): 22-28.
[26]	ZHAO H J, LIN M G, FANG K G, ZHOU J, LIU Z Y, ZENG G F, SUN Y H. A novel Cu-Mn/Ca-Zr catalyst for the synthesis of methyl formate from syngas[J]. RSC Adv, 2015, 5(83): 67630-67637. doi: 10.1039/C5RA13555A
[27]	DAI W L, SUN Q, DENG J F, WU D, SUN Y H. XPS studies of Cu/ZnO/Al₂O₃ ultra-fine catalysts derived by a novel gel oxalate co-precipitation for methanol synthesis by CO₂+H₂[J]. Appl Surf Sci, 2001, 177(3): 172-179. doi: 10.1016/S0169-4332(01)00229-X
[28]	GUO X M, MAO D S, LU G Z, WANG S, WU G S. Glycine-nitrate combustion synthesis of CuO-ZnO-ZrO₂ catalysts for methanol synthesis from CO₂ hydrogenation[J]. J Catal, 2010, 271(2): 178-185. doi: 10.1016/j.jcat.2010.01.009
[29]	BONURA G, CORDARO M, CANNILLA C, ARENA F, FRUSTERI F. The changing nature of the active site of Cu-Zn-Zr catalysts for the CO₂ hydrogenation reaction to methanol[J]. Appl Catal B: Environ, 2014, 152-153: 152-161. https://www.researchgate.net/publication/260166753_The_changing_nature_of_the_active_site_of_Cu-Zn-Zr_catalysts_for_the_CO2_hydrogenation_reaction_to_methanol
[30]	GUO X M, MAO D S, LU G Z, WANG S, WU G S. CO2 hydrogenation to methanol over Cu/ZnO/ZrO₂ catalysts prepared via a route of solid-state reaction[J]. Catal Commun, 2011, 12(12): 1095-1098. doi: 10.1016/j.catcom.2011.03.033
[31]	李基涛, 张伟德, 陈明旦, 区泽棠. 铜基催化剂上CO₂吸附的TPD和TPSR研究[J]. 天然气化工, 1998, 23(5): 14-17. LI Ji-tao, ZHANG Wei-de, CHEN Ming-dan, OU Ze-tang. Study of TPD and TPSR of CO₂ adsorption on Cu based catalyst[J].Nat gas Chem Eng, 1998, 23(5): 14-17.
[32]	HATTORI H. Heterogeneous basic catalysis[J]. Chem Rev, 1995, 95(3): 537-558. doi: 10.1021/cr00035a005
[33]	ARENA F, ITALIANO G, BARBERA K, BORDIGA S, BONURA G, SPADARO L, FRSTERI F. Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO₂ catalysts in the CO₂ hydrogenation to CH3OH[J]. Appl Catal A: Gen, 2008, 350(1): 16-23. doi: 10.1016/j.apcata.2008.07.028
[34]	徐友明, 沈本贤, 何金海, 罗锡辉. 用PASCA及NH₃-TPD法表征Al₂O₃载体表面酸度[J]. 分析测试学报, 2006, 25(1): 41-44. XU You-ming, SHEN Ben-xian, HE Jin-hai, LUO Xi-hui. Study of surface acidity of γ-Al₂O₃ support by PASCA and NH₃-TPD[J]. J Inst Anal, 2006, 25(1): 41-44.
[35]	JUNG K T, BEL A T. The effects of synthesis and pretreatment conditions on the bulk structure and surface properties of zirconia[J]. J Mol Catal A: Chem, 2000, 163(1/2): 27-42. https://www.researchgate.net/publication/229127074_The_effects_of_synthesis_and_pretreatment_conditions_on_the_bulk_structure_and_surface_properties_of_zirconia
[36]	SAMSON K, ŠLIWA M, SOCHA R P, GORA-MAREK K., MUCHA D, RUTKOWSKA-ZBIK D, PAUL J F, RUGGIERO-MIKOLAJCZYK M, GRABOWSKI R, SŁOCZYNKI J. Influence of ZrO₂ structure and copper electronic state on activity of Cu/ZrO₂ catalysts in methanol synthesis from CO₂[J]. ACS Catal, 2014, 4(10): 3730-3741.