Zn-ZrO_2/H-ZSM-5双功能催化剂上合成气转化制汽油馏分的研究
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摘要
针对合成气直接转化制汽油馏分反应,合成了Zn-ZrO_2金属氧化物与沸石分子筛复合的双功能催化剂,结果显示Zn-ZrO_2/H-ZSM-5具有较高的CO转化率和汽油馏分选择性。考察了反应温度和接触时间对Zn-ZrO_2和Zn-ZrO_2/H-ZSM-5双功能催化剂的影响,证实了合成气经甲醇/二甲醚中间体制汽油馏分的反应路径。研究了Zn/Zr摩尔比、H-ZSM-5分子筛的Si/Al比对催化性能的影响,结果表明Zn/Zr摩尔比为1∶32、Si/Al为200时可获得了较好的转化率(52%)和汽油馏分选择性(62%),且催化剂经100h测试稳定性良好。
Hybrid catalysts combined Zn-ZrO_2oxide with different zeolites were synthesized and used for the direct conversion of syngas.It was found that the Zn-ZrO_2/H-ZSM-5catalyst exhibited higher CO conversion as well as gasoline fuel selectivity than other catalysts.The effects of reaction temperature and contact time on catalytic performances over Zn-ZrO_2oxide and Zn-ZrO_2/H-ZSM-5were further investigated,and the results suggested that methanol and dimethyl ether intermediates were firstly formed over Zn-ZrO_2and then further transformed into gasoline fuel over H-ZSM-5zeolite.The Zn/Zr molar ratio and Si/Al molar ratio of H-ZSM-5over Zn-ZrO_2/H-ZSM-5bifunctional catalyst were also studied.The results showed that the Zn/Zr molar ratio at1∶32and the Si/Al ratio of H-ZSM-5at 200over Zn-ZrO_2/H-ZSM-5were beneficial to the conversion of syngas and the formation of gasoline fuel.Moreover,the catalyst was stable,there was no significant deactivation in 100h.
Hybrid catalysts combined Zn-ZrO_2oxide with different zeolites were synthesized and used for the direct conversion of syngas.It was found that the Zn-ZrO_2/H-ZSM-5catalyst exhibited higher CO conversion as well as gasoline fuel selectivity than other catalysts.The effects of reaction temperature and contact time on catalytic performances over Zn-ZrO_2oxide and Zn-ZrO_2/H-ZSM-5were further investigated,and the results suggested that methanol and dimethyl ether intermediates were firstly formed over Zn-ZrO_2and then further transformed into gasoline fuel over H-ZSM-5zeolite.The Zn/Zr molar ratio and Si/Al molar ratio of H-ZSM-5over Zn-ZrO_2/H-ZSM-5bifunctional catalyst were also studied.The results showed that the Zn/Zr molar ratio at1∶32and the Si/Al ratio of H-ZSM-5at 200over Zn-ZrO_2/H-ZSM-5were beneficial to the conversion of syngas and the formation of gasoline fuel.Moreover,the catalyst was stable,there was no significant deactivation in 100h.
引文
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[3]MARTINEZ A,PRIETO G.The application of zeolites and periodic mesoporous silicas in the catalytic conversion of synthesis gas[J].Topics in Catalysis,2009,52(1/2):75-90.
[4]SUN B,QIAO M,FAN K,et al.Fischer-Tropsch synthesis over molecular sieve supported catalysts[J].ChemCatChem,2011,3(3):542-550.
[5]LI Y,WANG T,WU C,et al.Gasoline-range hydrocarbon synthesis over cobalt-based Fischer-Tropsch catalysts supported on SiO2/HZSM-5[J].Energy&Fuels,2008,22(3):1897-1901.
[6]KANG J,CHENG K,ZHANG L,et al.Mesoporous zeolite-supported ruthenium nanoparticles as highly selective Fischer-Tropsch catalysts for the production of C5-C11isoparaffins[J].Angewandte Chemie International Edition,2011,50(22):5200-5203.
[7]CHENG K,ZHANG L,KANG J,et al.Selective transformation of syngas into Gasoline-Range hydrocarbons over mesoporous H-ZSM-5-supported cobalt nanoparticles[J].Chemistry-A European Journal,2015,21(5):1928-1937.
[8]CHENG K,GU B,LIU X,et al.Direct and highly selective conversion of synthesis gas into lower olefins:design of a bifunctional catalyst combining methanol synthesis and carbon-carbon coupling[J].Angewandte Chemie International Edition,2016,128(15):4803-4806.
[9]JIAO F,LI J,PAN X,et al.Selective conversion of syngas to light olefins[J].Science,2016,351(6277):1065-1068.
[10]ZHAO B,ZHAI P,WANG P,et al.Direct transformation of syngas to aromatics over Na-Zn-Fe5C2and hierarchical HZSM-5tandem catalysts[J].Chemistry,2017,3(2):323-333.
[11]GAO P,LI S,BU X,et al.Direct conversion of CO2into liquid fuels with high selectivity over a bifunctional catalyst[J].Nature Chemistry,2017,9(10):1019-1024.
[12]CHENG K,ZHOU W,KANG J,et al.Bifunctional catalysts for one-step conversion of syngas into aromatics with excellent selectivity and stability[J].Chemistry,2017,3(2):334-347.
[13]YANG J,PAN X,JIAO F,et al.Direct conversion of syngas to aromatics[J].Chemical Communications,2017,53(81):11146-11149.
[14]ZHANG P,TAN L,YANG G,et al.One-pass selective conversion of syngas to para-xylene[J].Chemical Science,2017,8(12):7941-7946.
[15]LIU X,ZHOU W,YANG Y,et al.Design of efficient bifunctional catalysts for direct conversion of syngas into lower olefins via methanol/dimethyl ether intermediates[J].Chemical Science,2018,9(20):4708-4718.
[16]WANG Y,JIA A P,LUO M F,et al.Highly active spinel type CoCr2O4catalysts for dichloromethane oxidation[J].Applied Catalysis B:Environmental,2015,165:477-486.
[17]OLSBYE U,SVELLE S,BJRGEN M,et al.Conversion of methanol to hydrocarbons:how zeolite cavity and pore size controls product selectivity[J].Angewandte Chemie International Edition,2012,51(24):5810-5831.
[18]LI Y,HE D,ZHU Q,et al.Effects of redox properties and acid-base properties on isosynthesis over ZrO2-based catalysts[J].Journal of Catalysis,2004,221(2):584-593.
[19]SHEN X,KANG J,NIU W,et al.Impact of hierarchical pore structure on the catalytic performances of MFI zeolites modified by ZnO for the conversion of methanol to aromatics[J].Catalysis Science&Technology,2017,7(16):3598-3612.