碱助剂对完全液相-热解法CuZnAl催化合成低碳醇性能的影响
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摘要
采用完全液相技术结合热解方法制备了固定床用CuZnAl催化剂,研究表明,该方法能保留完全液相技术赋予催化剂的特殊性能,可以发展成为将完全液相技术拓展于固定床催化剂的通用方法.在所制催化剂中引入碱助剂同样可以增加C_(2+)醇的选择性,但主要不是异丁醇,与现行常规方法制备的催化剂不同.通过对催化剂进行XRD、 H_2-TPR、 NH_3-TPD-MS、 BET等表征,结果表明,不同碱助剂对催化剂的作用方式和影响程度不同,使得催化剂中Cu物种的存在形式和数量、催化剂表面的酸碱性和量以及孔道结构存在差异,进而对催化剂性能产生影响.
CuZnAl catalysts for a fixed bed reactor were prepared by the complete liquid phase technology combined with pyrolysis method. The results showed that this method could retain the special properties of the catalysts entrusted by the complete liquid phase technology, and could be developed into a general method of extending the complete liquid phase technology to fixed bed catalyst preparation. The selectivity of C_(2+) alcohols can also be increased when introducing alkali promoters were added into the prepared catalysts, but C_(2+) alcohols was mainly not isobutanol, which was different from the catalysts prepared by conventional methods. XRD, H_2-TPR, NH_3-TPD-MS and BET measurement results showed that different alkali promoters had different action way and effects over the catalysts, which resulted in difference of active metals existing forms and amount, the catalyst surface acidic and basic strength and amount as well as pore structure, thus affecting the performance of the catalysts.
CuZnAl catalysts for a fixed bed reactor were prepared by the complete liquid phase technology combined with pyrolysis method. The results showed that this method could retain the special properties of the catalysts entrusted by the complete liquid phase technology, and could be developed into a general method of extending the complete liquid phase technology to fixed bed catalyst preparation. The selectivity of C_(2+) alcohols can also be increased when introducing alkali promoters were added into the prepared catalysts, but C_(2+) alcohols was mainly not isobutanol, which was different from the catalysts prepared by conventional methods. XRD, H_2-TPR, NH_3-TPD-MS and BET measurement results showed that different alkali promoters had different action way and effects over the catalysts, which resulted in difference of active metals existing forms and amount, the catalyst surface acidic and basic strength and amount as well as pore structure, thus affecting the performance of the catalysts.
引文
[1] Xiao Kang,Bao Zhenghong,Qi Xingzhen,et al.Structural evolution of CuFe bimetallic nanoparticles for higher alcohol synthesis[J].J Mol Catal:Chem,2013,378(11):319-325.
[2] Ho Ting Luk,Cecilia Mondelli,Daniel Curulla Ferré,et al.Status and prospects in higher alcohols synthesis from syngas[J].Chem Soc Rev,2017,46(5):1358-1426.
[3] Ge Qing-jie(葛庆杰),Xu Heng-yong(徐恒泳),Li wen-zhao(李文钊),et al.The key technology of producing liquid fuel from coalbed methane by syngas(煤层气经合成气制液体燃料的关键技术)[J].Chem Pro (化工进展),2009,28(6):917-921.
[4] a.Zaman S F,Smith K J.Synthesis gas conversion over a Rh-K-MoP/SiO2 catalyst[J].Catal Today,2011,171(1):266-274.b.Lu Peng(吕鹏),Xu Ding(徐钉),Shen Dong-ming(申东明),et al.Preparation of Cu-based catalyst by solid-phase grinding method with citric acid assisting and performance research in methanol synthesis reaction from CO2 hydrogenation(柠檬酸辅助固相研磨法制备铜基催化剂及在CO2加氢合成甲醇反应中的性能研究) [J].J Mol Catal(China)(分子催化),2017,31(2):141-151.
[5] Zhenghong Bao,Kang Xiao,Xingzhen Qi,et al.Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2+OH[J].J Ener Chem,2013,22(1):107-113.
[6] Heracleous E,Liakakou E T,Lappas A A,et al.Investigation of K-promoted Cu-Zn-Al,Cu-X-Al and Cu-Zn-X (X=Cr,Mn) catalysts for carbon monoxide hydrogenation to higher alcohols[J].Appl Catal:Gener,2013,455:145-154.
[7] Debao Li,Cheng Yang,Ning Zhao,et al.The performances of higher alcohol synthesis over nickel modified K2CO3/MoS2 catalyst[J].Fuel Proce Technol,2007,88(2):125-127.
[8] Yongjun Liu,Chaobo Liu,Xuan Deng,et al.A study on deactivation of Cu-Zn-Al catalyst for higher alcohols synthesis[J].RSC Adv,2015,5(12):9923-9927.
[9] Yongjun Liu,Zhi-jun Zuo,Chao Li,et al.Effect of preparation method on CuZnAl catalysts for ethanol synthesis from syngas[J].Appl Surf Sci,2015,356:124-127.
[10] Tian Hui-hui(田慧辉),Li Lei-lei(李磊磊),Dong Wei-bing(董伟兵),et al.Effect of the polyethylene glycols medium on catalytic performance for the ethanol synthesis from syngas in slurry reactor(聚乙二醇介质对浆态床合成气制乙醇催化性能的影响) [J].J Mol Catal(China)(分子催化),2016,30(3):235-242.
[11] Chunhui Luan,Anrong Zhang,Xiaodong Wang,et al.Catalytic activity of liquid phase prepared Cu-Zn-Al catalyst for CO hydrogenation in a fixed bed reactor[J].Indi J Chem,2012,51:1663-1668.
[12] de la Peňa O Shea V A,Menéndez N N,Tornero J D,et al.Unusually high selectivity to C2+ alcohols on bimetallic CoFe catalysts during CO hydrogenation[J].Catal Lett,2003,3/4(88):123-128.
[13] Nguyen Tien-Thao,Hassan Zahedi-Niaki M,Houshang Alamdari,et al.Effect of alkali additives over nanocrystalline Co-Cu-based perovskites as catalysts for higher-alcohol synthesis[J].J Catal,2007,245(2):348-357.
[14] Shi Xue-min(史雪敏),Yang Xu-zhuang(杨绪壮),Bai Feng-hua(白凤华) et al.Progress in additives of molybdenum based catalysts for higher alcohol synthesis from syngas(合成气制低碳醇钼基催化剂助剂的研究进展)[J].Chem Indus Engineer Pro(化工进展),2010,29(12):2291-2297.
[15] Fu Yi-lu(伏义路),Bao jun(鲍骏),Bian Guo-zhu(卞国柱),et al.Catalytic properties and structure of K-Co-Mo catalysts prepared by sol-gel method for mixed alcohol synthesis——effect of k content(溶胶—凝胶法制备K—Co—Mo催化剂的结构及其合成低碳醇性能研究——钾含量的影响)[J].J Mol Catal(China)(分子催化),1999,13(5):357-361.
[16] Yongjun Liu,Chaobo Liu,Chao Li,et al.CO hydrogenation to higher alcohols over Cu/Zn/Al catalysts without alkalis or fischer-tropsch elements:The effect of triethanolamine content[J].Catal Commun,2016,76:29-32.
[17] Chinchen G,Mansfied K,Spencer M.Methanol Synthesis[J].Chemtech,1990,11:693-699.
[18] Wei Jun-yi(魏珺谊),Gao Zhi-hua(高志华),Huang Wei(黄伟).Effect of structural ordering on the performance of mesoporous carbon supported CuCoCe catalyst in the synthesis of higher alcohols from syngas(介孔碳有序度对其负载的CuCoCe催化剂催化合成气制低碳醇性能的影响)[J].Chem J Chin Univer(高等学校化学学报),2018,39(8):1741-1749.
[19] Polster C S,Nair H ,Baertsch C D.Study of active sites and mechanism responsible for highly selective CO oxidation in H2 rich atmospheres on a mixed Cu and Ce oxide catalyst[J].J Catal,2009,266(2):308-319.
[20] Sun Jie,Cai Qiu-xia,Wan Yan,et al.Promotional effects of cesium promoter on higher alcohol synthesis from syngas over cesium-promoted Cu/ZnO/Al2O3 catalysts[J].ACS Catal,2016,6(9):5771-5785.
[21] Liakakou E T,Heracleous E,Triantafyllidis K S,et al.K-promoted NiMo catalysts supported on activated carbon for the hydrogenation reaction of CO to higher alcohols:Effect of support and active metal[J].Appl Catal:Environ,2015,165:296-305.
[22] Rungravee Phienluphon,Kitima Pinkaew,Guohui Yang,et al.Designing core (Cu/ZnO/Al2O3)-shell (SAPO-11) zeolite capsule catalyst with a facile physical way for dimethyl ether direct synthesis from syngas[J].Chem Engineer J,2015,270:605-611.
[2] Ho Ting Luk,Cecilia Mondelli,Daniel Curulla Ferré,et al.Status and prospects in higher alcohols synthesis from syngas[J].Chem Soc Rev,2017,46(5):1358-1426.
[3] Ge Qing-jie(葛庆杰),Xu Heng-yong(徐恒泳),Li wen-zhao(李文钊),et al.The key technology of producing liquid fuel from coalbed methane by syngas(煤层气经合成气制液体燃料的关键技术)[J].Chem Pro (化工进展),2009,28(6):917-921.
[4] a.Zaman S F,Smith K J.Synthesis gas conversion over a Rh-K-MoP/SiO2 catalyst[J].Catal Today,2011,171(1):266-274.b.Lu Peng(吕鹏),Xu Ding(徐钉),Shen Dong-ming(申东明),et al.Preparation of Cu-based catalyst by solid-phase grinding method with citric acid assisting and performance research in methanol synthesis reaction from CO2 hydrogenation(柠檬酸辅助固相研磨法制备铜基催化剂及在CO2加氢合成甲醇反应中的性能研究) [J].J Mol Catal(China)(分子催化),2017,31(2):141-151.
[5] Zhenghong Bao,Kang Xiao,Xingzhen Qi,et al.Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2+OH[J].J Ener Chem,2013,22(1):107-113.
[6] Heracleous E,Liakakou E T,Lappas A A,et al.Investigation of K-promoted Cu-Zn-Al,Cu-X-Al and Cu-Zn-X (X=Cr,Mn) catalysts for carbon monoxide hydrogenation to higher alcohols[J].Appl Catal:Gener,2013,455:145-154.
[7] Debao Li,Cheng Yang,Ning Zhao,et al.The performances of higher alcohol synthesis over nickel modified K2CO3/MoS2 catalyst[J].Fuel Proce Technol,2007,88(2):125-127.
[8] Yongjun Liu,Chaobo Liu,Xuan Deng,et al.A study on deactivation of Cu-Zn-Al catalyst for higher alcohols synthesis[J].RSC Adv,2015,5(12):9923-9927.
[9] Yongjun Liu,Zhi-jun Zuo,Chao Li,et al.Effect of preparation method on CuZnAl catalysts for ethanol synthesis from syngas[J].Appl Surf Sci,2015,356:124-127.
[10] Tian Hui-hui(田慧辉),Li Lei-lei(李磊磊),Dong Wei-bing(董伟兵),et al.Effect of the polyethylene glycols medium on catalytic performance for the ethanol synthesis from syngas in slurry reactor(聚乙二醇介质对浆态床合成气制乙醇催化性能的影响) [J].J Mol Catal(China)(分子催化),2016,30(3):235-242.
[11] Chunhui Luan,Anrong Zhang,Xiaodong Wang,et al.Catalytic activity of liquid phase prepared Cu-Zn-Al catalyst for CO hydrogenation in a fixed bed reactor[J].Indi J Chem,2012,51:1663-1668.
[12] de la Peňa O Shea V A,Menéndez N N,Tornero J D,et al.Unusually high selectivity to C2+ alcohols on bimetallic CoFe catalysts during CO hydrogenation[J].Catal Lett,2003,3/4(88):123-128.
[13] Nguyen Tien-Thao,Hassan Zahedi-Niaki M,Houshang Alamdari,et al.Effect of alkali additives over nanocrystalline Co-Cu-based perovskites as catalysts for higher-alcohol synthesis[J].J Catal,2007,245(2):348-357.
[14] Shi Xue-min(史雪敏),Yang Xu-zhuang(杨绪壮),Bai Feng-hua(白凤华) et al.Progress in additives of molybdenum based catalysts for higher alcohol synthesis from syngas(合成气制低碳醇钼基催化剂助剂的研究进展)[J].Chem Indus Engineer Pro(化工进展),2010,29(12):2291-2297.
[15] Fu Yi-lu(伏义路),Bao jun(鲍骏),Bian Guo-zhu(卞国柱),et al.Catalytic properties and structure of K-Co-Mo catalysts prepared by sol-gel method for mixed alcohol synthesis——effect of k content(溶胶—凝胶法制备K—Co—Mo催化剂的结构及其合成低碳醇性能研究——钾含量的影响)[J].J Mol Catal(China)(分子催化),1999,13(5):357-361.
[16] Yongjun Liu,Chaobo Liu,Chao Li,et al.CO hydrogenation to higher alcohols over Cu/Zn/Al catalysts without alkalis or fischer-tropsch elements:The effect of triethanolamine content[J].Catal Commun,2016,76:29-32.
[17] Chinchen G,Mansfied K,Spencer M.Methanol Synthesis[J].Chemtech,1990,11:693-699.
[18] Wei Jun-yi(魏珺谊),Gao Zhi-hua(高志华),Huang Wei(黄伟).Effect of structural ordering on the performance of mesoporous carbon supported CuCoCe catalyst in the synthesis of higher alcohols from syngas(介孔碳有序度对其负载的CuCoCe催化剂催化合成气制低碳醇性能的影响)[J].Chem J Chin Univer(高等学校化学学报),2018,39(8):1741-1749.
[19] Polster C S,Nair H ,Baertsch C D.Study of active sites and mechanism responsible for highly selective CO oxidation in H2 rich atmospheres on a mixed Cu and Ce oxide catalyst[J].J Catal,2009,266(2):308-319.
[20] Sun Jie,Cai Qiu-xia,Wan Yan,et al.Promotional effects of cesium promoter on higher alcohol synthesis from syngas over cesium-promoted Cu/ZnO/Al2O3 catalysts[J].ACS Catal,2016,6(9):5771-5785.
[21] Liakakou E T,Heracleous E,Triantafyllidis K S,et al.K-promoted NiMo catalysts supported on activated carbon for the hydrogenation reaction of CO to higher alcohols:Effect of support and active metal[J].Appl Catal:Environ,2015,165:296-305.
[22] Rungravee Phienluphon,Kitima Pinkaew,Guohui Yang,et al.Designing core (Cu/ZnO/Al2O3)-shell (SAPO-11) zeolite capsule catalyst with a facile physical way for dimethyl ether direct synthesis from syngas[J].Chem Engineer J,2015,270:605-611.