热处理时间对CuZnAl催化剂合成C_(2+)OH性能的影响
|
摘要
采用完全液相法在不同热处理时间下制备了CuZnAl催化剂,利用X射线光电子能谱(XPS)、X射线衍射(XRD)、H_2程序升温还原(H_2-TPR)、NH_3吸附-脱附(NH_3-TPD-M S)和N_2物理吸附-脱附等方法对其结构进行了表征分析,并在浆态床反应器上对其催化合成气制C_(2+)OH的性能进行了研究。研究发现,延长热处理时间增强了催化剂中Cu和Al物种之间的相互作用力,改变了其中Cu~+的量,从而影响Cu~+-Cu~0活性位的协同作用。同时,热处理时间的延长减少了催化剂的表面酸量,增大了孔容和孔径;催化剂表面较少的弱酸位及较大孔容和孔径均有利于C_(2+)OH的生成。热处理时间为7 h时所制备的CuZnAl催化剂表现出了优良的低碳醇合成催化活性,CO转化率和总醇中C_(2+)OH的质量分数分别达到了38.1%和65.9%。
A series of CuZnAl catalysts were prepared by the complete liquid-phase method with different heat treatment times and characterized by XPS,XRD,H_2-TPR,NH_3-TPD-M S and N_2 adsorption-desorption; their catalytic performances in the synthesis of higher alcohols from syngas were investigated in a slurry bed reactor.The results indicate that an increase in the heat treatment time can enhance the interaction between the Cu and Al species and alter the amount of Cu+species over the CuZnAl catalysts,influencing the synergistic effect of Cu~+-Cu~0 sites. In addition,with the increase of heat treatment time,the surface acidity of CuZnAl catalyst decreases,accompanying with an increase in the pore volume and pore size; small amount of surface weak acid sites,large pore volume and large pore size are beneficial to the formation of higher alcohols. The CuZnAl catalyst obtained by heat-treating for 7 h exhibits excellent performance in the synthesis of higher alcohols,with a CO conversion of 38.1% and a higher alcohols mass fraction of 65.9% in the total alcohols.
A series of CuZnAl catalysts were prepared by the complete liquid-phase method with different heat treatment times and characterized by XPS,XRD,H_2-TPR,NH_3-TPD-M S and N_2 adsorption-desorption; their catalytic performances in the synthesis of higher alcohols from syngas were investigated in a slurry bed reactor.The results indicate that an increase in the heat treatment time can enhance the interaction between the Cu and Al species and alter the amount of Cu+species over the CuZnAl catalysts,influencing the synergistic effect of Cu~+-Cu~0 sites. In addition,with the increase of heat treatment time,the surface acidity of CuZnAl catalyst decreases,accompanying with an increase in the pore volume and pore size; small amount of surface weak acid sites,large pore volume and large pore size are beneficial to the formation of higher alcohols. The CuZnAl catalyst obtained by heat-treating for 7 h exhibits excellent performance in the synthesis of higher alcohols,with a CO conversion of 38.1% and a higher alcohols mass fraction of 65.9% in the total alcohols.
引文
[1]SUBRAMANI V,GANGWAL S K.A review of recent literature to search for an efficient catalytic process for the conversion of syngas to ethanol[J].Energy Fuels,2008,22(2):117-136.
[2]GUPTA M,SMITH M L,SPIVEY J J.Heterogeneous catalytic conversion of dry syngas to ethanol and higher alcohols on cu-based catalysts[J].Acs Catal,2011,1(6):641-656.
[3]LUK H T,MONDELLI C,FERRE D C,STEWART J A,PEREZ R.Status and prospects in higher alcohols synthesis from syngas[J].Chem Soc Rev,2017,46(5):1358-1426.
[4]JAKOBSEN J G,JAKOBSEN M,CHORKENDORFF I,SEHESTED J.Methane steam reforming kinetics for a rhodium-based catalyst[J].Catal Lett,2010,140(3):90-97.
[5]BAEK S C,BAE J W,CHEON J Y,JUN K W,LEE K Y.Combined steam and carbon dioxide reforming of methane on Ni/MgAl2O4:Effect of CeO2promoter to catalytic performance[J].Catal Lett,2011,141(2):224-234.
[6]MEI D,ROUSSEAU R,KATHMANN S M.Ethanol synthesis from syngas over Rh-based/SiO2catalysts:A combined experimental and theoretical modeling study[J].J Catal,2010,271(2):325-342.
[7]YANG X M,WEI Y,SU Y L,ZHOU L P.Characterization of fused Fe-Cu based catalyst for higher alcohols synthesis and DRIFTSinvestigation of TPSR[J].Fuel Process Technol,2010,91(9):1168-1173.
[8]HERACLEOUS E,LIAKAKOU E T,LAPPAS A A,LEMONIDOU A A.Investigation of K-promoted Cu-Zn-Al,Cu-X-Al and Cu-Zn-X(X=Cr,M n)catalysts for carbon monoxide hydrogenation to higher alcohols[J].Appl Catal A:Gen,2013,455(2):145-154.
[9]GAO Z H,HAO L F,HUANG W,XIE K C.A novel liquid-phase technology for the preparation of slurry catalysts[J].Catal Lett,2005,102(3/4):139-141.
[10]HUANG W,YU L M,LI W H,MA Z L.Synthesis of methanol and ethanol over CuZnAl slurry catalyst prepared by complete liquid-phase technology[J].Front Chem Eng China,2010,4(4):472-475.
[11]喻仕瑞.浆态床合成乙醇Cu基催化剂制备及其性能研究[D].太原:太原理工大学,2013.(YU Shi-rui.Study on the preparation and performance of Cu-based catalyst for ethanol synthesis in slurry reactor[D].Taiyuan:Taiyuan University of Technology,2013.)
[12]刘勇军.CuZnAl催化剂催化合成气直接制乙醇的研究[D].太原:太原理工大学,2016.(LIU Yong-jun.Study on the ethanol synthesis from syngas over CuZnAl catalysts[D].Taiyuan:Taiyuan University of Technology,2016.)
[13]董伟兵.热处理条件对CuZnAl催化剂合成低碳醇性能的影响[D].太原:太原理工大学,2017.(DONG Wei-bing.Effect of heat treatment conditions on catalytic performance of CuZnAl catalysts for higher alcohol synthesis[D].Taiyuan:Taiyuan University of Technology,2017.)
[14]SCHULZ H.Short history and present trends of Fischer-Tropsch synthesis[J].Appl Catal A:Gen,1999,186(1/2):3-12.
[15]叶同奇,张朝霞,徐勇,颜世志,朱九方,刘勇,李全新.Na促进的CuCoMn催化剂催化生物质合成气合成高醇[J].物理化学学报,2011,27(6):1493-1500.(YE Tong-qi,ZHANG Zhao-xia,XU Yong,YAN Shi-zhi,ZHU Jiu-fang,LIU Yong,LI Quan-xin.Higher alcohol synthesis from biosyngas over Na-promoted CuCoM n catalyst[J].Acta Phys-Chim Sin,2011,27(6):1493-1500.)
[16]BOZ I.Higher alcohol synthesis over a K-promoted Co2O3/CuO/ZnO/Al2O3catalyst[J].Catal Lett,2003,87(3/4):187-194.
[17]LI Z H,ZUO Z J,HUANG W,XIE K C.Research on Si-Al based catalysts prepared by complete liquid-phase method for DME synthesis in a slurry reactor[J].Appl Surf Sci,2011,257(6):2180-2183.
[18]SUH Y W,MOON S H,RHEE H K.Active sites in Cu/ZnO/ZrO2catalysts for methanol synthesis from CO/H2[J].Catal Today,2000,63(2/4):447-452.
[19]GAO W,ZHAO Y F,LIU J M,HUANG Q W,HE S,LI C M,ZHAO J W,WEI M.Catalytic conversion of syngas to mixed alcohols over CuFe-based catalysts derived from layered double hydroxides[J].Catal Sci Technol,2013,3(5):1324-1332.
[20]FIGUEIREDO R T,MARTINEZ-ARIAS A,GRANADOS M L,FIERRO J L G.Spectroscopic evidence of Cu-Al interactions in Cu-Zn-Al mixed oxide catalysts used in CO hydrogenation[J].J Catal,1998,178(1):146-152.
[21]高志华,黄伟,李俊芳,阴丽华,谢克昌.以拟薄水铝石为铝源制备浆态床二甲醚合成催化剂[J].高等学校化学学报,2009,30(3):534-538.(GAO Zhi-hua,HUANG Wei,LI Jun-fang,YIN Li-hua,XIE Ke-chang.Liquid-phase preparation of DME slurry catalysts using pseudoboehmite as aluminum source[J].Chem J Chin Univ,2009,30(3):534-538.)
[22]房德仁,刘中民,刘德臣,张慧敏,孟霜鹤,王立刚.铝盐加入方式对CuO/ZnO/Al2O3系催化剂性能的影响[J].石油化工,2004,33(11):1041-1045.(FANG De-ren,LIU Zhong-min,LIU De-chen,ZHANG Hui-min,MENG Shuang-he,WANG Li-gang.Influence of Al salt addition methods on performance of CuO/ZnO/Al2O3catalysts[J].Petrochem Technol,2004,33(11):1041-1045.)
[23]LIU Y J,ZUO Z J,LIU C B,LI C,DENG X,HUANG W.Higher alcohols synthesis via CO hydrogenation on Cu/Zn/Al/Zr catalysts w ithout alkalis and F-T elements[J].Fuel Process Technol,2016,144:186-190.
[24]董伟兵,郝树宏,高志华.预热液体石蜡对CuZnAl催化剂合成低碳醇的影响[J].天然气化工,2017,42(5):27-33.(DONG Wei-bing,HAO Shu-hong,GAO Zhi-hua.Effect of preheating liquid paraffin on synthesis of higher alcohols by CuZnAl catalyst[J].Nat Gas Chem Ind,2017,42(5):27-33.)
[25]毛东森,郭强胜,俞俊,韩璐蓬,卢冠忠.Ce添加对Cu-Fe/SiO2催化合成气制低碳醇性能的影响[J].物理化学学报,2011,27(11):2639-2645.(MAO Dong-sen,GUO Qiang-sheng,YU Jun,HAN Lu-peng,LU Guan-zhong.Effect of cerium addition on the catalytic performance of Cu-Fe/SiO2for the synthesis of low er alcohols from syngas[J].Acta Phys-Chim Sin,2011,27(11):2639-2645.)
[26]徐慧远,储伟,士丽敏,张辉,邓思玉.射频等离子体对合成低碳醇用CuCoAl催化剂的改性作用[J].燃料化学学报,2009,37(2):212-216.(XU Hui-yuan,CHU Wei,SHI Li-min,ZHANG Hui,DENG Si-yu.Effect of glow discharge plasma on copper-cobalt-aluminum catalysts for higher alcohols synthesis[J].J Fuel Chem Technol,2009,37(2):212-216.)
[27]CHU W,KIEFFER R,KIENNEMANN A,HINDERMANN J P.Conversion of syngas to C1-C6 alcohol mixtures on promoted CuLa2Zr2O7catalysts[J].Appl Catal A:Gen,1995,27(121):95-111.
[28]OKAMOTO Y,FUKINO K,IMANAKA T,TERANISHI S.Surface characterization of copper(II)oxide-zinc oxide methanol-synthesis catalysts by x-ray photoelectron spectroscopy.2.Reduced catalysts[J].J Phys Chem,1983,87(19):3740-3747.
[29]樊金串,杨瑞卿,赵杰,黄伟.液体石蜡体系中含铜物种的化学变化[J].应用化学,2013,30(1):67-72.(FAN Jin-chuan,YANG Rui-qing,ZHAO Jie,HUANG Wei.Chemical change of copper species in liquid paraffin[J].Chin J Appl Chem,2013,30(1):67-72.)
[30]吕晓东.Cu-Zn-Al催化剂的完全液相制备及催化合成乙醇的研究[D].太原:太原理工大学,2015.(LV Xiao-dong.The study of preparation and synthesis of ethanol of Cu-Zn-Al catalyst by complete liquid-phase technology[D].Taiyuan:Taiyuan University of Technology,2015.)
[31]孙凯,张小雨,张琳,边仲凯,黄伟,赵志换.酸碱性硅溶胶对浆状Cu/Zn/Al催化剂性能的影响[J].燃料化学学报,2015,43(10):1221-1229.(SUN Kai,ZHANG Xiao-yu,ZHANG Lin,BIAN Zhong-kai,HUANG Wei,ZHAO Zhi-huan.Influence of acidic and alkaline silica sols on the performance of Cu/Zn/Al slurry catalysts[J].J Fuel Chem Technol,2015,43(10):1221-1229.)
[32]马强,黄伟,樊金串,赵杰,任杰.完全液相法制备的Cu-Zn-Si-Al浆状催化剂一步法合成二甲醚的失活研究[J].分子催化,2009,23(6):499-505.(MA Qiang,HUANG Wei,FAN Jin-chuan,ZHAO Jie,REN Jie.Study on the deactivation of Cu-Zn-Si-Al slurry catalyst prepared by complete liquid-phase for one-step dimethyl ether synthesis[J].J M ol Catal(China),2009,23(6):499-505.)
[33]GAO Z H,LIU Y,LI L L,LI S S,HUANG W.CuZnAl catalysts prepared by precipitation-hydrothermal method for higher alcohols synthesis from syngas[J].Energy Source Part A,2017,39(6):1-7.
[34]刘建国,定明月,王铁军,马隆龙.Cu-Fe基双孔载体催化剂结构和低碳醇合成反应性能[J].物理化学学报,2012,28(8):1964-1970.(LIU Jian-guo,DING Ming-yue,WANG Tie-jun,MA Long-long.Structure and performance of Cu-Fe bimodal support for higher alcohol syntheses[J].Acta Phys-Chim Sin,2012,28(8):1964-1970.)
[2]GUPTA M,SMITH M L,SPIVEY J J.Heterogeneous catalytic conversion of dry syngas to ethanol and higher alcohols on cu-based catalysts[J].Acs Catal,2011,1(6):641-656.
[3]LUK H T,MONDELLI C,FERRE D C,STEWART J A,PEREZ R.Status and prospects in higher alcohols synthesis from syngas[J].Chem Soc Rev,2017,46(5):1358-1426.
[4]JAKOBSEN J G,JAKOBSEN M,CHORKENDORFF I,SEHESTED J.Methane steam reforming kinetics for a rhodium-based catalyst[J].Catal Lett,2010,140(3):90-97.
[5]BAEK S C,BAE J W,CHEON J Y,JUN K W,LEE K Y.Combined steam and carbon dioxide reforming of methane on Ni/MgAl2O4:Effect of CeO2promoter to catalytic performance[J].Catal Lett,2011,141(2):224-234.
[6]MEI D,ROUSSEAU R,KATHMANN S M.Ethanol synthesis from syngas over Rh-based/SiO2catalysts:A combined experimental and theoretical modeling study[J].J Catal,2010,271(2):325-342.
[7]YANG X M,WEI Y,SU Y L,ZHOU L P.Characterization of fused Fe-Cu based catalyst for higher alcohols synthesis and DRIFTSinvestigation of TPSR[J].Fuel Process Technol,2010,91(9):1168-1173.
[8]HERACLEOUS E,LIAKAKOU E T,LAPPAS A A,LEMONIDOU A A.Investigation of K-promoted Cu-Zn-Al,Cu-X-Al and Cu-Zn-X(X=Cr,M n)catalysts for carbon monoxide hydrogenation to higher alcohols[J].Appl Catal A:Gen,2013,455(2):145-154.
[9]GAO Z H,HAO L F,HUANG W,XIE K C.A novel liquid-phase technology for the preparation of slurry catalysts[J].Catal Lett,2005,102(3/4):139-141.
[10]HUANG W,YU L M,LI W H,MA Z L.Synthesis of methanol and ethanol over CuZnAl slurry catalyst prepared by complete liquid-phase technology[J].Front Chem Eng China,2010,4(4):472-475.
[11]喻仕瑞.浆态床合成乙醇Cu基催化剂制备及其性能研究[D].太原:太原理工大学,2013.(YU Shi-rui.Study on the preparation and performance of Cu-based catalyst for ethanol synthesis in slurry reactor[D].Taiyuan:Taiyuan University of Technology,2013.)
[12]刘勇军.CuZnAl催化剂催化合成气直接制乙醇的研究[D].太原:太原理工大学,2016.(LIU Yong-jun.Study on the ethanol synthesis from syngas over CuZnAl catalysts[D].Taiyuan:Taiyuan University of Technology,2016.)
[13]董伟兵.热处理条件对CuZnAl催化剂合成低碳醇性能的影响[D].太原:太原理工大学,2017.(DONG Wei-bing.Effect of heat treatment conditions on catalytic performance of CuZnAl catalysts for higher alcohol synthesis[D].Taiyuan:Taiyuan University of Technology,2017.)
[14]SCHULZ H.Short history and present trends of Fischer-Tropsch synthesis[J].Appl Catal A:Gen,1999,186(1/2):3-12.
[15]叶同奇,张朝霞,徐勇,颜世志,朱九方,刘勇,李全新.Na促进的CuCoMn催化剂催化生物质合成气合成高醇[J].物理化学学报,2011,27(6):1493-1500.(YE Tong-qi,ZHANG Zhao-xia,XU Yong,YAN Shi-zhi,ZHU Jiu-fang,LIU Yong,LI Quan-xin.Higher alcohol synthesis from biosyngas over Na-promoted CuCoM n catalyst[J].Acta Phys-Chim Sin,2011,27(6):1493-1500.)
[16]BOZ I.Higher alcohol synthesis over a K-promoted Co2O3/CuO/ZnO/Al2O3catalyst[J].Catal Lett,2003,87(3/4):187-194.
[17]LI Z H,ZUO Z J,HUANG W,XIE K C.Research on Si-Al based catalysts prepared by complete liquid-phase method for DME synthesis in a slurry reactor[J].Appl Surf Sci,2011,257(6):2180-2183.
[18]SUH Y W,MOON S H,RHEE H K.Active sites in Cu/ZnO/ZrO2catalysts for methanol synthesis from CO/H2[J].Catal Today,2000,63(2/4):447-452.
[19]GAO W,ZHAO Y F,LIU J M,HUANG Q W,HE S,LI C M,ZHAO J W,WEI M.Catalytic conversion of syngas to mixed alcohols over CuFe-based catalysts derived from layered double hydroxides[J].Catal Sci Technol,2013,3(5):1324-1332.
[20]FIGUEIREDO R T,MARTINEZ-ARIAS A,GRANADOS M L,FIERRO J L G.Spectroscopic evidence of Cu-Al interactions in Cu-Zn-Al mixed oxide catalysts used in CO hydrogenation[J].J Catal,1998,178(1):146-152.
[21]高志华,黄伟,李俊芳,阴丽华,谢克昌.以拟薄水铝石为铝源制备浆态床二甲醚合成催化剂[J].高等学校化学学报,2009,30(3):534-538.(GAO Zhi-hua,HUANG Wei,LI Jun-fang,YIN Li-hua,XIE Ke-chang.Liquid-phase preparation of DME slurry catalysts using pseudoboehmite as aluminum source[J].Chem J Chin Univ,2009,30(3):534-538.)
[22]房德仁,刘中民,刘德臣,张慧敏,孟霜鹤,王立刚.铝盐加入方式对CuO/ZnO/Al2O3系催化剂性能的影响[J].石油化工,2004,33(11):1041-1045.(FANG De-ren,LIU Zhong-min,LIU De-chen,ZHANG Hui-min,MENG Shuang-he,WANG Li-gang.Influence of Al salt addition methods on performance of CuO/ZnO/Al2O3catalysts[J].Petrochem Technol,2004,33(11):1041-1045.)
[23]LIU Y J,ZUO Z J,LIU C B,LI C,DENG X,HUANG W.Higher alcohols synthesis via CO hydrogenation on Cu/Zn/Al/Zr catalysts w ithout alkalis and F-T elements[J].Fuel Process Technol,2016,144:186-190.
[24]董伟兵,郝树宏,高志华.预热液体石蜡对CuZnAl催化剂合成低碳醇的影响[J].天然气化工,2017,42(5):27-33.(DONG Wei-bing,HAO Shu-hong,GAO Zhi-hua.Effect of preheating liquid paraffin on synthesis of higher alcohols by CuZnAl catalyst[J].Nat Gas Chem Ind,2017,42(5):27-33.)
[25]毛东森,郭强胜,俞俊,韩璐蓬,卢冠忠.Ce添加对Cu-Fe/SiO2催化合成气制低碳醇性能的影响[J].物理化学学报,2011,27(11):2639-2645.(MAO Dong-sen,GUO Qiang-sheng,YU Jun,HAN Lu-peng,LU Guan-zhong.Effect of cerium addition on the catalytic performance of Cu-Fe/SiO2for the synthesis of low er alcohols from syngas[J].Acta Phys-Chim Sin,2011,27(11):2639-2645.)
[26]徐慧远,储伟,士丽敏,张辉,邓思玉.射频等离子体对合成低碳醇用CuCoAl催化剂的改性作用[J].燃料化学学报,2009,37(2):212-216.(XU Hui-yuan,CHU Wei,SHI Li-min,ZHANG Hui,DENG Si-yu.Effect of glow discharge plasma on copper-cobalt-aluminum catalysts for higher alcohols synthesis[J].J Fuel Chem Technol,2009,37(2):212-216.)
[27]CHU W,KIEFFER R,KIENNEMANN A,HINDERMANN J P.Conversion of syngas to C1-C6 alcohol mixtures on promoted CuLa2Zr2O7catalysts[J].Appl Catal A:Gen,1995,27(121):95-111.
[28]OKAMOTO Y,FUKINO K,IMANAKA T,TERANISHI S.Surface characterization of copper(II)oxide-zinc oxide methanol-synthesis catalysts by x-ray photoelectron spectroscopy.2.Reduced catalysts[J].J Phys Chem,1983,87(19):3740-3747.
[29]樊金串,杨瑞卿,赵杰,黄伟.液体石蜡体系中含铜物种的化学变化[J].应用化学,2013,30(1):67-72.(FAN Jin-chuan,YANG Rui-qing,ZHAO Jie,HUANG Wei.Chemical change of copper species in liquid paraffin[J].Chin J Appl Chem,2013,30(1):67-72.)
[30]吕晓东.Cu-Zn-Al催化剂的完全液相制备及催化合成乙醇的研究[D].太原:太原理工大学,2015.(LV Xiao-dong.The study of preparation and synthesis of ethanol of Cu-Zn-Al catalyst by complete liquid-phase technology[D].Taiyuan:Taiyuan University of Technology,2015.)
[31]孙凯,张小雨,张琳,边仲凯,黄伟,赵志换.酸碱性硅溶胶对浆状Cu/Zn/Al催化剂性能的影响[J].燃料化学学报,2015,43(10):1221-1229.(SUN Kai,ZHANG Xiao-yu,ZHANG Lin,BIAN Zhong-kai,HUANG Wei,ZHAO Zhi-huan.Influence of acidic and alkaline silica sols on the performance of Cu/Zn/Al slurry catalysts[J].J Fuel Chem Technol,2015,43(10):1221-1229.)
[32]马强,黄伟,樊金串,赵杰,任杰.完全液相法制备的Cu-Zn-Si-Al浆状催化剂一步法合成二甲醚的失活研究[J].分子催化,2009,23(6):499-505.(MA Qiang,HUANG Wei,FAN Jin-chuan,ZHAO Jie,REN Jie.Study on the deactivation of Cu-Zn-Si-Al slurry catalyst prepared by complete liquid-phase for one-step dimethyl ether synthesis[J].J M ol Catal(China),2009,23(6):499-505.)
[33]GAO Z H,LIU Y,LI L L,LI S S,HUANG W.CuZnAl catalysts prepared by precipitation-hydrothermal method for higher alcohols synthesis from syngas[J].Energy Source Part A,2017,39(6):1-7.
[34]刘建国,定明月,王铁军,马隆龙.Cu-Fe基双孔载体催化剂结构和低碳醇合成反应性能[J].物理化学学报,2012,28(8):1964-1970.(LIU Jian-guo,DING Ming-yue,WANG Tie-jun,MA Long-long.Structure and performance of Cu-Fe bimodal support for higher alcohol syntheses[J].Acta Phys-Chim Sin,2012,28(8):1964-1970.)