改性HZSM-5对甲醇制汽油反应性能的影响
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摘要
对HZSM-5分子筛改性是提高甲醇制汽油反应催化性能的有效方式,分别用非金属、稀土金属及水热处理对HZSM-5分子筛催化剂进行改性,考察改性方法对HZSM-5分子筛酸性、孔径和比表面积等性质的影响,同时对改性HZSM-5分子筛催化剂催化甲醇制汽油的汽油收率和芳烃含量等指标进行比较。结果表明,经La改性的催化剂可明显提高汽油收率,水热处理的催化剂反应产物汽油中的均四甲苯含量大幅增加。改性催化剂对反应的影响可一定程度验证相关理论。
Modification of HZSM-5 molecular sieve is an effective way to improve the catalytic performance for methanol to gasoline. HZSM-5 zeolite catalyst is modified with nonmetal,rare earth metal and hydrothermal treatment respectively. Effects of these modification methods on acidity,pore size and surface area of HZSM-5 zeolite were investigated. Meanwhile,gasoline yield and aromatic hydrocarbon content of modified HZSM-5 zeolite catalysts were studied. The results showed that yield of gasoline could be obviously increased over La modified catalyst,and content of durene in gasoline produced on hydrothermal treated catalyst is greatly increased. Influence of modified catalysts on reaction can verify the relevant theory to some extent.
Modification of HZSM-5 molecular sieve is an effective way to improve the catalytic performance for methanol to gasoline. HZSM-5 zeolite catalyst is modified with nonmetal,rare earth metal and hydrothermal treatment respectively. Effects of these modification methods on acidity,pore size and surface area of HZSM-5 zeolite were investigated. Meanwhile,gasoline yield and aromatic hydrocarbon content of modified HZSM-5 zeolite catalysts were studied. The results showed that yield of gasoline could be obviously increased over La modified catalyst,and content of durene in gasoline produced on hydrothermal treated catalyst is greatly increased. Influence of modified catalysts on reaction can verify the relevant theory to some extent.
引文
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[2]胡津仙,胡靖文,王俊杰,等.甲醇在不同酸性ZSM-5上转化为汽油(MTG)的研究[J].天然气化工,2001,6(26):1-3.Hu Jinxian,Hu Jingwen,Wang Junjie,et al. Study of MTG process with ZSM-5 zeolites which have different acid properties[J]. Natural Gas Chemical Industry,2001,26(6):1-3.
[3]张文杰,于杨,李可心. Na ZSM-5分子筛磷酸改性对Ti O2/ZSM-5光催化的影响[J].功能材料,2012,43(10):1308-1315.Zhang Wenjie,Yu Yang,Li Kexin. Effects of phosphoric acid modification of Na ZSM-5 zeolite on the properties of Ti O2/ZSM-5 photocatalyst[J]. Journal of Functional Materials,2012,43(10):1308-1315.
[4]周钰明,韩刚,丁营如. Zn改性HZSM-5沸石上甲醇的转化反应[J].催化学报,1996,17(1):64-67.Zhou Yuming,Han Gang,Ding Yingru. A study of methanol conversion on Zn modified HZSM-5 zeolite[J]. Chinese Journal of Catalysis,1996,17(1):64-67.
[5]Freeman D,Wells R P K,Hutchings G J,et al. Conversion of methanol to hydrocarbons over Ga2O3/HZSM-5 and Ga2O3/WO3Catalysts[J]. Journal of Catalysis,2002,205(2):358-365.
[6]Rahman A,Lemay G,Adnot A,et al. Spectroscopic and catalytic study of P-modified ZSM-5[J]. Journal of Catalysis,1988,(2):453-463.
[7]Wang K Y,Wang X S,Li G. A study on acid sites relatedto activity of nanoscale ZSM-5 in toluenedisproportionation[J]. Catalyst Commun,2007,8(3):324-328.
[8]盛清涛,凌开成,李振荣,等.水蒸汽及盐酸处理对ZSM-5分子筛性能的影响[J].太原理工大学学报,2012,43(4):425-430.Sheng Qingtao,Ling Kaicheng,Li Zhenrong,et al. Effect of steam treatment and HCl solution treatment on catalytic performance of ZSM-5 zeolite for the conversion of ethanol to ethylene[J]. Journal of Taiyuan University of Technology,2012,43(4):425-430.
[9]Jacobs P A,Beyer H K. Evidence for the nature of true Lewis sites in faujasite-type zeolites[J]. Journal of Physical Chemistry B,1979,83(9):174-1177.
[10]张婉静,于勤,魏国祥,等.高温水蒸汽处理后ZSM-5分子筛结构的变化[J].石油学报(石油加工),1985,1(1):41-51.Zhang Wanjing,Yu Qin,Wei Guoxiang,et al. Structural changes of ZSM-5 molecular sieves after high temperature steam treatment[J]. Acta Petrolei Sinica(Petroleum Processing Section),1985,1(1):41-51.
[11]Ding C. Characterization and catalytic alkylation of hydrothermally dealuminated nanoscale ZSM-5 zeolite catalyst[J]. Catalyst Commun,2007,9(4):487-493.
[12]Kaarshom M,Joensen F,Nerlov J,et al. Phosphorousmodified ZSM-5:Deactivation and product distribution for MTO[J]. Chem Eng Sci,2007,62(18-20):5527-5532.
[13] Rahman A,Lemay G,Adnot A,et al. Spectroscopic and catalytic study of P-modified ZSM-5[J]. Journal of Catalysis,1988,(2):453-463.
[14]Sun L,Guo X,Liu M,et al. Ethylation of coking benzene over nanoscale HZSM-5 zeolites:Effects of hydrothermal treatment,calcination and La2O3modification[J]. Applied Catalysis A:General,2009,355(1-2):184-191.
[15]汪树军,梁娟,郭文硅,等. ZSM-5沸石骨架铝迁移规律的研究Ⅰ.水热处理条件及沸石硅铝比的影响[J].催化学报,1992,13(1):38-43.Wang Shujun,Liang Juan,Guo Wengui,et al. Studies on the migration of framework al of ZSM-5 zeoliteⅠ. Effect of hydrothermal treatment and silica alumina ratio[J].Chinese Journal of Catalysis,1992,13(1):38-43.
[16]Campbell S M,Bibby D M,Coddington J M,et al. Dealumination of HZSM-5ZeolitesⅡ. Methanol to gasoline conversion[J]. Journal of Catalysis,1996,161(1):350-358.
[2]胡津仙,胡靖文,王俊杰,等.甲醇在不同酸性ZSM-5上转化为汽油(MTG)的研究[J].天然气化工,2001,6(26):1-3.Hu Jinxian,Hu Jingwen,Wang Junjie,et al. Study of MTG process with ZSM-5 zeolites which have different acid properties[J]. Natural Gas Chemical Industry,2001,26(6):1-3.
[3]张文杰,于杨,李可心. Na ZSM-5分子筛磷酸改性对Ti O2/ZSM-5光催化的影响[J].功能材料,2012,43(10):1308-1315.Zhang Wenjie,Yu Yang,Li Kexin. Effects of phosphoric acid modification of Na ZSM-5 zeolite on the properties of Ti O2/ZSM-5 photocatalyst[J]. Journal of Functional Materials,2012,43(10):1308-1315.
[4]周钰明,韩刚,丁营如. Zn改性HZSM-5沸石上甲醇的转化反应[J].催化学报,1996,17(1):64-67.Zhou Yuming,Han Gang,Ding Yingru. A study of methanol conversion on Zn modified HZSM-5 zeolite[J]. Chinese Journal of Catalysis,1996,17(1):64-67.
[5]Freeman D,Wells R P K,Hutchings G J,et al. Conversion of methanol to hydrocarbons over Ga2O3/HZSM-5 and Ga2O3/WO3Catalysts[J]. Journal of Catalysis,2002,205(2):358-365.
[6]Rahman A,Lemay G,Adnot A,et al. Spectroscopic and catalytic study of P-modified ZSM-5[J]. Journal of Catalysis,1988,(2):453-463.
[7]Wang K Y,Wang X S,Li G. A study on acid sites relatedto activity of nanoscale ZSM-5 in toluenedisproportionation[J]. Catalyst Commun,2007,8(3):324-328.
[8]盛清涛,凌开成,李振荣,等.水蒸汽及盐酸处理对ZSM-5分子筛性能的影响[J].太原理工大学学报,2012,43(4):425-430.Sheng Qingtao,Ling Kaicheng,Li Zhenrong,et al. Effect of steam treatment and HCl solution treatment on catalytic performance of ZSM-5 zeolite for the conversion of ethanol to ethylene[J]. Journal of Taiyuan University of Technology,2012,43(4):425-430.
[9]Jacobs P A,Beyer H K. Evidence for the nature of true Lewis sites in faujasite-type zeolites[J]. Journal of Physical Chemistry B,1979,83(9):174-1177.
[10]张婉静,于勤,魏国祥,等.高温水蒸汽处理后ZSM-5分子筛结构的变化[J].石油学报(石油加工),1985,1(1):41-51.Zhang Wanjing,Yu Qin,Wei Guoxiang,et al. Structural changes of ZSM-5 molecular sieves after high temperature steam treatment[J]. Acta Petrolei Sinica(Petroleum Processing Section),1985,1(1):41-51.
[11]Ding C. Characterization and catalytic alkylation of hydrothermally dealuminated nanoscale ZSM-5 zeolite catalyst[J]. Catalyst Commun,2007,9(4):487-493.
[12]Kaarshom M,Joensen F,Nerlov J,et al. Phosphorousmodified ZSM-5:Deactivation and product distribution for MTO[J]. Chem Eng Sci,2007,62(18-20):5527-5532.
[13] Rahman A,Lemay G,Adnot A,et al. Spectroscopic and catalytic study of P-modified ZSM-5[J]. Journal of Catalysis,1988,(2):453-463.
[14]Sun L,Guo X,Liu M,et al. Ethylation of coking benzene over nanoscale HZSM-5 zeolites:Effects of hydrothermal treatment,calcination and La2O3modification[J]. Applied Catalysis A:General,2009,355(1-2):184-191.
[15]汪树军,梁娟,郭文硅,等. ZSM-5沸石骨架铝迁移规律的研究Ⅰ.水热处理条件及沸石硅铝比的影响[J].催化学报,1992,13(1):38-43.Wang Shujun,Liang Juan,Guo Wengui,et al. Studies on the migration of framework al of ZSM-5 zeoliteⅠ. Effect of hydrothermal treatment and silica alumina ratio[J].Chinese Journal of Catalysis,1992,13(1):38-43.
[16]Campbell S M,Bibby D M,Coddington J M,et al. Dealumination of HZSM-5ZeolitesⅡ. Methanol to gasoline conversion[J]. Journal of Catalysis,1996,161(1):350-358.