Preparation of micro-mesoporous ZSM-5 zeolite through mixed alkali treatment and its catalytic performance in the alkylation of thiophene

LIU Dong-mei; TIE Da-xing; GAO Chen-yi; MAO Yan-hong; WANG Hai-yan; YU Hai-bing

Volume 45 Issue 2

Feb. 2017

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Article Navigation > Journal of Fuel Chemistry and Technology > 2017 > 45(2): 200-212

LIU Dong-mei, TIE Da-xing, GAO Chen-yi, MAO Yan-hong, WANG Hai-yan, YU Hai-bing. Preparation of micro-mesoporous ZSM-5 zeolite through mixed alkali treatment and its catalytic performance in the alkylation of thiophene[J]. Journal of Fuel Chemistry and Technology, 2017, 45(2): 200-212.

Citation:

LIU Dong-mei, TIE Da-xing, GAO Chen-yi, MAO Yan-hong, WANG Hai-yan, YU Hai-bing. Preparation of micro-mesoporous ZSM-5 zeolite through mixed alkali treatment and its catalytic performance in the alkylation of thiophene[J]. Journal of Fuel Chemistry and Technology, 2017, 45(2): 200-212.

Citation:

LIU Dong-mei, TIE Da-xing, GAO Chen-yi, MAO Yan-hong, WANG Hai-yan, YU Hai-bing. Preparation of micro-mesoporous ZSM-5 zeolite through mixed alkali treatment and its catalytic performance in the alkylation of thiophene[J]. Journal of Fuel Chemistry and Technology, 2017, 45(2): 200-212.

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Preparation of micro-mesoporous ZSM-5 zeolite through mixed alkali treatment and its catalytic performance in the alkylation of thiophene

1.
Collelege of Chemistry, Chemical Engineering and Environmental Engineering, Fushun 113001, China
2.
CNPC Fushun Petrochemical, Fushun 113001, China

Funds:

Natural Science Foundation of Liaoning Province 201202126

Received Date: 2016-08-16
Rev Recd Date: 2016-11-09

Available Online: 2021-01-23

Publish Date: 2017-02-10

Abstract

Abstract

ZSM-5 zeolite with a SiO₂/Al₂O₃ mol ratio of 50 as the raw material was treated either by adding tetrapropylammonium hydroxide solution for secondary crystallization after pre-treating with Na₂CO₃ solution or directly by Na₂CO₃/TPAOH mixed solution, to prepare the micro-mesoporous hierarchical HZSM-5 catalyst;the catalytic performance of resultant micro-mesoporous HZSM-5 in thiophene alkylation was then investigated.The results showed that if the raw ZSM-5 material is first pre-treated with 4 mol/L Na₂CO₃ and then crystallized for the second time in the presence of 0.3 mol/L TPAOH and at 170℃ for about 24 h, the resultant micro-mesoporous HZSM-5(CO₃^2--TPA⁺, 0.3-24-170) has a moderate pore diameter and acidity and exhibits the highest conversion of thiophene (99.1%) in alkylation.However, if the raw ZSM-5 is treated by the mixed solution of Na₂CO₃ and TPAOH, the dissolved SiO₂ may block the pores and channels, leading to lower acidity and smaller pores, which is not suitable for the thiophene alkylation.
- mixed alkali treatment,
- hierarchical,
- secondary crystallization,
- ZSM-5,
- alkylation

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References(28)

References

[1]	方向晨, 关明华, 廖士纲. 加氢精制[M]. 北京:中国石化出版社, 2006:28-29. (FANG Xiang-chen, GUAN Ming-hua, LIAO Shi-gang. Hydrogenation Refining[M]. Beijing:Sinopec press, 2006:28-29.)
[2]	柯明, 周爱国, 赵振盛, 蒋庆哲, 宋昭峥. FCC汽油烷基化脱硫技术进展[J]. 化工进展, 2006, 25(4):357-361. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJZ200604001.htm (KE Ming, ZHOU Ai-guo, ZHAO Zhen-sheng, JIANG Qing-zhe, SONG Zhao-zheng. Progress in the production technology of FCC gasoline alkylation[J]. Prog Chem, 2006, 25(4):357-361.) http://www.cnki.com.cn/Article/CJFDTOTAL-HGJZ200604001.htm
[3]	GISLASONL J. Phillips sulfur-removal processne nears commercialization[J]. Oil Gas J, 2001, 99(47):72-76. https://www.researchgate.net/publication/279578250_Phillips_sulfur-removal_process_nears_commercialization
[4]	张睿心, 潘喜强, 程华, 王红梅, 陈湘琴. 汽油烷基化脱硫技术进展[J]. 化学工程师, 2014, 28(9):40-43. http://www.cnki.com.cn/Article/CJFDTOTAL-HXGC201409016.htm (ZHANG Rui-xin, PAN Xi-qiang, CHENG Hua, WANG Hong-mei, CHEN Xiang-qin. Progress in the production technology of gasoline alkylation[J]. Chem Eng, 2014, 28(9):40-43.) http://www.cnki.com.cn/Article/CJFDTOTAL-HXGC201409016.htm
[5]	郭晓野, 张泽凯, 刘盛林, 李玉宁, 戴洪义, 徐龙伢. 汽油在钾修饰MCM-22分子筛上的烷基化脱硫[J]. 工业催化, 2008, 16(6):31-34. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH200806012.htm (GUO Xiao-ye, ZHANG Ze-kai, LIU Sheng-lin, LI Yu-ning, DAI Hong-yi, XU Long-ya. Alkylation desulfurization of gasoline on MCM-22 zeolite modified by kalium[J]. Catal Ind, 2008, 16(6):31-34.) http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH200806012.htm
[6]	许昀, 龙军, 张久顺, 吴志国. 分子筛催化体系中汽油噻吩类含硫化合物烷基化反应脱硫的研究[J]. 石油炼制与化工, 2005, 36(2):38-42. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH200502017.htm (XU Jun, LONG Jun, ZHANG Jiu-shun, WU Zhi-guo. Study on alkylation reaction of thiophene sulfur compounds in molecular sieve catalytic system[J]. Pet Process Petrochem, 2005, 36(2):38-42.) http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH200502017.htm
[7]	姜蕾, 张占柱, 毛俊义, 渠红亮, 吴梅. 采用改性磺酸树脂催化剂的催化裂化汽油的烷基化脱硫[J]. 石油学报(石油加工), 2006, 22(1):22-26. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG200601003.htm (JIANG Lei, ZHANG Zhan-zhu, MAO Jun-yi, QU Hong-liang, WU Mei. Alkylation desulfurization of catalytic cracking gasoline by using modified sulfonic acid resin catalyst[J]. Acta Pet Sin(Pet Process Sect), 2006, 22(1):22-26.) http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG200601003.htm
[8]	罗国华, 徐新, 单希林, 佟泽民, 彭少逸. 催化噻吩类硫化物与烯烃烷基化硫转移反应的固体酸催化剂的失活机理[J]. 催化学报, 2004, 25(8):648-652. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200408013.htm (LUO Guo-hua, XU Xin, SHAN Xi-lin, TONG Xin-min, PENG Shao-yi. Deactivation mechanism of solid acid catalysts for the catalytic alkylation of thiophene sulfide with olefin[J]. Chin J Catal, 2004, 25(8):648-652.) http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200408013.htm
[9]	张泽凯, 牛雄雷, 朱向学, 刘盛林, 王清遐, 徐龙伢. 汽油烷基化脱硫中己烯的聚合及对噻吩烷基化的影响[J]. 中国石油大学学报(自然科学版), 2008, 32(1):123-127. http://www.cnki.com.cn/Article/CJFDTOTAL-SYDX200801031.htm (ZHANG Ze-kai, NIU Xiong-lei, ZHU Xiang-xue, LIU Sheng-lin, WANG Qing-xia, XU Long-ya. Polymerization of olefins in the process of oil alkylation desulfurization and its effect on thiophene alkylation[J]. J China Petro Univ (Nat Sci Ed), 2008, 32(1):123-127.) http://www.cnki.com.cn/Article/CJFDTOTAL-SYDX200801031.htm
[10]	罗国华, 徐新, 佟泽民. 分子筛催化噻吩类硫化物与烯烃烷基化脱硫研究[J]. 化学反应工程与工艺, 2005, 21(2):133-137. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY200502008.htm (LUO Guo-hua, XU Xin, TONG Ze-min, Study on alkylation desulfurization of thiophene and olefin by molecular sieve catalyst[J]. Chem React Eng Technol, 2005, 21(2):133-137.) http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY200502008.htm
[11]	CALVEY H, DAVIS M, WILLIAMS R. Alkali-treatment technique-new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J]. Appl Catal A:Gen, 2001, 219(1/2):33-43. https://www.researchgate.net/publication/222877270_Alkali-treatment_technique_-_New_method_for_modification_of_structural_and_acid-catalytic_properties_of_ZSM-5_zeolites
[12]	SUZUKI T, OKUHARA T. Change in pore structure of MFI zeolite by treatment with NaOH aqueous solution[J]. Microporous Mesoporous Mater, 2001, 43(1):83-89. doi: 10.1016/S1387-1811(00)00349-8
[13]	TAO Y, KANOH H, KANEKO K. Developments and structures of mesopores in alkaline-treated ZSM-5 zeolites[J]. Adsorption, 2006, 12(5):309-316. http://www.docin.com/p-815549621.html
[14]	SONG Y Q, FENG Y L, LIU F, KANG C L, ZHOU X L, XU L Y, YU G X. Effect of variations in pore structure and acidity of alkali treated ZSM-5 on the isomerization performance[J]. J Mol Catal A:Chem, 2009, 310(1/2):130-137. https://www.researchgate.net/profile/X_Zhou5/publication/244278995_Effect_of_variations_in_pore_structure_and_acidity_of_alkali_treated_ZSM-5_on_the_isomerization_performance/links/56837ebc08ae1e63f1f16f5c.pdf?origin=publication_detail
[15]	赵岑, 刘冬梅, 魏民, 孙志岩, 王海彦. 多级孔ZSM-5分子筛的制备及催化噻吩烷基化性能研究[J]. 燃料化学学报, 2013, 41(10):1256-1261. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18282.shtml (ZHAO Cen, LIU Dong-mei, WEI Min, SUN Zhi-yan, WANG Hai-yan. Preparation and catalytic performance of ZSM-5 molecular sieve with hierarchical pore[J]. J Fuel Chem Technol, 2013, 41(10):1256-1261.) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18282.shtml
[16]	马健, 刘冬梅, 魏民, 王海彦, 王坤, 张晶卫. Na₂CO₃溶液处理对Ni-Mo/HZSM-5分子筛硫醚化催化性能的影响[J]. 燃料化学学报, 2014, 43(9):1128-1134. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18493.shtml (MA Jian, LIU Dong-mei, WEI Min, WANG Hai-yan, WANG Kun, ZHANG Jing-wei. Effect of Na₂CO₃ solution treatment on properties of Ni-Mo/HZ.SM-5 thioetherfication catalyst[J]. J Fuel Chem Technol, 2014, 43(9):1128-1134.) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18493.shtml
[17]	张培青, 王祥生, 郭洪臣, 徐舟波, 赵乐平, 胡永康. 水热处理对纳米HZSM-5沸石酸性质及其降低汽油烯烃性能的影响[J]. 催化学报, 2003, 24(12):900-904. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200312004.htm (ZHANG Pei-qing, WANG Xiang-sheng, GUO Hong-chen, XU Zhou-bo, ZHAO Le-ping, HU Yong-kang. Effect of hydrothermal treatment on the properties of nano HZSM-5 zeolite and its reduction of olefin properties[J]. Chin J Catal, 2003, 24(12):900-904.) http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200312004.htm
[18]	OGURA M, SHINOMIYA S Y, TATENO J, NARA Y, NOMURA M. Alkali-treatment technique-new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J]. Appl Catal A:Gen, 2001, 219(1/2):33-34. https://www.researchgate.net/publication/222877270_Alkali-treatment_technique_-_New_method_for_modification_of_structural_and_acid-catalytic_properties_of_ZSM-5_zeolites
[19]	SONG Y Q, ZHANG X X, SONG Y. An effective method to enhance the stability on-stream of butene aromatization:Post-treatment of ZSM-5 by alkali solution of sodium hydroxide[J]. Appl Catal A:Gen, 2006, 302(1):69-77. doi: 10.1016/j.apcata.2005.12.023
[20]	GROEN J C, PEFFER LAA, MOULIJN J A, PÉREZ-RAMÍREZ. Mesoporosity development in ZSM-5 zeolite upon optimized desilination conditions in alkaline medium[J]. Colloid Surf A, 2004, 241(1/3):53-58.
[21]	OGURA M, SHINOMIYA S Y, TATENO J, NARA Y, NOMURA M. Alkali-treatment technique-new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J]. Appl Catal A:Gen, 2001, 219(1):33-43. https://www.researchgate.net/publication/222877270_Alkali-treatment_technique_-_New_method_for_modification_of_structural_and_acid-catalytic_properties_of_ZSM-5_zeolites
[22]	王素珍, 罗国华, 徐新, 佟泽民, 彭少逸. 介孔分子筛MCM-41的合成及其催化噻吩与异丁烯烷基化反应性能[J]. 石油化工, 2004, 33(2):113-117. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200402004.htm (WANG Su-zhen, LUO Guo-hua, XU Xin, TONG Ze-min, PENG Shao-yi. Synthesis and catalytic alkylation of thiophene and isobutene properties of MCM-41 mesoporous molecular sieve[J]. Petrochem Technol, 2004, 33(2):113-117.) http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200402004.htm
[23]	ZHENG X D, DONG H J, WANG X, SHI L. Study on olefin alkylation of thiophenic sulfur in FCC gasoline using La₂O₃-modified HY zeolite[J]. Catal Lett, 2009, 127(1/2):70-74.
[24]	何英萍, 刘民, 代成义, 徐舒涛, 魏迎旭, 刘中民, 郭新闻. 四丙基氢氧化铵改性纳米HZSM-5分子筛及其在甲醇制汽油中的催化性能[J]. 催化学报, 2013, 34(6):1148-1158. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA201306017.htm (HE Ying-ping, LIU Min, DAI Cheng-yi, XU Shu-tao, WEI Ying-xu, LIU Zhong-min, GUO Xin-wen. The modification of nano HZSM-5 molecular sieve by TPAOH and its catalytic performance on methanol to gasoline[J]. Chin J Catal, 2013, 34(6):1148-1158.) http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA201306017.htm
[25]	李莎, 李玉平, 狄春雨, 张鹏飞, 潘瑞丽, 窦涛. TPAOH/NaOH 混合碱体系对 ZSM-5 沸石的改性及其催化性能研究[J]. 燃料化学学报, 2012, 40(5):583-588. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17947.shtml (LI Sha, LI Yu-ping, DI Chun-yu, ZHANG Peng-fei, PAI Rui-li, DOU Tao. Modification and catalyst performance of ZSM-5 zeolite by treatment with TPAOH/NaOH mixed alkali[J]. J Fuel Chem Technol, 2012, 40(5):583-588.) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17947.shtml
[26]	黄先亮. 二次晶化法修饰改性TS-1及催化环己酮氨氧化反应的研究[D]. 湘潭:湘潭大学, 2008. HUANG Xian-liang. Study on the modification of TS-1 by two crystallization method and the catalytic cyclohexanone ammoxidation reaction[D]. Xiangtan:Xiangtan University, 2008.)
[27]	RAJANI K V, RAJESH S, MURALI K P, MOHANAN P, RATHEESH R. Preparation and microwave charaterization of PTFE/PEEK blends[J]. Polym Compos, 2009, 30(3):296-300. doi: 10.1002/pc.v30:3
[28]	WEI S, XU Y, XU X, WANG J. Kinetics of alkylation of thiophene over HY zeolite[J]. Chem React Eng Technol, 2012, 28(2):159-163. https://www.researchgate.net/publication/286163965_Kinetics_of_alkylation_of_thiophene_over_HY_zeolite