Study on thiophene alkylation performance of hierarchical ZSM-5 zeolites modified by different alikali
-
摘要: 用Na2CO3、TPAOH和TPA+/CO32-混合碱分别处理HZSM-5分子筛,采用FT-IR、XRD、XRF、N2吸附脱附、SEM、NH3-TPD及Py-FTIR表征手段对各类碱处理前后的HZSM-5分子筛进行表征。结果表明,3种类型的碱处理HZSM-5分子筛后,均能形成微孔-介孔多级孔道的HZSM-5(A)催化剂,并能调变催化剂的酸性,其中,TPA+/CO32-混合碱处理得到的HZSM-5(TPA+/CO32-)催化剂,比表面积最大,介孔数量最多。在小型固定床反应器上,考察了HZSM-5和HZSM-5(A)催化剂的噻吩烷基化性能,结果表明,HZSM-5(TPA+/CO32-)催化剂因为具有适当的多级孔孔道和较多的B酸中心而表现出较高的噻吩转化率和1-己烯对噻吩的选择性。Abstract: HZSM-5 zeolites were respectively treated by Na2CO3,TPAOH and mixed alkali solution of TPA+/CO32-. The samples were characterized by FT-IR XRD, XRF, N2 adsorption/desorption, SEM, NH3-TPD and Py-FTIR techniques. It was found that the microporous and mesoporous hierarchical HZSM-5 (A) catalysts were formed after the treatment and their acidity were modulated. The largest surface area and the most mesoporous were found in the HZSM-5(TPA+/CO32-) treated by the mixed alkali of TPA+/CO32- s. The thiophene alkylation performance of HZSM-5 and HZSM-5(A) zeolites was investigated in a small-scale fixed bed reactor with model compounds as feedstock. The co-sequences displayed that HZSM-5 (TPA+/CO32-) catalysts exhibited the higher conversion of thiophene and selectivity of 1-hexene because the zeolites had proper hierarchical pore diameter and more B-acid sites.
-
Key words:
- Na2CO3 /
- TPAOH /
- ZSM-5 /
- hierarchical pore /
- thiophene alkylation
-
ZHANG Z K, LIU S L, ZHU X X, WANG Q X, XU L Y. Modification of Hβ zeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline[J]. Fuel Process Technol, 2008, 89(1):103-110. DUPUY B, LAFORGE S, BACHMANN C, MAGNOUX P, RICHARD F. Desulfurization of model FCC feedstocks by alkylation:Transformation of thiophenic compounds in presence of 2-methyl-1-pentene over acidic zeolites[J]. J Mol Catal A:Chem, 2012, 363-364:273-282. ZHANG Z K, NIU X L, LIU S L, ZHU X X, YU H W, XU L Y. The performance of HMCM-22 zeolite catalyst on the olefin alkylation thiophenic sulfur in gasoline[J]. Catal Commun, 2008, 9(1):60-64. 魏书梅, 徐亚荣, 徐新良, 王吉德. HY分子筛催化噻吩类硫化物的烷基化反应动力学[J]. 化学反应工程与工艺, 2012, 28(2):159-163. (WEI Shu-mei, XU Ya-rong, XU Xin-liang, WANG Ji-de. Kinetics of alkylation of thiophene over HY zeolite[J]. Chem React Eng Technol, 2012, 28(2):159-163.) DUPUY B, LAFORGE S, MORAIS C, BACHMANN C, MAGNOUX P, RICHARD F. Alkylation of 3-methylthiophene by 2-methyl-1-pentene over HY, HBEA and HMCM-22 acidic zeolites[J]. Appl Catal A:Gen, 2012, 413-414(31):192-204. PRADHAN V R, BURNETT P A, STACEY M D, HODGES M. Multistage process for removal of sulfur from components for blending of transportation fuels:US, 6733660[P]. 2004-05-11. 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, 2012, 40(5):583-588. (ZHAO Cen, LIU Dong-mei, Wei Min, SUN Zhi-yan, WANG Hai-yan. Preparation and thiophene alkylation performance of hierarchical ZSM-5 zeolites[J]. J Fuel Chem Technol, 2012, 40(5):583-588.) LI Y N, LIU S L, ZHANG Z K, XIE S J, ZHU X X, XU L Y. Aromatization and isomerization of 1. Hexene over alkali-treated HZSM-5 zeolites:Improved Reaction Stability [J]. Appl Catal A:Gen, 2008, 338(4):100-113. NAGABHATLA V, SANDEEP K S, JITENDRA K, PATA S, DEVAKI N. Catalytic performanceof nano crystalline HZSM-5 in ethanol to gasoline(ETG)reaction[J]. Fuel, 2012, 95(1):298-304. 何英萍, 刘民, 代成义. 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. (HE Ying-ping, LIU Min, DAI Cheng-yi. HZSM-5 zeolites modified tetrapropylammonium hydroxide and the catalytic properties in methanol gasoline[J]. Chin J Catal, 2013, 34(6):1148-1158.) 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. (LI Sha, LI Yu-ping, DI Chun-yu, ZHANG Peng-fei, PAN Rui-li, DOU Tao. Study on catalytic properties of ZSM-5 zeolites modified by TPAOH/NaOH mixed alkali system[J]. J Fuel Chem Technol, 2012, 40(5):583-588.) 石冈, 林秀英, 范煜, 鲍晓军. ZSM-5分子筛的脱硅改性及加氢改质性能[J]. 燃料化学学报, 2013, 41(5):589-600. (SHI Gang, LIN Xiu-ying, FAN Yu, BAO Xiao-jun. Desilication modification of ZSM-5 zeolite and its catalytic properties in hydro-upgrading[J]. J Fuel Chem Technol, 2013, 41(5):589-600.) 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 secondary crystallization method modified TS-1and catalytic ammoxidation of cyclohexanone[D]. Xiangtan:Xiangtan University, 2008.) OGURA M, SHINOMIYA S Y, TATNEO J, NARA Y, NOMURA M, KIKUCHI E, MATSUKATA M. Alkali-treatment technique-new method for modification of structure and acid-catalytic properties of ZSM-5 zeolites[J]. Appl Catal A:Gen, 2001, 219(1/2):33-43. JELINEK J L, KOVATS E. True surface areas from nitrogen adsorption experiments[J]. Langmuir, 1994, 10(11):4225-4231. MORTEN B, FINN J, MARTIN S H, UNNI O, KARL-PETTER L, STIAN S. Methanol to gasoline over zeolite H-ZSM-5:Improved catalystperformance by treatment with NaO[J]. Appl Catal A:Gen, 2008, 345(1):43-50. 肖何, 高俊华, 胡津仙, 章斌, 刘平, 张侃. 酸碱改性HZSM-5分子筛上甲醇制取均四甲苯的研究[J]. 燃料化学学报, 2013, 41(1):102-109. (XIAO He, GAO Jun-hua, HU Jin-xian, ZHANG Bin, LIU Ping, ZHANG Kan. Research on four toluene prepared methanol properity of HZSM-5 zeolites modified acid[J]. J Fuel Chem Technol, 2013, 41(1):102-109.) 梁战桥, 顾昊辉, 赵斌. 水热处理ZSM-5沸石对乙苯转化型二甲苯异构化催化剂性能的影响[J]. 石油化工, 2009, 38(9):940-944. (LIANG Zhan-qiao, GU Hao-hui, ZHAO Bin. Hydrothermal treatment of ZSM-5 zeolites influence on the conversion of ethlbenzen and xyene isomerization catalyst[J]. Petrochemical, 2009, 38(9):940-944.) 聂宁, 沈健. USY分子筛催化噻吩烷基化性能的研究[J]. 石化技术与应用, 2013, 31(2):110-113. (NIE Ning, SHEN Jian. Research on thiophene alkylation performance of USY zeolite catalytic[J]. Petrochem Technol Appl, 2013, 31(2):110-113.) BABICH I V, MOULIJN J A. Science and technology of novel processes for deep desulfurization of oil refinery streams:A review[J]. Fuel, 2003, 82(6):607-631. 柯明, 汤奕婷, 曹文智, 彭洪湃, 周爱国. 二烯烃与噻吩烷基化反应研究[J]. 西安石油大学学报(自然科学版), 2008, 23(5):75-80. (KE Ming, TANG Yi-ting, CAO Wen-zhi, PENG Hong-pai, ZHOU Ai-guo. Study on alkylation reaction of diolefin with thiophene[J]. J Xi'an Shiyou Univ, 2008, 23(5):75-80.) 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. (GUO Xiao-ye, ZHANG Ze-kai, LIU Sheng-lin, LI Yu-ning, DAI Hong-yi, XU Long-ya. Alyalation desulfurization of thiophene in gasoline over potassium modified MCM-22 zeolites[J]. Ind Catal, 2008, 16(6):31-34.)
点击查看大图
计量
- 文章访问数: 369
- HTML全文浏览量: 40
- PDF下载量: 369
- 被引次数: 0