纳米Ga-ZSM-5分子筛的合成及其在苯和稀乙烯烷基化反应中的应用

doi:10.19964/j.issn.1006-4990.2021-0251

Abstract

Abstract:

A series of nano Ga-ZSM-5 zeolites with different Si/Ga ratio were synthesized with seed-oriented method.Ga-ZSM-5 catalysts were obtained with extrusion molding,acid pickling and high temperature roasting.The structure and acid properties of Ga-ZSM-5 zeolites were characterized by various techniques and their catalytic performance in the alkylation of benzene with dilute ethylene were evaluated.The results showed that hydrothermal synthesized Ga-ZSM-5 molecular sieves exhibited intergrown morphologies and uniform particle size.Compared with Al-ZSM-5 zeolites with the same n（Si）/n（T）（T was metal atom）,the acid content and acid strength of Ga-ZSM-5 zeolites were significantly reduced.Under the reaction conditions of T=360 ℃,P=1.4 MPa,weight hourly space velocity（WHSV） of ethylene=1.5 h^-1,n（benzene）∶n（ethylene）=1∶1,n（ethylene）∶n（nitrogen）=1∶5.67,Ga-ZSM-5 zeolites catalysts showed higher ethylbenzene selectivity and 30%~50% reduction for xylene selectivity compared with Al-ZSM-5.In addition,Ga-ZSM-5 zeolites catalyst remained stable during the time on stream of 100 h with stronger coke-resistant capacity.

Key words: Ga-ZSM-5, alkylation of benzene with dilute ethylene, ethylbenzene, acid properties

CLC Number:

TQ127.2

XIE Zhuohan,HAN He,LI Xiaoguo,ZHANG Yongkun,HOU Zhanggui,BIAN Kai,ZHANG Anfeng,GUO Xinwen,SONG Chunshan. Synthesis of nano Ga-ZSM-5 zeolite and its application in alkylation of benzene with dilute ethylene[J]. Inorganic Chemicals Industry, 2022, 54(2): 123-128.

Figures/Tables 12

Fig.1

Fig.2

Fig.3

Fig.4

Table 1

Fig.5

Fig.6

Table 2

Fig.7

Fig.8

Table 3

Fig.9

References 23

[1]	GUSHCHIN P A, KOLESNIKOV I M, VINOKUROV V A, et al. Al-kylation of benzene with ethylene in the presence of dimethyldichlo-rosilane[J]. Journal of Catalysis, 2017, 352:75-82. doi: 10.1016/j.jcat.2017.05.004
[2]	ODEDAIRO T, AL-KHATTAF S. Ethylation of benzene:Effect of zeolite acidity and structure[J]. Applied Catalysis A:General, 2010, 385(1/2):31-45. doi: 10.1016/j.apcata.2010.06.041
[3]	张永强, 杨克勇, 杜泽学, 等. 乙苯合成的研究进展[J]. 石油化工, 2001(10):796-799.
[4]	程志林, 赵训志, 邢淑建. 乙苯生产技术及催化剂研究进展[J]. 工业催化, 2007(7):4-9.
[5]	杨为民, 孙洪敏, 杨书江, 等. 苯和乙烯气相烷基化制乙苯ZSM型沸石催化剂的研究[J]. 上海化工, 2002, 27(Z2):16-18.
[6]	BIAN K, ZHANG A, YANG H, et al. Synjournal and characterization of Fe-SUbstituted ZSM-5 zeolite and its catalytic performance for alkylation of benzene with dilute ethylene[J]. Industrial & Engin-eering Chemistry Research, 2020, 59(52):22413-22421.
[7]	孙洪敏. 乙苯生产技术及市场分析[J]. 石油化工技术与经济, 2019, 35(5):18-23.
[8]	SUN L, LIU C L, QIAO Q, et al. The influence of water on the cata-lyst behavior of nanosized HZSM-5 zeolites in the ethylation of cok-ing benzene[J]. Journal of the Taiwan Institute of Chemical Engi-neers, 2016, 64:9-15.
[9]	张振亮, 王文英. 国内外干气制乙苯工艺对比[J]. 现代化工, 1998(9):32-34.
[10]	薛明伟. 干气综合利用生产技术进展[J]. 石油化工技术与经济, 2019, 35(1):56-62.
[11]	杨学萍, 薛明伟, 瞿勇. 炼化一体化企业利用稀乙烯资源潜力很大[J]. 中国石化, 2019(5):48-49.
[12]	YANG W, WANG Z, SUN H, et al. Advances in development and industrial applications of ethylbenzene processes[J]. Chinese Jo-urnal of Catalysis, 2016, 37(1).Doi: 10.1016/S1872-2067(15)60965-2. doi: 10.1016/S1872-2067(15)60965-2
[13]	孙洪敏, 杨为民, 关海延, 等. AB-97-T型气相烷基转移制乙苯催化剂的工业应用[J]. 工业催化, 2005(9):17-19.
[14]	张振. SEB-08催化剂在干气制乙苯装置的工业应用[J]. 广东化工, 2018, 45(3):150-151.
[15]	刘付华, 林亚祥, 练弢. SEB-08催化剂在300 kt/a 稀乙烯制乙苯装置上的工业应用[J]. 工业催化, 2018, 26(6):49-52.
[16]	陈福存, 朱向学, 谢素娟, 等. 催化干气制乙苯技术工艺进展[J]. 催化学报, 2009, 30(8):817-824.
[17]	SUN L P, GUO X W, LIU M, et al. Ethylation of coking benzene over nanoscale HZSM-5 zeolites:Effects of hydrothermal treat-ment,calcination and La₂O₃ modification[J]. Applied Catalysis A:General, 2009, 355(1/2):184-191. doi: 10.1016/j.apcata.2008.12.015
[18]	边凯, 候章贵, 段欣瑞, 等. 二维HZSM-5纳米片的合成及催化苯与稀乙烯烷基化制乙苯[J]. 高等学校化学学报, 2019, 40(4):784-792.
[19]	孙林平, 乔迁, 刘民, 等. 纳米和微米ZSM-5分子筛在焦化苯乙基化反应体系中稳定性比较[J]. 石油学报:石油加工, 2013, 29(1):46-50.
[20]	陈海军. 干气制乙苯过程建模与优化[D]. 大连:大连理工大学, 2017.
[21]	高志贤, 程昌瑞, 谭长瑜. Ga-Al-Si-ZSM-5 的合成、表征与催化性能[J]. 石油学报, 1996(1):42-48.
[22]	MENTZEL U V, HØJHOLT K T, HOLM M S, et al. Conversion of methanol to hydrocarbons over conventional and mesoporous H-ZSM-5 and H-Ga-MFI:Major differences in deactivation behav-ior[J]. Applied Catalysis A:General, 2012,417-418:290-297.
[23]	KOSSLICK H, TUAN V A, PARLITZ B, et al. Disruption of the MFI framework by the incorporation of gallium[J]. Journal of the Che-mical Society Faraday Transactions, 1993, 89(7):1131-1138.

样品	BET比表面积/ （m²·g^-1）	总孔容/ （cm³·g^-1）	微孔孔容/ （cm³·g^-1）
Z5-Al-80	418	0.61	0.15
Z5-Al-100	440	0.62	0.16
Z5-Al-120	428	0.61	0.16
Z5-Al-160	430	0.61	0.16
Z5-Ga-80	419	0.60	0.15
Z5-Ga-100	449	0.58	0.17
Z5-Ga-120	452	0.65	0.17
Z5-Ga-160	458	0.62	0.17

样品	n（Si）/n（T）^a （T=Ga或Al）	弱酸峰温度^b/℃	强酸峰温度^b/℃	酸量^b/（μmol·g^-1）
样品	n（Si）/n（T）^a （T=Ga或Al）	弱酸峰温度^b/℃	强酸峰温度^b/℃	弱酸	强酸	总酸量
Z5-Ga-80	131.7	246	395	39	23	62
Z5-Ga-100	160.6	235	380	30	22	52
Z5-Ga-120	193.8	228	397	25	18	43
Z5-Ga-160	269.1	223	398	22	20	42
Z5-Al-80	78.5	237	463	129	94	223
Z5-Al-160	144.8	256	437	72	53	125

样品	苯转化率/%	乙基选择性/%	二甲苯选择性/%
Z5-Al-80	43.6	92.8	0.39
Z5-Al-100	42.9	93.5	0.33
Z5-Al-120	42.1	93.2	0.28
Z5-Al-160	42.8	94.3	0.22
Z5-Ga-80	39.7	92.5	0.22
Z5-Ga-100	40.1	94.4	0.18
Z5-Ga-120	38.9	94.7	0.17
Z5-Ga-160	39.1	94.8	0.16

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Synthesis of nano Ga-ZSM-5 zeolite and its application in alkylation of benzene with dilute ethylene

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 23

Related Articles 2

Metrics

Comments

Recommended 0

[1]	ZHANG Yongkun, CHANG Yang, LI Xiaoguo, LIU Yan, XING Changxin, GAO Jinping, XIAO Jiawang, HOU Zhanggui. Study on modification of HZSM-5 catalyst and its pilot catalytic performance for alkylation of benzene with dilute ethylene [J]. Inorganic Chemicals Industry, 2023, 55(5): 137-142.
[2]	Sun Zhenhai,Li Bin,Guo Chunlei,Zang Jiazhong,Li Ben,Fan Jingxin,Wang Yang. Study on synthesis of mesoporous silica and its adsorption and separation properties [J]. Inorganic Chemicals Industry, 2021, 53(7): 68-72.