改性ZSM-5-SBA-15及甲苯甲醇烷基化性能研究

詹金友; 张璐璐; 孙尧; 沈健

改性ZSM-5-SBA-15及甲苯甲醇烷基化性能研究

辽宁石油化工大学石油化工学院, 辽宁抚顺 113001

详细信息

中图分类号: TQ426.6
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出版历程
- 收稿日期: 2015-10-13
- 修回日期: 2016-01-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-04-30

Modified ZSM-5-SBA-15 and its alkylation performance for toluene with methanol

College of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China

More Information

Corresponding author: E-mail: lnshenjian@126.com.

摘要

摘要: 通过浸渍法对ZSM-5进行金属M(M为Mg、Ni、Sr)改性,合成法制备了M-ZSM-5-SBA-15复合分子筛,采用XRD、N₂吸附-脱附、FT-IR、NH₃-TPD和Py-FTIR等技术对样品进行表征,考察了HZSM-5的硅铝比、不同金属对ZSM-5-SBA-15复合分子筛烷基化性能的影响。结果表明,HZSM-5的硅铝比为80时,ZSM-5-SBA-15复合分子筛的烷基化性能较好,Sr的引入钝化了ZSM-5-SBA-15(80)的强B酸中心,降低了B酸与L酸的比值,Sr-ZSM-5-SBA-15(80)的甲苯甲醇烷基化性能明显提高,甲苯转化率为30.15%,对二甲苯选择性为77.41%。
- ZSM-5-SBA-15 /
- 金属改性 /
- 烷基化 /
- 对二甲苯
Abstract: ZSM-5 was modified by metal M (M for Mg, Ni or Sr) using impregnation method first, then the micro-mesoporous composite molecular sieve of M-ZSM-5-SBA-15 was synthesized by post synthesis. The samples were characterized by means of XRD, N₂ adsorption-desorption, FT-IR, NH₃-TPD and Py-FTIR. The influence of silica alumina ratio of the HZSM-5 and different metals modification on alkylation performance were investigated. The results showed that the ZSM-5/SBA-15 composite molecular sieve with silica alumina ratio of 80 showed the best performance in alkylation. The introduction of Sr passivated strong Brnsted acid centers and reduced the ratio of Brnsted acid and Lewis acid of ZSM-5-SBA-15(80), resulting in good performance in alkylation with a toluene conversion of 30.15% and a p-xylene selectivity of 77.41%.
- ZSM-5-SBA-15 /
- metal modified /
- alkylation /
- p-xylene

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图 1 样品的小角XRD谱图

Figure 1 X-ray powder diffraction patterns of the samples

a: SBA-15; b: ZSM-5-SBA-15(25); c: ZSM-5-SBA-15(50); d: ZSM-5-SBA-15(80); e: ZSM-5-SBA-15(120); f: ZSM-5-SBA-15(150)

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图 2 样品的广角XRD谱图

Figure 2 X-ray powder diffraction patterns of the samples

a: ZSM-5; b: ZSM-5-SBA-15(25); c: ZSM-5-SBA-15(50); d: ZSM-5-SBA-15(80); e: ZSM-5-SBA-15(120); f: ZSM-5-SBA-15(150)

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图 3 样品的小角XRD谱图

Figure 3 X-ray powder diffraction patterns of the samples

a: ZSM-5-SBA-15(80); b: Mg-ZSM-5-SBA-15(80); c: Ni-ZSM-5-SBA-15(80); d: Sr-ZSM-5-SBA-15(80)

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图 4 样品的大角XRD谱图

Figure 4 X-ray powder diffraction patterns of the samples

a: ZSM-5-SBA-15(80); b: Sr-ZSM-5-SBA-15(80); c: Ni-ZSM-5-SBA-15(80); d: Mg-ZSM-5-SBA-15(80)

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图 5 样品的红外光谱谱图

Figure 5 Infrared spectra of the samples

a: ZSM-5; b: SBA-15; c: ZSM-5-SBA-15(80); d: Sr-ZSM-5-SBA-15(80)

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图 6 样品的N₂吸附-脱附曲线

Figure 6 N₂ adsorption-desorption isotherms of the samples

▼: ZSM-5; ▲: SBA-15; ●: ZSM-5-SBA-15(80); ■: Sr-ZSM-5-SBA-15(80)

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图 7 样品的NH₃-TPD谱图

Figure 7 NH₃-TPD spectra of of the samples

a: ZSM-5; b: ZSM-5-SBA-15(80); c: Sr-ZSM-5-SBA-15(80)

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表 1 样品的甲苯甲醇烷基化性能

Table 1 Alkylation catalytic properties of the samples

Catalyst	Conversion x_T /%		Selectivity s_PX /%		Yield w_PX /%
Catalyst	400℃	420℃	400℃	420℃	400℃	420℃
ZSM-5-SBA-15(25)	32.43	33.52	52.35	53.88	16.98	18.06
ZSM-5-SBA-15(50)	31.35	32.22	59.71	57.78	18.72	18.62
ZSM-5-SBA-15(80)	28.72	30.31	67.78	64.03	19.47	19.41
ZSM-5-SBA-15(120)	26.84	27.42	68.68	67.29	18.43	18.45
ZSM-5-SBA-15(150)	23.15	24.34	69.78	68.42	16.15	16.65

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表 2 样品的甲苯甲醇烷基化性能

Table 2 Alkylation catalytic properties of the samples

Catalyst	Conversion x_T /%		Selectivity s_PX /%		Yield w_PX /%
Catalyst	400℃	420℃	400℃	420℃	400℃	420℃
ZSM-5-SBA-15(80)	28.72	30.31	67.78	64.03	19.47	19.41
Sr-ZSM-5-SBA-15(80)	30.15	31.67	77.41	73.08	23.34	23.15
Ni-ZSM-5-SBA-15(80)	25.37	26.43	69.98	67.48	17.75	17.83
Mg-ZSM-5-SBA-15(80)	20.24	21.42	70.67	69.04	14.30	14.78

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表 3 样品的结构参数

Table 3 Structural properties of the the samples

Sample	Specific surface area A/(m²·g^-1)	Porevolume v/(cm³·g^-1)	Porediameterd/(nm)
ZSM-5(Si/Al=80)	325.58	0.10	0.57
SBA-15	844.07	1.11	5.27
ZSM-5-SBA-15(80)	820.08	0.94	4.46
Sr-ZSM-5-SBA-15(80)	811.69	0.94	4.18

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表 4 ZSM-5-SBA-15(80)和Sr-ZSM-5-SBA-15(80)样品的Py-FTIR表征

Table 4 Brönsted acid sites and Lewis acid sites of ZSM-5-SBA-15(80) and Sr-ZSM-5-SBA-15(80) by Py-FTIR

	ZSM-5-SBA-15(80)			Sr-ZSM-5-SBA-15(80)
	B and L	B	L	B and L	B	L
160℃	0.014	0.172	0.186	0.012	0.183	0.195
250℃	0.009	0.087	0.096	0.011	0.092	0.103
350℃	0.069	0.092	0.161	0.109	0.094	0.203
450℃	0.065	0.011	0.076	0.009	0.007	0.016
Total acid sites	0.157	0.362	0.519	0.141	0.376	0.517
B: Brönsted acid sites ; L: Lewis acid sites; B and L: Brönsted acid sites and Lewis acid sites

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参考文献(19)

[1]	王莉, 朱景利, 李华宝, 王艳辉. 甲苯和甲醇烷基化反应热力学分析与计算[J]. 化学工程, 2008, 36(10): 48-51. http://www.cnki.com.cn/Article/CJFDTOTAL-IMIY200810017.htm WANG Li, ZHU Jing-li, LI Hua-bao, WANG Yan-hui. Thermodynamic analysis and calculation of alkylation of toluene with methanol[J]. Chem Eng, 2008, 36(10): 48-51. http://www.cnki.com.cn/Article/CJFDTOTAL-IMIY200810017.htm
[2]	陈庆龄, 孔德金, 杨卫胜. 对二甲苯增产技术发展趋向[J]. 石油化工, 2004, 33(10): 909-915. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200410001.htm CHEN Qing-ling, KONG De-jin, YANG Wei-sheng. Developmental trends in p-xylene production increasing technology[J]. Petrochem Technol, 2004, 33(10): 909-915. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200410001.htm
[3]	ZHAO Y, TAN W, WU H Y, ZHANG A F, LIU M, LI G M, WANG X S, SONG C S, GUO X W. Effect of Pt on stability of nano-scale ZSM-5 catalyst for toluene alkylation with methanol into p-xylene[J]. Catal Today, 2011, 160(1): 179-183. doi: 10.1016/j.cattod.2010.05.036
[4]	DING C H, WANG X S, GUO X W, ZHANG S G. Characterization and catalytic alkylation of hydrothermally dealuminated nanoscale ZSM-5 zeolite catalyst[J]. Catal Commun, 2008, 9(4): 487-493. doi: 10.1016/j.catcom.2007.07.013
[5]	BROWN S H, MATHIAS M F, WARE R A, OLSON D H. Selective para-xylene production by toluene methylation: US, EP 0935591 A1. 1999-11-15.
[6]	VOS A M, ROZANSKA X, SCHOONHEYDT R A, SANTEN R U, HUTSCHKA F, HAFNER J. A theoretical study of the alkylation reaction of toluene with methanol catalyzed by acidic mordenite [J]. J Am Chem Soc, 2001, 123(12): 2799-2809. doi: 10.1021/ja001981i
[7]	许峰, 顾建峰, 关乃佳, 袁忠勇. Mg改性ZSM-5/AlPO4-5复合分子筛用于甲苯甲醇侧链烷基化反应[J]. 石油学报(石油加工), 2008, 24(B10): 346-349. http://cpfd.cnki.com.cn/Article/CPFDTOTAL-ZGHY200811001081.htm XU Feng, GU Jian-feng, GUAN Nai-jia, YUAN Zhong-yong. Magnesium modified ZSM-5/AIPO4-5 composite zeolite for side-chain alkylation of toluene with methanol[J]. Acta Pet Sin (Pet Process Sect), 2008, 24(B10): 346-349. http://cpfd.cnki.com.cn/Article/CPFDTOTAL-ZGHY200811001081.htm
[8]	ZHU Z R, XIE Z K, CHEN Q L, KONG D J, LI W, YANG W M, LI C. Chemical liquid deposition with polysiloxane of ZSM-5 and its effect on acidity and catalytic properties[J]. Microporous Mesoporous Mater, 2007, 101(1/2): 169-175. https://www.researchgate.net/publication/229193156_Chemical_liquid_deposition_with_polysiloxane_of_ZSM-5_and_its_effect_on_acidity_and_catalytic_properties
[9]	DUNG VAN VU, MIYAMOTO M, NISHIYAMA N, ICHIKAWA S, EGASHIRA Y, UEYAMA K. Catalytic activities and structures of silicalite-1/H-ZSM-5 zeolite composites[J]. Microporous Mesoporous Mater, 2008, 115(1/2): 106-112. https://www.researchgate.net/publication/248293134_Catalytic_activities_and_structures_of_silicalite-1H-ZSM-5_zeolite_composites
[10]	NISHIYAMA N, MIYAMOTO M, EGASHIRA Y, UEYAMA K. Zeolite membrane on catalyst particles for selective formation of p-xylene in the disproportionation of toluene[J].Chem Commun, 2001, 18(18): 1746-1747.
[11]	纪永军, 张斌, 张坤, 徐乐, 彭洪根, 吴鹏. ZSM-5@Mesoporous Silica 核壳复合结构分子筛的制备及其甲苯甲醇烷基化择形催化性能的研究[J].化学学报, 2013, 71(3): 371-380. doi: 10.6023/A12110980 JI Yong-jun, ZHANG Bin, ZHANG Kun, XU Le, PENG Hong-gen, WU Peng. Core/shell-structured ZSM-5@mesoporous silica composites for shape-selective alkylation of toluene with methanol[J]. Acta Chim Sin, 2013, 71(3): 371-380. doi: 10.6023/A12110980
[12]	王政, 陈娟, 王林, 马清祥, 赵天生. MFI 型核壳分子筛在甲苯甲醇烷基化反应中的催化性能[J]. 石油学报 (石油加工), 2011, 27(5): 812-816. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201105030.htm WANG Zheng, CHEN Juan, WANG Lin, MA Qing-xiang, ZHAO Tian-sheng. Catalytic activity of MFI type core-shell zeolite for alkylation of toluene with methanol[J]. Acta Pet Sin (Pet Process Sect), 2011, 27(5): 812-816. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201105030.htm
[13]	刘鹏, 沈健. ZSM-5-SBA-15复合分子筛制备及甲苯甲醇烷基化性能研究[J]. 燃料化学学报, 2015, 43(9): 1147-1152. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1314.shtml# LIU Peng, SHEN Jian. Preparation of ZSM-5-SBA-15 composite molecular sieves and its performance for toluene alkylation with methanol[J]. J Fuel Chem Technol, 2015, 43(9): 1147-1152. http://rlhxxb.sxicc.ac.cn/CN/volumn/volumn_1314.shtml#
[14]	FARAMAWY S. Selective toluene-methanol alkylation over modified ZSM-5 zeolite catalysts[J]. Pet Sci Technol, 1999, 17(3/4): 249-271.
[15]	刘鹏, 沈健. ZSM-5-SBA-15 复合分子筛的制备[J]. 硅酸盐学报, 2015, 43(7): 875-881. http://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201507006.htm LIU Peng, SHEN Jian. Investigation on the preparation of ZSM-5-SBA-15 composite molecular sieves[J]. J Chin Silic Soc, 2015, 43(7): 875-881. http://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201507006.htm
[16]	吴淑杰, 黄家辉, 吴通好, 宋科, 王虹苏, 邢丽红, 徐海燕, 徐玲, 管景奇, 阚秋斌. Al-SBA-15介孔分子筛的合成、表征及其在苯酚叔丁基化反应中的催化性能[J]. 催化学报, 2006, 27(1): 9-14. doi: 10.1016/S1872-2067(06)60004-1 WU Shu-jie, HUANG Jia-hui, WU Tong-hao, SONG Ke, WANG Hong-su, XING Li-hong, XU Hai-yan, XU Ling, GUAN Jing-qi, KAN Qiu-bin. Synthesis, characterization, and catalytic performance of mesoporous Al-SBA-15 for Tert-butylation of phenol[J]. Chin J Catal, 2006, 27(1): 9-14. doi: 10.1016/S1872-2067(06)60004-1
[17]	吴静. 多级孔ZSM-5分子筛的合成及其在甲醇制芳烃中的应用[D]. 上海: 华东理工大学, 2014. WU Jing. Synthesis and aftertreatment of hierarchical ZSM-5 and its application in MTA[D]. Shanghai: East China University of Science and Technology, 2014.
[18]	于龙, 庞文琴. 杂原子W-ZSM-5分子筛的合成与表征[J]. 催化学报, 1991, 12(5): 376-380. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA199105007.htm YU Long, PANG Wen-qin. Synthesis and characterization of heteroatom type W-ZSM-5 molecular sieves[J]. Chin J Catal, 1991, 12(5): 376-380. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA199105007.htm
[19]	张若杰, 万海, 张乐, 宋丽娟. 双金属改性ZSM-5/L复合分子筛的制备及其催化芳构化反应性能[J]. 石油炼制与化工, 2015, 46(7): 67-72. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201507030.htm ZHANG Ruo-jie, WAN Hai, ZHANG Le, SONG Li-juan. Synthesis of bimetal ZSM-5/L composite zeolite and its catalytic performance for aromatization reaction[J]. Pet Process Petrochem, 2015, 46(7): 67-72. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201507030.htm