不同金属改性对ZSM-5分子筛催化正戊烷甲醇共芳构化反应性能的影响

石油炼制与化工 ›› 2019, Vol. 50 ›› Issue (8): 46-51.

不同金属改性对ZSM-5分子筛催化正戊烷甲醇共芳构化反应性能的影响

侯扬飞,于明煊,张娇玉,祝晓琳,李春义

中国石油大学（华东）重质油国家重点实验室

收稿日期:2018-12-20 修回日期:2019-02-25 出版日期:2019-08-12 发布日期:2019-08-27
通讯作者: 李春义 E-mail:chyli@upc.edu.cn
基金资助:
国家自然科学基金青年科学基金;山东省自然科学基金博士基金

EFFECT OF MODIFIED ZSM-5 ZEOLITE WITH DIFFERENT METALS ON n-PENTANE AND METHANOL CO-AROMATIZATION

Received:2018-12-20 Revised:2019-02-25 Online:2019-08-12 Published:2019-08-27
Contact: Li Chunyi E-mail:chyli@upc.edu.cn
Supported by:

摘要/Abstract

摘要： 通过浸渍法对ZSM-5分子筛进行改性，得到不同金属、不同负载量改性的分子筛，采用XRD和Py-IR方法对催化剂进行表征。在固定床微型反应装置上，系统探究了不同金属改性对ZSM-5分子筛催化正戊烷和甲醇共芳构化反应性能的影响。结果表明：Zn，Ag，Ni，Cu改性ZSM-5分子筛均能提高共芳构化反应的芳烃选择性，Ni、Ag改性ZSM-5分子筛表现出更优的芳构化效果，在最优金属负载量下，共芳构化反应中正戊烷和甲醇转化率保持在100%，芳烃选择性高达37.69%；Zn，Ag，Ni，Cu改性ZSM-5分子筛均有新的L酸位形成，B酸量减少，L酸量增加，促进了脱氢反应，反应过程中有更多的烯烃中间体转化为芳烃，提高了芳烃选择性；不同金属改性ZSM-5分子筛，产物芳烃组成中有不同组分含量的提高。

关键词: ZSM-5分子筛, 金属, 锌, 银, 铜, 正戊烷, 甲醇, 共芳构化

Abstract: ZSM-5 molecular sieve were modified with different metals by impregnation method to obtain zeolite catalysts with different metals loads. The catalysts were characterized by XRD, Py-IR techniques. The aromatization performance of the samples in n-pentane and methanol co-aromatization was investigated in a fixed-bed micro-reactor. The results showed that Zn, Ag, Ni, and Cu, modified catalysts improved the aromatic selectivity, among which the Ni and Ag modified catalysts showed the better aromatization effects. With the optimal metal load, the conversions of n-pentane and methanol were 100%; the aromatic selectivity was up to 37.69%. The catalysts modified with Zn, Ag, Ni, and Cu showed the formation of new L acid, decrease of B acid and increase of L acid, which promoted the dehydrogenation reaction, forming more aromatics from olefin intermediates and improving the aromatic selectivity. The content of different aromatic components in the products increased with the modification of different metals

Key words: ZSM-5 molacular sieve, metal, zinc, silver, copper, n-pentane, methanol, co-aromatization

中图分类号:

侯扬飞于明煊张娇玉祝晓琳李春义. 不同金属改性对ZSM-5分子筛催化正戊烷甲醇共芳构化反应性能的影响[J]. 石油炼制与化工, 2019, 50(8): 46-51.

参考文献

[1] Giannetto G, Monque R, Galiasso R, et al. Transformation of LPG into aromatic hydrocarbons and hydrogen over zeolite catalysts[J]. Catalysis Reviews: Science and Engineering, 1994, 36(2):271-304.
[2] 李涛. 碳一化工的技术、产品现状及发展方向[J]. 化工进展, 2012,31(S1):124-128.
[3] 邵平. 甲苯甲醇合成对二甲苯的新技术及市场分析[J]. 炼油与化工, 2012,23(5):6-8.
[4] Li Xiujie, Liu Shenglin, Zhu Xiangxue, et al. Effects of zinc and magnesium addition to ZSM-5 on the catalytic performances in 1-hexene aromatization reaction[J]. Catalysis Letters, 2011, 141(7): 1498–1505.
[5] Abdelsayed V, Smith M W, Shekhawat D. Investigation of the stability of Zn-based HZSM-5 catalysts for methane dehydroaromatization[J]. Applied Catalysis A:General, 2015, 505(25): 365–374.
[6] Li Yuning, Liu Shenglin, Xie Sujuan, et al. Promoted metal utilization capacity of alkali-treated zeolite: Preparation of Zn/ZSM-5 and its application in 1-hexene aromatization[J]. Applied Catalysis A: General, 2009, 360(1): 8–16.
[7] 田涛, 骞伟中, 汤效平, 等. 甲醇芳构化反应中Ag/ZSM-5催化剂的失活特性[J]. 物理化学学报, 2010, 26(12): 3305-3309.
[8] 王恒强, 张成华, 吴宝山, 等. Ga、Zn改性方法对HZSM-5催化剂丙烯芳构化性能的影响[J]. 燃料化学学报, 2010, 38(5): 576-581.
[9] Wei Yingxu, Liu Zhongmin, Wang Gongwei, et al. Production of light olefins and aromatic hydrocarbons through catalytic cracking of naphtha at lowered temperature[J]. Studies in Surface Science and Catalysis, 2005, 158(B): 1223-1230.
[10] Lu Jiangyin, Zhao Zhen, Xu Chunming, et al. FeHZSM-5 molecular sieves – highly active catalysts for catalytic cracking of isobutene to produce ethylene and propylene[J]. Catalysis Communications, 2006, 7(4): 199–203.
[11] Sadrameli S. M. Thermal/catalytic cracking of liquid hydrocarbons for the production of olefins: A state-of-the-art review II: Catalytic cracking review[J]. Fuel, 2016, 173(1): 285-297.
[12] Wang Guowei, Wang Haoren, Zhang Huanling, et al. Highly Selective and Stable NiSn/SiO2 Catalyst for Isobutane Dehydrogenation: Effects of Sn Addition[J]. Chemcatchem Catalysis, 2016, 8(19): 3137-3145.
[13] Zhang Guiquan, Bai Ting, Chen Tengfei, et al. Conversion of methanol to light aromatics on Zn-modified nano-HZSM-5 zeolite catalysts[J]. Industrial & Engineering Chemistry Research, 2014, 53(39): 14932–14940.
[14] Song Chao, Li Xiujie, Zhu Xiangxue, et al. Influence of the state of Zn species over Zn-ZSM-5/ZSM-11 on the coupling effects of cofeeding n-butane with methanol [J]. Applied Catalysis A: General, 2016, 519(1): 48-55.
[15] Su Xiaofang, Zan Wang, Bai Xuefeng, et al. Synthesis of microscale and nanoscale ZSM-5 zeolites: effect of particle size and acidity of Zn modified ZSM-5 zeolites on aromatization performance [J]. Catalysis Science & Technology, 2017, 7(4): 1943-1952.
[16] Almutairi S M T, Mezari B, Magusin P C M M, et al. Structure and reactivity of Zn-modified ZSM-5 zeolites: the importance of clustered cationic Zn complexes [J]. ACS Catalysis, 2012, 2(1): 71-83.
[17] 尹双凤, 陈懿, 林洁, 等. 正己烷在Zn/HZSM-5上芳构化反应机理的探讨[J]. 工业催化, 2002, 10(1): 34-37.
[18] 程谟杰, 杨亚书. ZnHZSM-5上脱氢环化芳构化过程的探讨[J]. 分子催化, 1996, 10(6): 418-422.
[19] Bi Yi, Wang Yingli, Chen Xin, et al. Methanol aromatization over HZSM-5 catalysts modified with different zinc salts[J]. Chinese Journal of Catalysis, 2014, 35(10): 1740-1751.
[20] 田涛, 骞伟中, 孙玉建, 等. Ag/ZSM-5催化剂上甲醇芳构化程[J]. 现代化工, 2009, 29(1): 55-58.
[21] Marco C, Qian H, Yulia R, et al. Modified zeolite ZSM-5 for the methanol to aromatics reaction[J]. Catalysis Science & Technology, 2012, 2(1): 105-112.