甲苯与甲醇择形催化制对二甲苯技术进展

doi:10.16085/j.issn.1000-6613.2022-0117

化工进展 ›› 2022, Vol. 41 ›› Issue (11): 5783-5799.DOI: 10.16085/j.issn.1000-6613.2022-0117

甲苯与甲醇择形催化制对二甲苯技术进展

韩贺¹(), 张锌豪¹(), 张安峰¹, 赵成浩², 石川¹, 于政锡³, 宋春山¹^,⁴, 郭新闻¹()

^1.大连理工大学化工学院精细化工国家重点实验室，辽宁大连 116024
^2.中国石化大连（抚顺）石油化工研究院，辽宁大连 116041
^3.中国科学院大连化学物理研究所甲醇制烯烃国家工程实验室，辽宁大连 116023
^4.香港中文大学理学院，香港 999077

收稿日期:2022-01-08 修回日期:2022-04-08 出版日期:2022-11-25 发布日期:2022-11-28
通讯作者: 郭新闻
作者简介:韩贺（1988—），男，博士后，助理研究员，研究方向为分子筛合成与多相催化。E-mail：hehan@dlut.edu.cn
张锌豪，硕士研究生，研究方向为甲苯甲醇烷基化。E-mail：919276768@mail.dlut.edu.cn。
基金资助:
国家自然科学基金青年基金(22008019);中国博士后科学基金(2021T140083);兴辽英才项目(XLYC2008032)

Development of shape-selective alkylation of toluene with methanol to para-xylene

HAN He¹(), ZHANG Xinhao¹(), ZHANG Anfeng¹, ZHAO Chenghao², SHI Chuan¹, YU Zhengxi³, SONG Chunshan¹^,⁴, GUO Xinwen¹()

^1.State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^2.Sinopec Dalian (Fushun) Research Institute of Petroleum and Petrochemicals, Dalian 116041, Liaoning, China
^3.National Engineering Laboratory for Methanol to Olefins, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^4.Faculty of Science, The Chinese University of Hong Kong, Hong Kong 999077, China

Received:2022-01-08 Revised:2022-04-08 Online:2022-11-25 Published:2022-11-28
Contact: GUO Xinwen

摘要/Abstract

摘要：

对二甲苯是一种重要的芳烃原料，在石油化工行业中有着举足轻重的地位。近十年来，我国对二甲苯的需求保持持续增长的态势，为了保障我国对二甲苯产业健康、稳步的发展，迫切需要开发更为低成本、高效的对二甲苯生产工艺。甲苯与甲醇择形催化制对二甲苯是目前最具前景和竞争力的新技术之一，然而如何在保持高选择性的前提下提高催化剂的稳定性是该技术面临的严峻挑战。低碳烯烃的生成是导致催化剂积炭失活的主要原因之一。本文通过对催化反应机理和催化剂研究进展的介绍，认为开发高选择性、高稳定性的催化剂可以从合成既有择形效应又有优良扩散特性的分子筛母体、协同调控分子筛的孔结构和酸性质以及抑制低碳烯烃的形成三个方向发力。

关键词: 催化剂, 沸石, 分子筛, 对二甲苯, 择形催化

Abstract:

Para-xylene is an important aromatic material in petrochemical industry. In recent decades, China’s demand for para-xylene has been growing. In order to ensure the healthy and steady development of para-xylene industry in China, it is urgent to develop a more low-cost and efficient para-xylene production process. Shape-selective alkylation of toluene with methanol to para-xylene is one of the most promising and competitive new technologies for para-xylene production. However, how to improve the stability of the catalysts while maintaining their high selectivity is still challenging. The formation of low-carbon olefins is one of the main reasons for the deactivation of the catalysts. Based on the discussion of the catalytic reaction mechanisms and research progress of the catalyst, we believe that the exploitation of highly selective and stable catalysts can be driven from three directions: synthesis of molecular sieve parent of shape-selective effect and excellent diffusion property, coordinated regulation of the pore structure and acid properties of molecular sieves, and inhibition of the formation of low-carbon olefins.

Key words: catalyst, zeolite, molecular sieves, para-xylene, shape-selective catalysis

中图分类号:

TQ426

韩贺, 张锌豪, 张安峰, 赵成浩, 石川, 于政锡, 宋春山, 郭新闻. 甲苯与甲醇择形催化制对二甲苯技术进展[J]. 化工进展, 2022, 41(11): 5783-5799.

HAN He, ZHANG Xinhao, ZHANG Anfeng, ZHAO Chenghao, SHI Chuan, YU Zhengxi, SONG Chunshan, GUO Xinwen. Development of shape-selective alkylation of toluene with methanol to para-xylene[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5783-5799.

图/表 10

图1 以石脑油为原料的现代芳烃联合装置中的工艺单元及流程简图[7]

图2 ZSM-5沸石上甲苯与甲醇择形催化制对二甲苯[10]

图3 分子筛催化剂上甲醇转化的反应机理[20]

图4 甲醇转化反应中双循环机理示意图[24]

表1 不同分子筛的孔结构性质及其甲苯与甲醇烷基化反应性能

名称	拓扑结构	分子筛结构	孔道尺寸	反应条件	改性条件	对二甲苯选择性/%	甲苯转化率/%	参考文献
SAPO-5	AFI	一维十二元环孔道	直孔道0.73nm×0.73nm	400℃；常压； F/W=0.24mol·g^-1·h^-1； n(T)/n(M)=2	未改性	25.0	16.0	［30］
β	BEA	三维十二元环孔道	直孔道0.73nm×0.60nm 弯曲孔道0.56nm×0.56nm	300℃；常压； WHSV=17.3min^-1； n(T)/n(M)=4	未改性	29.4	6.7	［31］
Y	FAU	由SOD笼和六方柱笼连接围成八面沸石笼，笼间通过十二元环相连	孔口直径0.74~0.74nm	225℃；常压； F/W=0.008mol·g^-1·h^-1； n(T)/n(M)=2	阳离子交换	51.0	28.9	［26］
Mordenite	MOR	c轴方向十二元环主孔道和平行的八元环侧通道	主孔道0.65nm×0.70nm 侧通道0.28nm×0.57nm	400℃；常压；催化剂/进料比例为5 n(T)/n(M)=1	未改性	24.2	49.6	［32］
ZSM-12	MTW	十二元环构成的一维线性非交叉孔道	0.57nm×0.61nm	300℃；常压；LHSV=2.5h^-1 n(T)/n(M)=0.5	未改性	50.9	61.7	［33］
SAPO-11	AEL	一维十元环孔道	0.39nm×0.64nm	450℃；常压； WHSV=2h^-1 n(T)/n(M)=2	金属/非金属改性；硅氧烷试剂修饰	89.5	6.7	［34］
SAPO-41	AFO	一维椭圆十元环孔道	0.43nm×0.7nm	400℃；常压； WHSV=4.5h^-1 n(T)/n(M)=2	未改性	37.9	57.6	［35］
MCM-22	MWW	具有十元环交叉孔道、十元环开口的十二元环超笼及表面的十二元环孔穴	正弦孔道0.51nm×0.41nm 短孔道0.55nm×0.40nm	250℃；常压； F/W=0.47mol·g^-1·h^-1； n(T)/n(M)=1	三甲基吡啶处理	74.1	3.8	［36］
ZSM-5	MFI	由截面椭圆形的十元环直孔道和截面近乎圆形的正弦孔道相互交叉构成	直孔道0.53nm×0.56nm 正弦孔道0.51nm×0.55nm	460℃；常压； WHSV=2h^-1； n(T)/n(M)=2； n(H₂)/n(H₂O)/n(T+M)=8/8/1	Si-P-Mg 改性后负载Pt	98.0	23.0	［37］
ZSM-5	MFI	由截面椭圆形的十元环直孔道和截面近乎圆形的正弦孔道相互交叉构成	直孔道0.53nm×0.56nm 正弦孔道0.51nm×0.55nm	460℃；0.2MPa； WHSV=2.5h^-1； n(T)/n(M)=4； n(H₂)/n(H₂O)/n(T+M)=2/2/1	Si-P-Mg 改性后负载Pt	94.0	12.0	［38］

表1 不同分子筛的孔结构性质及其甲苯与甲醇烷基化反应性能

名称	拓扑结构	分子筛结构	孔道尺寸	反应条件	改性条件	对二甲苯选择性/%	甲苯转化率/%	参考文献
SAPO-5	AFI	一维十二元环孔道	直孔道0.73nm×0.73nm	400℃；常压； F/W=0.24mol·g^-1·h^-1； n(T)/n(M)=2	未改性	25.0	16.0	［30］
β	BEA	三维十二元环孔道	直孔道0.73nm×0.60nm 弯曲孔道0.56nm×0.56nm	300℃；常压； WHSV=17.3min^-1； n(T)/n(M)=4	未改性	29.4	6.7	［31］
Y	FAU	由SOD笼和六方柱笼连接围成八面沸石笼，笼间通过十二元环相连	孔口直径0.74~0.74nm	225℃；常压； F/W=0.008mol·g^-1·h^-1； n(T)/n(M)=2	阳离子交换	51.0	28.9	［26］
Mordenite	MOR	c轴方向十二元环主孔道和平行的八元环侧通道	主孔道0.65nm×0.70nm 侧通道0.28nm×0.57nm	400℃；常压；催化剂/进料比例为5 n(T)/n(M)=1	未改性	24.2	49.6	［32］
ZSM-12	MTW	十二元环构成的一维线性非交叉孔道	0.57nm×0.61nm	300℃；常压；LHSV=2.5h^-1 n(T)/n(M)=0.5	未改性	50.9	61.7	［33］
SAPO-11	AEL	一维十元环孔道	0.39nm×0.64nm	450℃；常压； WHSV=2h^-1 n(T)/n(M)=2	金属/非金属改性；硅氧烷试剂修饰	89.5	6.7	［34］
SAPO-41	AFO	一维椭圆十元环孔道	0.43nm×0.7nm	400℃；常压； WHSV=4.5h^-1 n(T)/n(M)=2	未改性	37.9	57.6	［35］
MCM-22	MWW	具有十元环交叉孔道、十元环开口的十二元环超笼及表面的十二元环孔穴	正弦孔道0.51nm×0.41nm 短孔道0.55nm×0.40nm	250℃；常压； F/W=0.47mol·g^-1·h^-1； n(T)/n(M)=1	三甲基吡啶处理	74.1	3.8	［36］
ZSM-5	MFI	由截面椭圆形的十元环直孔道和截面近乎圆形的正弦孔道相互交叉构成	直孔道0.53nm×0.56nm 正弦孔道0.51nm×0.55nm	460℃；常压； WHSV=2h^-1； n(T)/n(M)=2； n(H₂)/n(H₂O)/n(T+M)=8/8/1	Si-P-Mg 改性后负载Pt	98.0	23.0	［37］
ZSM-5	MFI	由截面椭圆形的十元环直孔道和截面近乎圆形的正弦孔道相互交叉构成	直孔道0.53nm×0.56nm 正弦孔道0.51nm×0.55nm	460℃；0.2MPa； WHSV=2.5h^-1； n(T)/n(M)=4； n(H₂)/n(H₂O)/n(T+M)=2/2/1	Si-P-Mg 改性后负载Pt	94.0	12.0	［38］

图5 中孔沸石上甲苯甲醇烷基化过程中所发生的反应[23]

图6 ZSM-5沸石形貌的变化对甲苯与甲醇烷基化反应性能的影响[42]（a） 2.5nm厚的ZSM-5纳米片（NS-2.5）的SEM照片；（b） NS-2.5的HRTEM照片；（c）平均厚度为20nm的ZSM-5纳米晶体（NC-20）的SEM照片；（d）平均厚度为200nm的ZSM-5块状晶体（B-200）的SEM照片；（e）不同ZSM-5沸石上甲苯甲基化反应的甲醇利用率；（f）不同ZSM-5沸石上甲苯转化率随反应时间的变化

图7 协同调控ZSM-5沸石孔结构和酸性质的策略（a） ZSM-5@Silicalite-1沸石的Silicalite-1与ZSM-5沸石界面处HRTEM照片（插图为HRTEM照片所选区域）；（b） ZSM-5@Silicalite-1沸石在[101]方向上的选取电子衍射图；（c） ZSM-5晶核表面生长Silicalite-1壳层模型示意图[47-48]；（d）具有孪生结构的ZSM-5沸石（ZSM-5-T）的SEM照片；（e） ZSM-5-T沸石的推理模型；（f）未经修饰的HZSM-5-T沸石在甲苯与甲醇烷基化反应中的催化性能[54]

图8 金属纳米颗粒或纳米团簇与分子筛的匹配策略（a）采用浸渍法制备的甲苯与甲醇烷基化反应高稳定性Pt/ZSM-5催化剂的TEM照片（Pt颗粒尺寸2~10 nm）[37]；（b）采用FAU-MFI转晶法制备的含Pt纳米团簇的MFI沸石的TEM照片（Pt颗粒尺寸1.0 nm）[58]；（c）采用离子交换法制备的含孤立PtO x 位点的KLTL沸石的STEM照片（Pt颗粒尺寸<1.0nm）[59]；（d）和（e）分别采用负载法和封装法制备的Pt/β（d）和Pt@β（e）沸石经空气中高温焙烧处理后的HRTEM照片[Pt颗粒尺寸：2.0~12.0 nm（d）和0.8~3.2nm（e）][60]

图9 高性能甲苯与甲醇烷基化催化剂的设计思路

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甲苯与甲醇择形催化制对二甲苯技术进展

Development of shape-selective alkylation of toluene with methanol to para-xylene

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