Progress in alkylation of gasoline with molecular sieve catalyst for benzene reduction

doi:10.16085/j.issn.1000-6613.2022-1204

Abstract

Abstract:

With the increasing awareness of environmental protection, the limitation of benzene content in gasoline is becoming more and more stringent. Benzene reduction technologies of gasoline mainly include saturation by hydrogenation, distillation, etherification and alkylation, among which alkylation technology has obvious advantages in improving the octane number and yield of gasoline. The process and reaction mechanism of alkylation with methanol and light hydrocarbons as alkylation reagents, which are widely used at present, are reviewed. The structure and characteristics of typical molecular sieves ZSM-5, MCM-22 and Beta, and their catalytic alkylation characteristics are analyzed in detail. It is pointed out that methanol, when used as an alkylation reagent, needs higher reaction temperature than the light hydrocarbons with high carbon number, but has less influence on the distillation range of gasoline. When light hydrocarbon is used as alkylation reagent, the activation temperature decreases with the increase of carbon number, but it has a great impact on the distillation range of gasoline, and the deactivation of molecular sieves would take place by their promotion of olefin polymerization at low temperature. At present, the application of the three kinds of molecular sieves is difficult to balance the benzene conversion, gasoline distillation range and energy consumption. The development of molecular sieves with suitable pore size, the preparation of composite molecular sieves and hierarchical porous molecular sieves are expected to solve this problem.

Key words: gasoline, benzene, methanol, light hydrocarbon, molecular sieve, catalysis

摘要：

随着世界各国环保意识的提高，对汽油中苯含量的要求也越来越严苛。汽油降苯技术主要包括加氢饱和、精馏分离、醚化以及烷基化等技术，其中烷基化技术无论从提高辛烷值还是增加汽油收率方面都具有明显优势。本文综述了目前应用最为广泛的甲醇和轻烃作为烷基化试剂的工艺路线和反应机理，对典型分子筛ZSM-5、MCM-22以及Beta的结构及特点、催化烷基化特性进行了具体分析。并指出：甲醇作为烷基化试剂相比于碳数较高的轻烃，需要更高的反应温度，但对汽油的馏程影响更小。轻烃作为烷基化试剂随着碳数的增加活化温度相应降低，但对汽油的馏程影响较大，且低温条件下促进烯烃的聚合引起分子筛的失活。3种分子筛的应用目前很难兼顾苯转化率、汽油馏程以及能耗，孔道大小适中分子筛的开发、复合分子筛和多级孔分子筛的制备有望成为解决该问题的重要方式。

关键词: 汽油, 苯, 甲醇, 轻烃, 分子筛, 催化

CLC Number:

TQ426.61

WANG Zijian, KE Ming, SONG Zhaozheng, LI Jiahan, TONG Yanbing, SUN Jinru. Progress in alkylation of gasoline with molecular sieve catalyst for benzene reduction[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2371-2389.

王子健, 柯明, 宋昭峥, 李佳涵, 童燕兵, 孙巾茹. 分子筛催化汽油烷基化降苯技术研究进展[J]. 化工进展, 2023, 42(5): 2371-2389.

Figures/Tables 16

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专利公司	年份	催化剂类型	苯含量（质量分数）	反应温度	反应压力	汽油甲醇比例	空速	降苯率
催化蒸馏技术公司（美国）^[19]	2011	ZSM-5、β等	—	93~371℃	1.4MPa（实例）	醇苯摩尔比(0.1~10)∶1	—	降至质量分数小于0.25%（轻馏分）
长岭石化科技开发有限公司^[20]	2009	ZSM-5、Y	20%~60%	380~450℃	0.1~0.6MPa	质量比(0.4~1)∶1	0.3~1.5h^-1	＞80%（质量分数）
中石化^①和石科院^②[21]	2012	中孔、大孔分子筛	＞0.5%	250~550℃ （第一反应区）	0.2~0.6MPa	质量比(1~100)∶1（第一反应区）	—	＞65%（体积分数）
中石化和洛阳院^③[22]	2014	ZSM-5、Y以及β	10%~50%	300~375℃	0.8~3.0MPa	质量比(2~10)∶1	1.0~5.0h^-1	＞75%（质量分数）
中石油^[23]	2018	ZSM-5、MCM-56以及β	38.1% （实例）	300~500℃	0.5~3.0MPa	甲醇∶苯(0.5~2)∶1（摩尔比）	6~10h^-1	＞50%（摩尔分数）
科创石化科技开发有限公司^[24]	2020	ZSM-5	20.5% （实例）	—	0.6~1.2MPa （表压）（实例）	乙烯∶苯∶甲醇1∶4∶1（摩尔比）（实例）	—	＞97%（质量分数）（实例）

专利公司	年份	催化剂类型	苯含量（质量分数）	反应温度	反应压力	汽油甲醇比例	空速	降苯率
催化蒸馏技术公司（美国）^[19]	2011	ZSM-5、β等	—	93~371℃	1.4MPa（实例）	醇苯摩尔比(0.1~10)∶1	—	降至质量分数小于0.25%（轻馏分）
长岭石化科技开发有限公司^[20]	2009	ZSM-5、Y	20%~60%	380~450℃	0.1~0.6MPa	质量比(0.4~1)∶1	0.3~1.5h^-1	＞80%（质量分数）
中石化^①和石科院^②[21]	2012	中孔、大孔分子筛	＞0.5%	250~550℃ （第一反应区）	0.2~0.6MPa	质量比(1~100)∶1（第一反应区）	—	＞65%（体积分数）
中石化和洛阳院^③[22]	2014	ZSM-5、Y以及β	10%~50%	300~375℃	0.8~3.0MPa	质量比(2~10)∶1	1.0~5.0h^-1	＞75%（质量分数）
中石油^[23]	2018	ZSM-5、MCM-56以及β	38.1% （实例）	300~500℃	0.5~3.0MPa	甲醇∶苯(0.5~2)∶1（摩尔比）	6~10h^-1	＞50%（摩尔分数）
科创石化科技开发有限公司^[24]	2020	ZSM-5	20.5% （实例）	—	0.6~1.2MPa （表压）（实例）	乙烯∶苯∶甲醇1∶4∶1（摩尔比）（实例）	—	＞97%（质量分数）（实例）

专利公司	年份	催化剂类型	反应温度	反应压力	烷基化试剂	降苯率
Mobil^[25]	1989	ZSM-5	316~399℃	0.79~0.83MPa	C_4-烯烃	—
Mobil^[26]	1994	ZSM-5	260~538℃	0.35~21MPa	C₂~C₅烯烃	＞40%（质量分数）
Mobil^[27]	1996	ZSM-5	260~538℃	0.35~21MPa	C₅₊烯烃	＞25%（质量分数）
EMRE^[28]	2006	MCM-22	150~350℃	＜7MPa	C₂~C₄烯烃	—
EMRE^[29]	2010	MCM-22	＜300℃	＞2.5MPa（表压）	烯烃（质量分数＞50%丙烯）	＞90%
贝吉尔技术许可公司^[30]	2021	Beta、Y以及MCM-22	50~300℃	0.1~15MPa	C₅₊烯烃	—
中石化和抚研院^[31]	2004	ZSM-5、Beta	340~440℃	2.5~4.5MPa	FCC汽油烯烃	降至1.5%（体积分数）
中石化和石科院^[32]	2009	Y	250~550℃	0.1~1.0MPa	干气、液化气	＞50%（体积分数）
中科院大连化物所^[33]	2009	ZSM-5/ZSM-11共晶	300~450℃	0.2~1.5MPa	干气、乙烯厂尾气	＞45%
中石化和石科院^[34]	2012	ZSM-5、MCM-22以及Beta等	100~300℃	0.1~6.0MPa	C₂~C₄烯烃	—

专利公司	年份	催化剂类型	反应温度	反应压力	烷基化试剂	降苯率
Mobil^[25]	1989	ZSM-5	316~399℃	0.79~0.83MPa	C_4-烯烃	—
Mobil^[26]	1994	ZSM-5	260~538℃	0.35~21MPa	C₂~C₅烯烃	＞40%（质量分数）
Mobil^[27]	1996	ZSM-5	260~538℃	0.35~21MPa	C₅₊烯烃	＞25%（质量分数）
EMRE^[28]	2006	MCM-22	150~350℃	＜7MPa	C₂~C₄烯烃	—
EMRE^[29]	2010	MCM-22	＜300℃	＞2.5MPa（表压）	烯烃（质量分数＞50%丙烯）	＞90%
贝吉尔技术许可公司^[30]	2021	Beta、Y以及MCM-22	50~300℃	0.1~15MPa	C₅₊烯烃	—
中石化和抚研院^[31]	2004	ZSM-5、Beta	340~440℃	2.5~4.5MPa	FCC汽油烯烃	降至1.5%（体积分数）
中石化和石科院^[32]	2009	Y	250~550℃	0.1~1.0MPa	干气、液化气	＞50%（体积分数）
中科院大连化物所^[33]	2009	ZSM-5/ZSM-11共晶	300~450℃	0.2~1.5MPa	干气、乙烯厂尾气	＞45%
中石化和石科院^[34]	2012	ZSM-5、MCM-22以及Beta等	100~300℃	0.1~6.0MPa	C₂~C₄烯烃	—

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