催化裂化汽油清洁化技术研究开发进展

doi:10.16085/j.issn.1000-6613.2018-1339

摘要/Abstract

摘要：

为满足日益严格的清洁汽油标准不断降低硫和烯烃含量的需求，国内外在汽油清洁化领域开展了大量的研究工作。本文综述了近年来相关研究开发工作的进展，概述了催化裂化汽油中硫化物和烯烃的分布及特点、各种烃类的辛烷值、各种烯烃的加氢反应活性及其对加氢脱硫反应的抑制作用，重点分析比较了国内外典型的催化裂化汽油清洁化工艺技术（包括选择性加氢脱硫工艺、选择性加氢脱硫-烯烃定向转化工艺、临氢吸附脱硫工艺以及选择性加氢脱硫-溶剂抽提组合工艺）的优缺点，简述了加氢脱硫催化剂的活性相模型及选择性加氢脱硫催化剂的研究开发现状，指出实现烯烃的定向转化将是未来催化裂化汽油清洁化技术的重点研发方向，以期为后续的研究开发提供参考。

关键词: 清洁汽油, 工艺, 催化剂, 脱硫, 烯烃含量降低

Abstract:

To meet the technical requirements of reducing sulfur and olefin contents in the increasingly stringent clean gasoline standards, extensive researches have been carried out in the field of gasoline cleaning technology over the world. In this review, the recent progresses were summarized from the following three aspects: (1) the distributions of sulfides and olefins in fluid catalytic cracking naphtha, the octane numbers of different hydrocarbons, and the hydrogenation reactivity of various olefins and their suppressing effects on hydrodesulfurization; (2) the advantages and disadvantages of the various fluid catalytic naphtha hydroupgrading processes, including selective hydrodesulfurization processes, the combined processes of selective hydrodesulfurization and directed olefin conversion, adsorption desulfurization, and the combined processes of selective hydrodesulfurization and solvent extraction; and (3) the typical models for active metal sulfides and the recent advances in catalyst development. The aim of this review is to provide a brief but comprehensive reference for researchers in the field of clean gasoline production technology.

Key words: clean gasoline, process, catalyst, hydrodesulfurization, olefin reduction

中图分类号:

王廷海, 李文涛, 常晓昕, 向永生, 鲍晓军. 催化裂化汽油清洁化技术研究开发进展[J]. 化工进展, 2019, 38(01): 196-207.

Tinghai WANG, Wentao LI, Xiaoxin CHANG, Yongsheng XIANG, Xiaojun BAO. Advances in fluid catalytic cracking naphtha cleaning technology[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 196-207.

图/表 11

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汽油中各组分	美国		欧洲			中国
汽油中各组分	2005	2014	欧IV	欧V	欧VI	国 IV	国 V	国 VIA	国 VIB
硫化物/mg·kg^–1	≤30	≤10	≤50	≤10	≤10	≤50	≤10	≤10	≤10
烯烃/%	≤10	≤10	≤18	≤18	≤18	≤28	≤24	≤18	≤15
芳烃/%	≤25	≤25	≤35	≤35	≤35	≤40	≤40	≤35	≤35
苯/%	≤1.0	≤1.0	≤1.0	≤1.0	≤1.0	≤1.0	≤1.0	≤0.8	≤0.8

汽油中各组分	美国		欧洲			中国
汽油中各组分	2005	2014	欧IV	欧V	欧VI	国 IV	国 V	国 VIA	国 VIB
硫化物/mg·kg^–1	≤30	≤10	≤50	≤10	≤10	≤50	≤10	≤10	≤10
烯烃/%	≤10	≤10	≤18	≤18	≤18	≤28	≤24	≤18	≤15
芳烃/%	≤25	≤25	≤35	≤35	≤35	≤40	≤40	≤35	≤35
苯/%	≤1.0	≤1.0	≤1.0	≤1.0	≤1.0	≤1.0	≤1.0	≤0.8	≤0.8

硫化物名称	硫化物含量/mg·kg^–1	占总噻吩比例/%
噻吩	69.2	6.3
2-甲基噻吩	109.8	10.0
3-甲基噻吩	152.6	13.8
二甲基噻吩	389.8	35.4
未知噻吩	43.9	4.0
异丙基噻吩	26.4	2.4
甲基,乙基噻吩	46.1	4.2
未知噻吩	17.6	1.6
三甲基噻吩	91.1	8.3
碳四烷基取代噻吩	116.4	10.5
未知噻吩	23.0	2.1

硫化物名称	硫化物含量/mg·kg^–1	占总噻吩比例/%
噻吩	69.2	6.3
2-甲基噻吩	109.8	10.0
3-甲基噻吩	152.6	13.8
二甲基噻吩	389.8	35.4
未知噻吩	43.9	4.0
异丙基噻吩	26.4	2.4
甲基,乙基噻吩	46.1	4.2
未知噻吩	17.6	1.6
三甲基噻吩	91.1	8.3
碳四烷基取代噻吩	116.4	10.5
未知噻吩	23.0	2.1

窄馏分	硫化物含量/mg·kg^–1
窄馏分	噻吩类	硫醇类	硫醚类	硫化氢	总硫
初馏点～50℃	94.7	167.5	13.0	1.0	275.2
50℃～干点	243.8	152.6	9.7	1.2	406.6
初馏点–120℃	678.3	20.5	100.3	0.4	799.5
120～148℃	843.5	9.7	155.5	—	1008.7
140～160℃	1239.9	35.3	168.1	—	1443.3
160～180℃	1284.3	32.4	133.5	—	1450.2
180℃～干点	1348.7	35.3	81.5	—	1465.5