Review of hydrodesulfurization technology based on the upgrading requirement of clean gasoline

doi:10.16085/j.issn.1000-6613.2018-1139

Abstract

Abstract:

To meet the“strictest in history”national Ⅵ gasoline quality standards, the development of low sulfur, olefin, and octane number clean gasoline production technology has become a hot research topic. The mainstream technology of clean gasoline production is selective hydrodesulfurization technology. This article expounded the research on the relationship between the octane number loss of FCC gasoline and the hydrogenation saturation law of olefins with different carbon numbers and structures in FCC gasoline. And the status of hydrodesulfurization technology under the background of Ⅵ upgrading in China was also analyzed in detail. The research progress of the hydrodesulfurization catalysts about the desulfurization selectivity and octane number recovery performance was reviewed. Based on the current status and problems of refinery development, the future development of the clean oil was suggested. Adhering to the concept of "molecular refining", the knowledges of the gasoline composition need to be improved so the continuous separation and efficient conversion of various hydrocarbons in gasoline composition will be realized, which can meet the upgrading requirements of clean oil products and the structural adjustment of future oil products.

Key words: clean gasoline, hydrodesulfurization, extractive servant, olefin

摘要：

为满足“史上最严”的国Ⅵ汽油质量标准，发展“低硫、控烯、保辛烷值”的清洁汽油生产新技术成为当前研究热点。当前清洁汽油生产的主流技术是选择性催化加氢脱硫技术，本文首先从催化裂化（FCC）汽油中汽油辛烷值损失与汽油中不同碳数和结构烯烃加氢饱和规律的研究开始，详细分析了当前国Ⅵ升级背景下的加氢脱硫技术发展现状，特别针对提高加氢脱硫催化剂脱硫选择性及辛烷值恢复性能的研究进展进行了综述。基于现有的炼油发展现状及难题，建议了未来清洁油品的发展方向：秉承“分子炼油”理念，进一步完善分子层次的汽油组成认知，不断实现汽油组成中各类烃的精准分离和高效转化，可满足清洁油品的升级需求，还可应对未来油品结构调整。

关键词: 清洁汽油, 加氢脱硫, 溶剂萃取, 烯烃

CLC Number:

TQ113.26

Lixia DONG, Butian XIA, Kaiwei LUO, Liang ZHAO, Jinsen GAO, Tianzhen HAO. Review of hydrodesulfurization technology based on the upgrading requirement of clean gasoline[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 208-216.

董立霞, 夏步田, 罗凯威, 赵亮, 高金森, 郝天臻. 清洁油品升级背景下加氢脱硫技术研究进展[J]. 化工进展, 2019, 38(01): 208-216.

Figures/Tables 4

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项目	国Ⅳ	国Ⅴ	国ⅥA	国ⅥB	目的
辛烷值（RON）	90,93,97	89,92,95	89,92,95	89,92,95
硫含量/μg·g^-1	≤50	≤10	≤10	≤10
苯体积分数/%	≤1.0	≤1.0	≤0.8	≤0.8	降低CO、HC、有毒物的排放，减少汽车燃烧室沉积物的产生
芳烃体积分数/%	≤40	≤40	≤35	≤35	降低CO、HC、有毒物的排放，减少汽车燃烧室沉积物的产生
烯烃体积分数/%	≤28	≤24	≤18	≤15	降低汽油蒸发排放造成的光化学污染和发动机沉积物的产生，提高汽油稳定性
氧质量分数/%	≯2.7	≯2.7	≯2.7	≯2.7
馏程
10%蒸发温度/℃	≤70	≤70	≤70	≤70
50%蒸发温度/℃	≤120	≤120	≤110	≤110	优化车辆尾气HC排放，降低发动机的颗粒物排放
90%蒸发温度/℃	≤190	≤190	≤190	≤190	—
终馏点/℃	≤205	≤205	≤205	≤205	—
残留量体积分数/%	≤2	≤2	≤2	≤2	降低发动机积炭及其他沉积物的产生

项目	国Ⅳ	国Ⅴ	国ⅥA	国ⅥB	目的
辛烷值（RON）	90,93,97	89,92,95	89,92,95	89,92,95
硫含量/μg·g^-1	≤50	≤10	≤10	≤10
苯体积分数/%	≤1.0	≤1.0	≤0.8	≤0.8	降低CO、HC、有毒物的排放，减少汽车燃烧室沉积物的产生
芳烃体积分数/%	≤40	≤40	≤35	≤35	降低CO、HC、有毒物的排放，减少汽车燃烧室沉积物的产生
烯烃体积分数/%	≤28	≤24	≤18	≤15	降低汽油蒸发排放造成的光化学污染和发动机沉积物的产生，提高汽油稳定性
氧质量分数/%	≯2.7	≯2.7	≯2.7	≯2.7
馏程
10%蒸发温度/℃	≤70	≤70	≤70	≤70
50%蒸发温度/℃	≤120	≤120	≤110	≤110	优化车辆尾气HC排放，降低发动机的颗粒物排放
90%蒸发温度/℃	≤190	≤190	≤190	≤190	—
终馏点/℃	≤205	≤205	≤205	≤205	—
残留量体积分数/%	≤2	≤2	≤2	≤2	降低发动机积炭及其他沉积物的产生

碳数	质量分数/%					总烯率 /%
碳数	正构烷烃	异构烷烃	烯烃	环烷烃	芳烃	总烯率 /%
4	0.1	0.0	0.6	—	—	1.6
5	1.2	7.8	18.0	—	—	44.2
6	1.1	5.9	11.9	2.0	0.8	29.3
7	0.9	2.2	4.3	3.2	3.7	10.7
8	0.4	2.7	3.6	1.8	6.4	8.9
9	0.3	1.6	1.4	1.3	7.8	3.4
10	0.2	0.7	0.7	0.2	4.0	1.5
11	0.3	1.2	0.1	0.0	1.0	0.4
12	0.0	0.3	0.0	—	—	0.0
合计	4.4	22.2	40.6	8.6	23.6	100

碳数	质量分数/%					总烯率 /%
碳数	正构烷烃	异构烷烃	烯烃	环烷烃	芳烃	总烯率 /%
4	0.1	0.0	0.6	—	—	1.6
5	1.2	7.8	18.0	—	—	44.2
6	1.1	5.9	11.9	2.0	0.8	29.3
7	0.9	2.2	4.3	3.2	3.7	10.7
8	0.4	2.7	3.6	1.8	6.4	8.9
9	0.3	1.6	1.4	1.3	7.8	3.4
10	0.2	0.7	0.7	0.2	4.0	1.5
11	0.3	1.2	0.1	0.0	1.0	0.4
12	0.0	0.3	0.0	—	—	0.0
合计	4.4	22.2	40.6	8.6	23.6	100

序号	烯烃结构变化	辛烷值变化情况
1	烯烃含量增加	辛烷值增加
2	烯烃分支增加	辛烷值减小
3	烯烃双键向分子中间移动	辛烷值减小
4	环烯取代基团增加	辛烷值减小
5	烯烃环数增加	辛烷值减小
6	烯烃分子量增加	辛烷值增加
7	环烯侧链增长	辛烷值增加
8	环烯环增大	辛烷值增加