催化裂化汽油脱硫精制技术研究进展

doi:10.16085/j.issn.1000-6613.2019-1118

摘要/Abstract

摘要：

催化裂化汽油是我国车用汽油的主要调和来源，但是硫含量远高于车用汽油质量标准的要求值；因此如何高效降低硫含量是催化裂化汽油精制处理的关键。本文综述了国内外催化裂化汽油脱硫精制生产技术。从选择性加氢脱硫技术（Prime-G⁺技术、SCANfining技术、CD Tech技术、RSDS技术、OCT-M技术和DSO技术），选择性加氢脱硫耦合辛烷值恢复技术（RIDOS技术和GARDES技术）以及吸附脱硫技术（S-Zorb技术）三方面来阐述国内外催化裂化汽油清洁化技术的原理、特点及其应用。指出深度脱硫和辛烷值保持、烯烃饱和率之间的矛盾，后续研究者仍需在工艺流程改进、工艺条件优化以及新型催化剂开发等方面做出巨大努力。

关键词: 催化裂化汽油, 加氢脱硫, 吸附脱硫, 工艺, 催化剂

Abstract:

Fluid catalytic cracking (FCC) naphtha is the main blending source of motor gasoline in China, but its sulfur content is always much higher than that of vehicle gasoline quality standards. Therefore, reducing sulfur content efficiently is the key to the refining treatment of FCC naphtha. The clean production technology of FCC naphtha was summarized in this paper from the following three aspects: selective hydrodesulfurization technologies (Prime-G⁺, SCANfining, CD Tech, RSDS, OCT-M and DSO), selective hydrodesulfurization coupled octane number recovery technologies (RIDOS and GARDES) and adsorption desulfurization technology (S-Zorb). The principle, features and applications of those technologies were introduced. The contradiction between deep desulfurization and octane number maintenance as well as olefin saturation was pointed out. The researches on the process modification, operating conditions optimization and new catalysts development should be carried out in the future.

Key words: catalytic cracking naphtha, hydrodesulfurization, adsorption desulfurization, process, catalyst

中图分类号:

TE624

王慧, 张睿, 刘海燕, 孟祥海. 催化裂化汽油脱硫精制技术研究进展[J]. 化工进展, 2020, 39(6): 2354-2362.

Hui WANG, Rui ZHANG, Haiyan LIU, Xianghai MENG. Advances in the desulfurization of fluid catalytic cracking naphtha[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2354-2362.

参考文献

1	王廷海, 李文涛, 常晓昕, 等. 催化裂化汽油清洁化技术研究开发进展[J]. 化工进展, 2019, 38(1): 196-207.
1	WANG T H, LI W T, CHANG X X, et al. Advances in fluid catalytic cracking naphtha cleaning technology[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 196-207.
2	王淑贵, 赵乐平, 庞宏. 催化汽油选择性加氢脱硫技术OCT-MD的工业应用[J]. 当代化工, 2010, 30(2): 88-89.
2	WANG S G, ZHAO L P, PANG H. Commercial application of OCT-MD technology for FCC gasoline selective hydrodesulfurization[J]. Contemporary Chemical Industry, 2010, 30(2): 88-89.
3	CHENG W C, KIM G, PETERS A W, et al. Environmental fluid catalytic cracking technology[J]. Catalysis Reviews, 1998, 40(1/2): 39-79.
4	YIN C L, ZHU G Q, XIA D H. A study of the distribution sulfur compounds in gasoline fraction produced in China. Part 2. The distribution of sulfur compounds in full-range FCC and RFCC naphthas[J]. Fuel Processing Technology, 2002, 79(2): 135-140.
5	NOCCA J L, COSYNS J, DEBUISSCHERT Q, et al. The domino interaction of refinery processes for gasoline quality attainment[C]//NPRA 2000 Annual Meeting, San Antonio, Texas, 2000.
6	I F P. Ultra low sulfur gasoline via catalytic distillation[J]. Hydrocarbon Process, 2000, 79(11): 114.
7	BACO F, DEBUISSCHERT Q, MARCHAL N, et al. Prime G⁺ process, desulfurization of FCC gasoline with minimized octane loss[C]//AIChE Spring National Meeting, Los Angeles, 2002: 180-188.
8	KAUFMANN T G, KALDOR A, STUNTZ G F, et al. Catalysis science and technology for cleaner transportation fuels[J]. Catalysis Today, 2000, 62(1): 77-90.
9	BRIGNAC G B. The SCANfining hydrotreatment process[J]. World Refining, 2000, 10(7): 14-18.
10	STUNTZ G F, PLANTENGA F L. New technologies to meet the low sulfur fuel challenge[C]//World Petroleum Congress, Rio de Janeiro, Brazil, 2002: 176-189.
11	SUGHRUE E L, KHARE G P, BERTUS B J, et al. Desulfurization and novel sorbents for same: US6254766B1[P]. 2001-06-03.
12	ROCK K L, FOLEY R M, PUTMAN H M, et al. Catalytic distillation to enhance gasoline quality: part I [J]. Petroleum Technology Quarterly, 1998(1): 51.
13	FOLEY R M, ROCK K L, BAKSHI A, et al. Catalytic distillation to enhance gasoline quality: part II [J]. Petroleum Technology Quarterly, 1998(2): 71-79.
14	CHU Y, LI M F, LI H F, et al. Development of new generation catalysts for selective hydrodesulfurization of FCC naphtha[J]. New Refining Technology, 2009(1): 19-23.
15	朱渝, 王一冠, 陈巨星, 等. 催化裂化汽油选择性加氢脱硫技术（RSDS）工业应用试验[J]. 石油炼制与化工, 2005, 36(12): 6-9.
15	ZHU Y, WANG Y G, CHEN J X, et al. Commercial trial of RSDS technology for FCC naphtha hydrodesulfurization[J]. Petroleum Processing and Petrochemicals, 2005, 36(12): 6-9.
16	陈勇, 习远兵, 周立新, 等. 第二代催化裂化汽油选择性加氢脱硫(RSDS-II)技术的中试研究及工业应用[J]. 石油炼制与化工, 2011, 42(10): 5-8.
16	CHEN Y, XI Y B, ZHOU L X, et al. Development and commercial application of RSDS-II technology[J]. Petroleum Processing and Petrochemicals, 2011, 42(10): 5-8.
17	张华, 何剑英. RSDS-III技术的工业应用[J]. 石油化工技术与经济, 2015, 31(3): 39-42.
17	ZHANG H, HE J Y. Commercial application of RSDS-III technology[J]. Technology & Economics in Petrochemicals, 2015, 31(3): 39-42.
18	兰玲, 鞠雅娜. 催化裂化汽油加氢脱硫（DSO）技术开发及工业试验[J]. 石油炼制与化工, 2010, 41(11): 53-56.
18	LAN L, JU Y N. Development and commercial trial of DSO technology for FCC gasoline hydrodesulfurization[J]. Petroleum Processing and Petrochemicals, 2010, 41(11): 53-56.
19	赵乐平, 周勇, 段为宇, 等. OCT-M催化裂化汽油选择性加氢脱硫技术[J]. 炼油技术与工程, 2004, 34(2): 6-8.
19	ZHAO L P, ZHOU Y, DUAN W Y, et al. OCT-M FCC gasoline selective hydrodesulfurization technology[J]. Petroleum Refinery Engineering, 2004, 34(2): 6-8.
20	李大东, 石亚华, 杨清雨. 生产低硫低烯烃汽油的RIDOS技术[J]. 中国工程科学, 2004, 6(4): 1-8.
20	LI D D, SHI Y H, YANG Q Y. Low sulfur low olefin gasoline production by RIDOS technology[J]. Engineering Science, 2004, 6(4): 1-8.
21	ZHANG C, LIU X Y, LIU T F, et al. Optimizing both the CoMo/Al₂O₃ catalyst and the technology for selectivity enhancement in the hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A: General, 2019, 575(1): 187-197.
22	石冈, 范煜, 鲍晓军, 等. 催化裂化汽油加氢改质GARDES技术的开发及工业试验[J]. 石油炼制与化工, 2013, 44(9): 66-72.
22	SHI G, FAN Y, BAO X J, et al. Development and application of GARDES technology for fluid catalytic cracking gasoline hydro-upgrading[J]. Petroleum Processing and Petrochemicals, 2013, 44(9): 66-72.
23	FAN Y, BAO X J, SHI G, et al. Method for hydro-upgrading inferior gasoline via ultra-deep desulfurization and octane number recovery: US8603324B2[P]. 2013-12-10.
24	GISLASON J. Phillips sulfur-removal process nears commercialization[J]. Oil & Gas Journal, 2001, 99(47): 72.
25	顾兴平. S-Zorb催化裂化汽油吸附脱硫技术[J]. 石油化工技术与经济, 2012, 28(3): 59-62.
25	GU X P. S-Zorb FCC gasoline adsorption desulfurization technology[J]. Technology & Economics in Petrochemicals, 2012, 28(3): 59-62.
26	MICHAEL C K, THOMAS F D, DAVID O, et al. Advanced catalyst technology and applications for high quality fuels and lubricants[J]. Catalysis Today, 2005, 104(1): 55-63.
27	SONG C S. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J]. Catalysis Today, 2003, 86(1/2/3/4): 211-263.
28	杨英, 郭郡, 肖立祯. 清洁汽油生产技术进展[J]. 石油化工技术与经济, 2017, 33(4): 60-65.
28	YANG Y, GUO J, XIAO L Z. Progress of clean gasoline production technology[J]. Petroleum Processing and Petrochemicals, 2017, 33(4): 60-65.
29	DAAGE M, CHUIANELLI R R, RUPPERT A F. Structure-function relations in layered transition metal sulfide catalysts[J]. Studies in Surface Science & Catalysis, 1993, 75(34): 571-584.
30	BAI C, SOLED S, MISEO S, et al. Selective catalysts for naphtha hydrodesulfurization: US8288305B2[P]. 2010-10-16.
31	刘笑, 高静洁, 罗辉. FCC汽油加氢脱硫工艺研究进展[J]. 当代化工, 2011, 40(4): 58-62.
31	LIU X, GAO J J, LUO H. Research progress in hydrodesulfurization process of FCC gasoline[J]. Contemporary Chemical Industry, 2011, 40(4): 58-62.
32	BABITH I V, MOULIJIN J A. Science and technology of novel processes for deep desulfurization of oil refinery streams: a review[J]. Fuel, 2003, 82(6): 607-631.
33	TECH C D. Ultra low sulfur gasoline via catalytic distillation[J]. Hydrocarbon Process， 2000, 79(11): 122-123.
34	HEARN D P, HICKEY T P. Gasoline desulfurization process: US5597476[P]. 1997-01-28.
35	孙守华, 孟祥东, 宋寿康, 等. 催化蒸馏技术在催化裂化重汽油加氢脱硫装置中的应用[J]. 石油炼制与化工, 2015, 46(5): 48-52.
35	SUN S H, MENG X D, SONG S K, et al. Process selection of selective hydrodesulfurization unit of catalytic cracking gasoline[J]. Petroleum Processing and Petrochemicals, 2015, 46(5): 48-52.
36	李明丰, 夏国富, 褚阳, 等. 催化裂化汽油选择性加氢脱硫催化剂RSDS-1的开发[J]. 石油炼制与化工, 2003, 34(7): 1-4.
36	LI M F, XIA G F, CHU Y, et al. Preparation of selective hydrodesulfurization catalyst RSDS-1 for FCC naphtha[J]. Petroleum Processing and Petrochemicals, 2003, 34(7): 1-4.
37	邢献杰, 许满兴, 赵乐平. OCT-M 装置生产“无硫”汽油工业应用[J]. 当代化工, 2015, 44(1): 60-62.
37	XING X J, XU M X, ZHAO L P. Commercial application of OCT-M desulfurization unit for producing sulfur-free gasoline[J]. Contemporary Chemical Industry, 2015, 44(1): 60-62.
38	尤百玲, 赵乐平, 庞宏, 等. OCT-MD技术生产“无硫汽油”的研究及工业应用[J]. 当代化工, 2012, 41(3): 264-266.
38	YOU B L, ZHAO L P, PANG H, et al. Study and commercial application of OCT-MD technology producing sulfur-free gasoline[J]. Contemporary Chemical Industry, 2012, 41(3): 264-266.
39	李鹏, 张英. 中国石化清洁汽油生产技术的开发和应用[J]. 炼油技术与工程, 2010, 40(12): 11-15.
39	LI P, ZHANG Y. Development of SINOPEC clean gasoline production technologies and application[J]. Petroleum Refinery Engineering, 2010, 40(12): 11-15.
40	邵春宇, 徐俊. DSO-M催化剂组合工艺在催化裂化汽油加氢装置设计中的首次应用[J]. 石化技术与应用, 2013, 31(1): 47-49.
40	SHAO C Y, XU J. First application of DSO-M catalyst combination process in design of fluidized-bed catalytic cracking gasoline hydrogenation unit[J]. Petrochemical Technology & Application, 2013, 31(1): 47-49.
41	张超群, 崔昕宇, 贺新. M+DSO工艺在玉门催化汽油加氢改质装置的应用[J]. 当代化工, 2017, 46(12): 2563-2565.
41	ZHANG C Q, CUI X Y, HE X. Application of M+DSO technology in Yumen FCC gasoline hydrotreating unit[J]. Contemporary Chemical Industry, 2017, 46(12): 2563-2565.
42	杨乾坚, 潘登, 张妮娜. 催化汽油M-DSO与溶剂抽提脱硫联合工艺的工业应用[J]. 石化技术与应用, 2018, 36(5): 69-72.
42	YANG Q J, PAN D, ZHANG N N. Industrial application of combined M-DSO and solvent extraction desulfurization processes for catalytic gasoline[J]. Petrochemical Technology & Application, 2018, 36(5): 69-72.
43	刘晓步, 夏少青, 刘瑞萍, 等. 采用DSO技术催化汽油加氢装置的首次工业应用[J]. 炼油技术与工程, 2014, 44(7): 28-31.
43	LIU X B, XIA S Q, LIU R P, et al. First commercial application of DSO technology in FCC gasoline hydrodesulfurization[J]. Petroleum Refinery Engineering, 2014, 44(7): 28-31.
44	GAO J S, ZHAO L, XU C M, et al. Method for upgrading catalytic cracking gasoline: US10266778B2[P]. 2019-03-23.
45	FAN Y, YIN J, SHI G, et al. A six-lump kinetic model for olefin hydrogenation, hydroisomerization and aromatization in FCC gasoline hydro-upgrading[J]. Catalysis Letters, 2009, 129(1/2): 181-188.
46	FAN Y, BAO X J, SHI G, et al. Method for production ultra-clean gasoline: US8597494B2[P]. 2013-12-03.
47	王豪, 范煜, 石冈, 等. 水热沉积法制备高分散W/Al₂O₃加氢脱硫催化剂[J]. 催化学报, 2007, 28(4): 364-370.
47	WANG H, FAN Y, SHI G, et al. Highly dispersed W/Al₂O₃ hydrodesulfurization catalyst prepared by hydrothermal deposition method[J]. Chinese Journal of Catalysis, 2007, 28(4): 364-370.
48	FAN Y, LEI D, SHI G, et al. Synthesis of ZSM-5/SAPO-11 composite and its application in FCC gasoline hydro-upgrading catalyst[J]. Catalysis Today, 2006, 114(4): 388-396.
49	FAN Y, BAO X J, LEI D, et al. A novel catalyst system based on quadruple silicoaluminophosphate and aluminosilicate zeolites for FCC gasoline upgrading[J]. Fuel, 2005, 84(4): 435-442.
50	MOCHIDA I, CHOI K H. Current progress in catalysts and catalysis for hydrotreating[J]. Practical Advances in Petroleum Processing, 2006, 9(1): 257-296.
51	吴杰, 张忠东, 李艳晗, 等. GARDES技术在大庆石化130万吨/年汽油加氢改质装置的工业应用[J]. 化工进展, 2014, 33(9): 2506-2509.
51	WU J, ZHANG Z D, LI Y H, et al. Industrial application of GARDES technology in 1.3Mt/year FCC gasoline hydrogenation unit of Daqing Petrochemical[J]. Chemical Industry and Engineering Progress, 2014, 33(9): 2506-2509.
52	张永泽, 李景锋, 刘昕, 等. GARDES技术在催化裂化汽油加氢装置上的工业应用[J]. 石化技术与应用, 2019, 37(1): 58-61.
52	ZHANGN Y Z, LI J F, LIU X, et al. Industrial application of GARDES technology in fluid catalytic cracking gasoline hydrogenation unit[J]. Petrochemical Technology & Application, 2019, 37(1): 58-61.
53	ITOO E, VEEN J A R V. On novel processes for removing sulfur from refinery streams[J]. Catalysis Today, 2006, 116(4): 446-460.
54	SCHMIDIT R, MORTON R W, GROSS J B, et al. Removal of sulfur compounds from a gas steam utilizing a zinc containing sorbent: NZ586653A[P]. 2008-10-09.
55	吴德飞, 孙丽丽, 黄泽川, 等. S-Zorb技术进展与工程应用[J]. 炼油技术与工程, 2014, 44(10): 1-4.
55	WU D F, SUN L L, HUANG Z C, et al. New development of S-Zorb process and engineering application[J]. Petroleum Refinery Engineering, 2014, 44(10): 1-4.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[6]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[7]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[8]	廖志新, 罗涛, 王红, 孔佳骏, 申海平, 管翠诗, 王翠红, 佘玉成. 溶剂脱沥青技术应用与进展[J]. 化工进展, 2023, 42(9): 4573-4586.
[9]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[10]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[11]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[12]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[13]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[14]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[15]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.