降低减压渣油延迟焦化石油焦产品硫含量的研究

石油炼制与化工 ›› 2019, Vol. 50 ›› Issue (7): 52-57.

降低减压渣油延迟焦化石油焦产品硫含量的研究

李康¹,陈辉²,雷杰¹,张德信³,陈建民⁴,刘雪东⁵,韩海波¹

1. 中石化炼化工程集团洛阳技术研发中心
2. 中国石油化工股份有限公司科技开发部
3. 中国石油大学（北京）
4. 中石化广州工程有限公司
5. 常州大学机械工程学院

收稿日期:2018-11-20 修回日期:2019-03-11 出版日期:2019-07-12 发布日期:2019-07-25
通讯作者: 韩海波 E-mail:hanhb.lpec@sinopec.com
基金资助:
中国石油化工股份有限公司项目资助

STUDY ON DESULFURIZATION OF PETROLEUM COKE FROM VACUUM RESIDUE DELAYED COKER

Li Kang,Chen Hui,Lei Jie,Zhang Dexin,Chen Jianmin,Liu Xuedong,Han Haibo

Received:2018-11-20 Revised:2019-03-11 Online:2019-07-12 Published:2019-07-25
Contact: Han Haibo E-mail:hanhb.lpec@sinopec.com
Supported by:

摘要/Abstract

摘要： 基于砜与亚砜的化学键键能低于噻吩化学键能，提出采用乙酸/双氧水氧化体系对减压渣油进行预氧化处理以降低延迟焦化石油焦产品的硫含量，同时考察了氧化减黏、水力空化强化氧化-减黏等工艺对延迟焦化石油焦硫含量的影响。结果表明，空化压力8 MPa，处理1次，并在410 ℃下减黏1 h时石油焦硫含量的降低效果最佳，硫质量分数由初始的4.12%降低至3.21%，同时产品分布数据表明，此条件下石油焦产率降低2.35百分点，液体收率提高1.93百分点。

关键词: 减压渣油, 水力空化, 减黏, 延迟焦化, 石油焦, 氧化脱硫

Abstract: Based on the knowledge that the chemical bond energy of sulfone and sulfone is lower than that of thiophene, it was proposed that the vacuum residue was pre-oxidized to reduce the sulfur content of the coke from delayed coking with acetic acid/hydrogen peroxide oxidation system. The effect of viscosity reduction by oxidation and the oxidation-viscosity reduction process assisted with hydrodynamic cavitation technology on the desulfurization of the petroleum coke were investigated. The results showed that the desulfurization of petroleum coke reached the best at the reaction conditions: cavitation pressure of 8 MPa，400℃，reaction time 1 h, and treating only once. The sulfur content of petroleum coke was reduced from 4.12% to 3.21%，and the coke yield reduced by 2.35 percentage points，the liquid yield increased by 1.93 percentage points.

Key words: vacuum residue, hydrodynamic cavitation, visbreaking, delayed coking, petroleum coke, oxidative desulfurization

中图分类号:

李康陈辉雷杰张德信陈建民刘雪东韩海波. 降低减压渣油延迟焦化石油焦产品硫含量的研究[J]. 石油炼制与化工, 2019, 50(7): 52-57.

Li Kang Chen Hui Lei Jie Zhang Dexin Chen Jianmin Liu Xuedong Han Haibo. STUDY ON DESULFURIZATION OF PETROLEUM COKE FROM VACUUM RESIDUE DELAYED COKER[J]. Petroleum Processing and Petrochemicals, 2019, 50(7): 52-57.

参考文献

[1] HU Qijing, Zhou Zhijie, LIU Xin, et al. Catalytic activity of ferric chloride for high-sulfur petroleum coke-carbon dioxide gasification[J]. Acta Petrolei Sinica （Petroleum Processing Section）, 2012,28(3): 463-469
[2] SHELWIT H, ALIBRAHIM M. Extraction of sulfur and vanadium from petroleum coke by means of saltroasting treatment[J]. Fuel, 2006,85(5):878-880
[3] LIU Xin, ZHANG Baoshen, ZHOU Zhijie, et al. Structure changes and gasification activity of petroleum coke after heat treatment[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2011,27(1): 138-143
[4] ZHAO Bin, LUO Yingtao, SU Ziwei, et al. Development on the petroleum coke desulfurization [J].Carbon Technologies, 2011,30(2): 30-32
[5] McMillen DF, Golden DM. Hydrocarbon bond dissociation energies[J]. Ann Rev Phys Chem, 1982,33:493–532
[6] Herron JT. (1988) Thermochemistry of sulfoxides and sulfones. In: Patai S, Rappoport Z, Stirling C (eds) The chemistry of sulphones and sulphoxides. Wiley, Chichester, pp 95–106
[7] Webster AB, Small NJH, Rigby R. Desulfurization of heavy oils. Patent US 3163593, 1964
[8] H C Lee, J B Butt. Kinetics of the desulfurization of thiophene: reactions of thiophene and butane[J]. J. Catal,1997, 49(3): 320-331
[9] De Filippis Paolo，Scarsella Marco，Verdone Nicola. Peroxyformic acid formation：A kinetic study[J]. Ind. Eng. Chem. Res,2009，48(3)：1372-1375.
[10] De Filippis Paolo, Scarsella Marco, Verdone Nicola. Oxidative desulfurization I：Peroxyformic acid oxidation of benzothiophene and dibenzothiophene[J]. Ind. Eng. Chem. Res,2010，49(10)：4594-4600.
[11]王继乾. 添加物对渣油热反应生焦的影响及作用机理研究.[博士学位论文].北京：中国石油大学,2006
[12] DICKIE J P, YEN T F. Macrostructure of the asphaltic fraction by various instrumental method[J]. Anal Chem, 1967,39(14):1847-1857
[13] 梁文杰主编.石油化学.第1版.北京：中国石油大学出版社, 2008. 305-306
[14] 李和杰. 一种延迟焦化工艺.中国, CN 101302443 A, 2008
[15] 李和杰. 一种改进的延迟焦化工艺. 美国, US 5006223 A, 1991
[16] MOHAMMAD ASKARIAN, ALI VATANI, MOHSEN EDALAT. Heavy oil upgrading via hydrodynamic cavitation in the presence of an appropriate hydrogen donor[J].Journal of Petroleum Scien-ce and Engineering, 2017,151:55-61.
[17] MOHAMMAD ASKARIAN, ALI VATANI, MOHSEN EDALAT. Heavy oil upgrading in a hydrodynamic cavitation system:CFD modelling,effect of the presence of hydrogen donor and metal nanoparticles[J]. The Canadian journal of chemical engineering,2017,95:670-679