CHANGES OF ASPHALTENE STABILITY DURING RESIDUE HYDROTREATING

Abstract

Abstract: The effects of polycyclic aromatic hydrocarbons on the removal of impurities and the inhibition of carbon accumulation on catalyst in the RICP technology were studied with an autoclave using Saudi Arab (light) atmospheric residue as raw material. A method based on Flory-Huggins activity coefficient model was established to investigate the stability of asphaltenes at 380 ℃ and 14.0 MPa. The parameter A/B ratio was calculated, where A represents the reactivity of active hydrogen for HDS, HDN, HDCCR, and B is the reactivity of active hydrogen for asphaltene hydrogenation. It shows the tendency of reactive hydrogen to focus on the reaction: larger A means the higher the efficiency of active hydrogen in removing impurities; while the smaller B is the more efficient active hydrogen in the hydrogenation of asphaltenes. The results showed that after hydrotreating, the solubility difference between asphaltene and residual oil (containing dissolved hydrogen) increased, and the stability of asphaltene became worse. When the catalysts RDM-32, RDM-53 and RCS-31 were graded at a ratio of 40:10:50, the value of A/B for Saudi Arab (light) residue reached the maximum at 380 ℃ and 14.0 MPa. It indicated that the introduction of high aromatic fraction is beneficial to further increase the value of A/B. The reason why PAHs improve the impurity removal and inhibit catalyst carbon accumulation is that PAHs optimize the efficiency of active hydrogen for impurity removal and asphaltene hydrogenation.

Key words: fixed bed residue hydritreating, Flory-Huggins model, asphaltene stability., parameter

CLC Number:

References

[1].聂红，杨清河，戴立顺，李大东. 重油高效转化关键技术的开发及应用[J]. 石油炼制与化工，2012, 43(1): 1-6.
[2].牛传峰，戴立顺，李大东.芳香性对渣油加氢反应的影响[J].石油炼制与化工，2008，39（6），1~5.
[3].牛传峰. 不同芳香性重馏分油对渣油加氢过程影响的研究[D].石油化工科学研究院，2001.
[4].李大东. 加氢处理工艺与工程[M]. 北京：中国石化出版社，2004.
[5].孙昱东，杨朝合，韩忠祥.沥青质含量对渣油加氢转化残渣油收率和性质的影响[J].燃料化学学报，2012，40（5），545~549.
[6].张会成，马波，李景斌，等.渣油加氢处理催化剂积炭分析[J].当代化工，2008，37（3），277~282.
[7].于双林，山红红，张龙力，等.常压渣油加氢反应产物体系的胶体稳定性[J].中国石油大学学报（自然科学版），2010，34（1），139-143.
[8].郭鑫. 渣油催化临氢热转化体系稳定性研究[D]. 北京，石油化工科学研究院，2018.
[9].A. Hirschberg, L. N. J. deJong, B. A. Schipper, et al. Influence of temperature and pressure on asphaltene flocculation[J]. Society of Petroleum Engineers Journal, 1984, 24(3), 283~293.
[10].S. I. Andersen, E. II. Stenby. Thermodynamics of asphaltene precipitation and dissolution investigation of temperature and solvent effects[J]. Fuel Science and Technology International, 1996, 14(1~2), 261~287.
[11].D. M. Garcia, S. Correra. A shortcut application of a Flory-like model to asphalteneprecipitation[J]. Journal of Dispersion Science and Technology, 2007, 28, 339~347.
[12].郑丹星.流体与过程热力学（第二版）[M]. 北京：化学工业出版社，2010.
[13].徐春明，杨朝合. 石油炼制工程（第四版）[M]. 北京：石油工业出版社，2009.
[14].陈新志，蔡振云，胡望明，等. 化工热力学（第三版）[M]. 北京：化学工业出版社，2009.
[15].K. C. Chao, J. D. Seader. A general correlation of vapor-liquid equilibria in hydrocarbon mixtures[J]. AIChE Journal, 1961, 7(4), 598-605.
[16].马沛生.化工热力学[M]. 北京：化学工业出版社，2005.
[17].Wiehe I. A., Kennedy R. J.. The oil compatibility model and crude oil incompatibility[J]. Energy & Fuels, 2000, 14(1), 56~59.
[18].于双林，山红红，张龙力，等. 常压渣油加氢反应查无体系的胶体稳定性[J]. 中国石油大学学报（自然科学版），2010，34(1)，139~143.
[19].Mofidi A. M., Edalat M.. A simplified thermodynamic modeling procedure for predicting asphalteneprecipitation[J]. Fuel, 2006, 85, 2616~2621.
[20].X. Y. Wang, Z. M. Xu, S. Q. Zhao, et al. Solubility Parameters of Bitumen-Derived Narrow VaccumResidFractions[J]. Energy & Fuels, 2009, 23, 386~391.
[21].石亚华，牛传峰，高永灿，戴立顺. 渣油加氢技术的研究II. 渣油加氢与催化裂化双向组合技术（RICP）的开发[J]. 石油炼制与化工，2005, 11: 21-24.
[22].高永灿，谢朝刚，牛传峰，龙军. 催化裂化操作单元在RICP组合技术中的作用及调整[J]. 石油炼制与化工，2008, 10: 1-5.
[23].牛传峰，张瑞弛，戴立顺，等.渣油加氢-催化裂化双向组合技术RICP[J].石油炼制与化工，2002，33（1），27~29.