Effect of catalyst hydrogenation ability on asphaltene composition and structure in vacuum residue

化学工业与工程

Chemcial Industry and Engineering

2024, Vol. 41

Issue (3) :1-10 DOI: 10.13353/j.issn.1004.9533.20220325

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Effect of catalyst hydrogenation ability on asphaltene composition and structure in vacuum residue

LIN Congfu¹, TIAN Lei², GUO Qiang^2,3, YANG Yong^2,3, FENG Fuxiang², LIU Yuan¹

1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China;
2. National Energy Center for Coal to Liquids, Synfuels China Technology Co., Ltd., Beijing 101407, China;
3. Synfuels China Technology (Inner Mongolia) Co., Ltd., Inner Mongolia, Ordos 010300, China

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Abstract The conversion performance of silica supported iron sulfur catalyst on Merey vacuum residue was evaluated in a slurry bed reactor. The influence of hydrogenation catalysts on the composition and structural transformation of asphaltene in Merey vacuum residue was studied using elemental analysis, GPC, XPS, ¹H-NMR, FT-IR, XRD and other methods, and the mechanism of inhibition of asphaltene coking transformation by hydrogenation catalysts was analyzed. The results show that with the increase of catalyst hydrogenation ability, the content of N and S in asphaltenes decreases continuously, and hydrodesulfurization reaction is the easiest to take place, the H/C ratio, the average alkyl chain length (n) and the condensation index (H_AU/C_A) increase, while the aromaticity index (f_A), the average height of the stack of aromatic sheets perpendicular to the plane of the sheet (L_c), the diameter of aromatic sheet (L_a) and the average number of aromatic sheets (M) decrease. This is mainly due to the fact that catalysts with strong hydrogenation ability can provide more hydrogen free radicals, causing the condensed aromatic rings in the asphaltene structure to undergo hydrogenation, resulting in longer side chains that hinder the formation of larger sized nanoaggregates in asphaltene, thereby inhibiting the precipitation and transformation of asphaltene from the oil phase to coke.

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	LIN Congfu
	TIAN Lei
	GUO Qiang
	YANG Yong
	FENG Fuxiang
	LIU Yuan

Keywords： asphaltene hydrogenation conversion slurry-bed reactor

Received 2022-04-25;

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LIN Congfu, TIAN Lei, GUO Qiang, YANG Yong, FENG Fuxiang, LIU Yuan.Effect of catalyst hydrogenation ability on asphaltene composition and structure in vacuum residue[J] Chemcial Industry and Engineering, 2024,V41(3): 1-10

[1] KAYUKOVA G P, GUBAIDULLIN A T, PETROV S M, et al. Changes of asphaltenes’ structural phase characteristics in the process of conversion of heavy oil in the hydrothermal catalytic system[J]. Energy & Fuels, 2016, 30(2): 773-783
[2] MULLINS O C. The modified yen model[J]. Energy & Fuels, 2010, 24(4): 2179-2207
[3] 李生华,刘晨光,阙国和,等.渣油热反应体系中第二液相的形成机制 [J]. 燃料化学学报,1998,26(5): 40-47 LI Shenghua, LIU Chenguang, QUE Guohe, et al. Formation mechanisms of second liquid phases in thermal reaction systems of vacuum residue[J]. Journal of Fuel Chemistry and Technology, 1998,26(5): 40-47(in chinese)
[4] ORTEGA G F J, MAR J E. Heavy oil hydrocracking on a liquid catalyst[J]. Energy & Fuels, 2017, 31(8): 7995-8000
[5] 李英峰, 卢贵武, 孙为, 等. 石油沥青质缔合体的分子动力学研究[J]. 石油学报(石油加工), 2007, 23(4):25-31 LI Yingfeng, LU Guiwu, SUN Wei, et al. Study on the molecular dynamics of petroleum-derived asphaltene aggregate[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2007, 23(4): 25-31(in Chinese)
[6] DICKIE J P, YEN T. Macrostructures of the asphaltic fractions by various instrumental methods[J]. Analytical Chemistry, 1967, 39(14): 1847-1852
[7] ALSHAREEF A H. Asphaltenes: Definition, properties, and reactions of model compounds[J]. Energy & Fuels, 2020, 34(1): 16-30
[8] GAWEL I, BOCIARSKA D, BISKUPSKI P. Effect of asphaltenes on hydroprocessing of heavy oils and residua[J]. Applied Catalysis A: General, 2005, 295(1): 89-94
[9] TREJO F, ANCHEYTA J, CENTENO G, et al. Effect of hydrotreating conditions on Maya asphaltenes composition and structural parameters[J]. Catalysis Today, 2005, 109(1/2/3/4): 178-184
[10] ANCHEYTA J, CENTENO G, TREJO F, et al. Asphaltene characterization as function of time on-stream during hydroprocessing of Maya crude[J]. Catalysis Today, 2005, 109(1/2/3/4): 162-166
[11] DU J, DENG W, LI C, et al. Reactivity and structure changes of coal tar asphaltene during slurry-phase hydrocracking[J]. Energy & Fuels, 2017, 31(2): 1858-1865
[12] SHAO R, SHEN Z, LI D, et al. Investigation on composition and structure of asphaltenes during low-temperature coal tar hydrotreatment under various reaction pressures[J]. Journal of Analytical and Applied Pyrolysis, 2018, 136: 44-52
[13] PEI L, LI D, LIU X, et al. Investigation on asphaltenes structures during low temperature coal tar hydrotreatment under various reaction temperatures[J]. Energy & Fuels, 2017, 31(5): 4705-4713
[14] SUN Z, WU Y, ZHENG M, et al. Investigation on asphaltene compositions and structures during hydroprocessing of low-temperature coal tar at different reaction temperatures on Ni-Mo-W/γ-Al₂O₃ catalysts[J].Reaction Kinetics, Mechanisms and Catalysis, 2020, 129(1): 443-456
[15] 陈晨, 李海杰, 白杨, 等. 预硫化温度对煤直接液化催化剂组分转变及其催化性能的影响[J]. 燃料化学学报, 2022, 50(1): 54-62 CHEN Chen, LI Haijie, BAI Yang, et al. Effect of sulfidation temperature on component transformation and catalytic performance of direct coal liquefaction catalyst[J]. Journal of Fuel Chemistry and Technology, 2022, 50(1): 54-62(in Chinese)
[16] 王现元, 张涛, 张龙力, 等. 渣油加氢反应样品中含铁和含钙化合物溶解性能研究[J]. 燃料化学学报, 2021, 49(6):771-779 WANG Xianyuan, ZHANG Tao, ZHANG Longli, et al. Study of the dissolution performance of ferrum and calcium compounds in residue hydrogenation reaction samples[J]. Journal of Fuel Chemistry and Technology, 2021, 49(6): 771-779(in Chinese)
[17] KELEMEN S R, GEORGE G N, GORBATY M L. Direct determination and quantification of sulphur forms in heavy petroleum and coals[J]. Fuel, 1990, 69(8): 939-944
[18] GENG W, KUMABE Y, NAKAJIMA T, et al. Analysis of hydrothermally-treated and weathered coals by X-ray photoelectron spectroscopy (XPS)[J]. Fuel, 2009, 88(4): 644-649
[19] HAN Z, SUN Y, YANG C. Effect of initial hydrogen pressure on hydrogenation reaction of asphaltenes in Tahe River[J]. Petroleum Processing and Petrochemicals, 2014,45(5): 21-24
[20] LIU D, LI Z, FU Y, et al. Investigation on asphaltene structures during Venezuela heavy oil hydrocracking under various hydrogen pressures[J]. Energy & Fuels, 2013, 27(7): 3692-3698
[21] BROWN J R, KASRAI M, BANCROFT G M, et al. Direct identification of organic sulphur species in Rasa coal from sulphur L-edge X-ray absorption near-edge spectra[J]. Fuel, 1992, 71(6): 649-653
[22] SUN Z, LI D, MA H, et al. Characterization of asphaltene isolated from low-temperature coal tar[J]. Fuel Processing Technology, 2015, 138: 413-418
[23] SUN Y, YANG C, ZHAO H, et al. Influence of asphaltene on the residue hydrotreating reaction[J]. Energy & Fuels, 2010, 24(9): 5008-5011
[24] CALEMMA V, IWANSKI P, NALI M, et al. Structural characterization of asphaltenes of different origins[J]. Energy & Fuels, 1995, 9(2): 225-230
[25] NGUYEN N T, KANG K, LEE C W, et al. Structure comparison of asphaltene aggregates from hydrothermal and catalytic hydrothermal cracking of C₅-isolated asphaltene[J]. Fuel, 2019, 235: 677-686
[26] SHIROKOFF J W, SIDDIQUI M N, ALI M F. Characterization of the structure of Saudi crude asphaltenes by X-ray diffraction[J]. Energy & Fuels, 1997, 11(3): 561-565
[27] TIAN K P, MOHAMED A R, BHATIA S. Catalytic upgrading of petroleum residual oil by hydrotreating catalysts: A comparison between dispersed and supported catalysts[J]. Fuel, 1998, 77(11): 1221-1227
[28] 蔡新恒, 龙军, 任强, 等. 沥青质分子聚集体的聚集内因[J]. 石油学报(石油加工), 2019, 35(5): 920-928 CAI Xinheng, LONG Jun, REN Qiang, et al. Aggregation mechanism of asphaltene molecular aggregates[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2019, 35(5): 920-928(in Chinese)
[29] 任强, 龙军, 代振宇, 等. 沥青质分子聚集体中π-π相互作用的研究[J]. 石油学报(石油加工), 2019, 35(4):751-758 REN Qiang, LONG Jun, DAI Zhenyu, et al. Theoretical study on π-π interactions in asphaltene molecular aggregates[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2019, 35(4): 751-758(in Chinese)
[30] KHORASHEH F, GRAY M R. High-pressure thermal cracking of n-hexadecane in aromatic solvents[J]. Industrial & Engineering Chemistry Research, 1993, 32(9): 1864-1876
[31] HECK R H, DIGUISEPPI F T. Kinetic and mechanistic effects in resid hydrocracking[J]. Energy & Fuels, 1994, 8(3): 557-560
[32] HECK R H, RANKEL L A, DIGUISEPPI F T. Conversion of petroleum residual from Maya crude: Effects of H-donors, hydrogen pressure and catalyst[J]. Fuel Processing Technology, 1992, 30(1): 69-81