Research progress of the oxidation desulfurization mechanism for fuel oil

doi:10.16085/j.issn.1000-6613.2019-0410

Abstract

Abstract: Due to the advantages of mild operating conditions, relatively low cost, high desulfurization rate and green environmental protection, oxidative desulfurization is considered to be one of the main techniques for reducing the high sulfur content of fuel oil among non-hydrodesulfurization techniques. In this paper, the research progress of the oxidative desulfurization mechanism of fuel oil at home and abroad in recent years is reviewed. The mechanism of catalytic oxidative desulfurization using different oxidants (such as hydrogen peroxide, oil-soluble oxidants, air, oxygen and solid oxidants) and the mechanism of oxidative desulfurization in ionic liquids are described in detail. The mechanism of oxidative desulfurization in deep eutectic solvents, ultrasound-assisted oxidative desulfurization mechanism, photocatalytic oxidative desulfurization mechanism and electrochemical oxidative desulfurization mechanism are briefly introduced. Moreover, my own opinions on the research direction of oxidative desulfurization mechanism are put forward. Deepening the research on the mechanism of oxidative desulfurization will be beneficial to find suitable catalysts and reaction conditions, provide a theoretical basis for better guiding the deep desulfurization of fuel oil and other oils. It also has important theoretical guiding significance for actual production.

Key words: fuel oil, catalysis, oxidative, desulfurization, reaction, mechanism

摘要： 由于操作条件温和、成本相对较低、脱硫率高以及绿色环保等优点，氧化脱硫被认为是非加氢脱硫技术中降低燃料油中高硫含量的主要技术之一。本文综述了近些年来国内外关于燃料油氧化脱硫机理的研究进展，详细叙述了使用不同氧化剂（H₂O₂、油溶性氧化剂、空气、氧气以及固体氧化剂）催化氧化脱硫机理和离子液体中的氧化脱硫机理，简要介绍了低共熔溶剂中的氧化脱硫机理、超声辅助氧化脱硫机理、光催化氧化脱硫机理以及电化学氧化脱硫机理，并对氧化脱硫机理的研究方向提出了见解。加深对氧化脱硫机理的研究将有利于寻求合适的催化剂和反应条件，为更好地指导燃料油以及其他油品深度脱硫的进行提供理论基础，对实际生产也具有重要的理论指导意义。

关键词: 燃料油, 催化, 氧化, 脱硫, 反应, 机理

CLC Number:

TE621

WANG Yong, SHEN Haiping, REN Lei, LI Zifeng. Research progress of the oxidation desulfurization mechanism for fuel oil[J]. Chemical Industry and Engineering Progress, 2019, 38(s1): 95-103.

王勇, 申海平, 任磊, 李子锋. 燃料油氧化脱硫机理的研究进展[J]. 化工进展, 2019, 38(s1): 95-103.

References

[1] BERTLEFF B, CLAUßNITZER J, KORTH W, et al. Extraction coupled oxidative desulfurization of fuels to sulfate and water-soluble sulfur compounds using polyoxometalate catalysts and molecular oxygen[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(5):4110-4118.
[2] ZHANG Y Q, WANG R. Synthesis of silica@C-dots/phosphotungstates core-shell microsphere for effective oxidative-adsorptive desulfurization of dibenzothiophene with less oxidant[J]. Applied Catalysis B:Environmental, 2018, 234:247-259.
[3] CRAVEN M, XIAO D, KUNSTMANN-OLSEN C, et al. Oxidative desulfurization of diesel fuel catalyzed by polyoxometalate immobilized on phosphazene-functionalized silica[J]. Applied Catalysis B:Environmental, 2018, 231:82-91.
[4] LAURITSEN J V, HELVEG S, LÆGSGAARD E, et al. Atomic-scale structure of Co-Mo-S nanoclusters in hydrotreating catalysts[J]. Journal of Catalysis, 2001, 197(1):1-5.
[5] CHANDRA S V. An evaluation of desulfurization technologies for sulfur removal from liquid fuels[J]. RSC Adv., 2012, 2(3):759-783.
[6] GU Q Q, WEN G D, DING Y X, et al. Reduced graphene oxide:a metal-free catalyst for aerobic oxidative desulfurization[J]. Green Chemistry, 2017, 19(4):1175-1181.
[7] BÖSMANN A, DATSEVICH L, JESS A, et al. Deep desulfurization of diesel fuel by extraction with ionic liquids[J]. Chemical Communications, 2001(23):2494-2495.
[8] SEREDYCH M, BANDOSZ T J. Template-derived mesoporous carbons with highly dispersed transition metals as media for the reactive adsorption of dibenzothiophene[J]. Langmuir, 2007, 23(11):6033-6041.
[9] JIA Y H, LI G, NING G L. Efficient oxidative desulfurization(ODS) of model fuel with H₂O₂ catalyzed by MoO₃/γ-Al₂O₃ under mild and solvent free conditions[J]. Fuel Processing Technology, 2011, 92(1):106-111.
[10] MOHEBALI G, BALL A S. Biodesulfurization of diesel fuels-Past, present and future perspectives[J]. International Biodeterioration & Biodegradation, 2016, 110:163-180.
[11] GARCÍA G J L, FUENTES G A, HERNÁNDEZ-TERÁN M E, et al. Ultra-deep oxidative desulfurization of diesel fuel by the Mo/MoO₃-H₂O₂ system:the effect of system parameters on catalytic activity[J]. Applied Catalysis A:General, 2008, 334(1):366-373.
[12] BAZYARI A, KHODADADI A A, HAGHIGHAT M A, et al. Microporous titania-silica nanocomposite catalyst-adsorbent for ultra-deep oxidative desulfurization[J]. Applied Catalysis B:Environmental, 2016, 180:65-77.
[13] CHEN K, ZHANG X M, YANG X F, et al. Electronic structure of heterojunction MoO₂/g-C₃N₄ catalyst for oxidative desulfurization[J]. Applied Catalysis B:Environmental, 2018, 238:263-273.
[14] LV H Y, REN W Z, LIAO W P, et al. Aerobic oxidative desulfurization of model diesel using a B-type Anderson catalyst[(C₁₈H₃₇)₂N(CH₃)₂]₃Co(OH)₆Mo₆O₁₈·3H₂O[J]. Applied Catalysis B:Environmental, 2013, (138/139):79-83.
[15] SUNDARARAMAN R, SONG C S. Catalytic oxidative desulfurization of diesel fuels using air in a two-step approach[J]. Industrial & Engineering Chemistry Research, 2014, 53(5):1890-1899.
[16] CHAN N Y, LIN T Y, YEN T F. Superoxides:alternative oxidants for the oxidative desulfurization process[J]. Energy & Fuels, 2008, 22(5):3326-3328.
[17] XU H, ZHANG D D, WU F M, et al. Deep oxidative desulfurization of fuels based on[C₄mimCl]CoCl₂ ionic liquid oxone solutions at room temperature[J]. Fuel, 2017, 208:508-513.
[18] GAO J J, MA W Y, YUAN L P, et al. Catalytic oxidative desulfurization mechanism in Lewis-Brønsted complex acid[J]. Applied Catalysis A:General, 2013, 467:187-195.
[19] BHUTTO A W, ABRO R, GAO S R, et al. Oxidative desulfurization of fuel oils using ionic liquids:a review[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 62:84-97.
[20] ZHU W S, LI H M, GU Q Q, et al. Kinetics and mechanism for oxidative desulfurization of fuels catalyzed by peroxo-molybdenum amino acid complexes in water-immiscible ionic liquids[J]. Journal of Molecular Catalysis A:Chemical, 2011, 336(1):16-22.
[21] LI F, WU B, LIU R, et al. An inexpensive N-methyl-2-pyrrolidone-based ionic liquid as efficient extractant and catalyst for desulfurization of dibenzothiophene[J]. Chemical Engineering Journal, 2015, 274:192-199.
[22] 毛春峰, 赵荣祥, 李秀萍. CH₃CONH₂/ZnCl₂低共熔溶剂脱除模拟油中的硫化物[J]. 辽宁石油化工大学学报, 2017, 37(5):1-7. MAO C F, ZHAO R X, LI X P. Removal of sulfides from simulated oil by CH₃CONH₂/ZnCl₂ deep eutectic solvent[J]. Journal of Liaoning Shihua University, 2017, 37(5):1-7.
[23] SUSLICK K S. Sonochemistry[J]. Science, 1990, 247(4949):1439-1445.
[24] BHASARKAR J B, CHAKMA S, MOHOLKAR V S. Mechanistic features of oxidative desulfurization using sono-fenton-peracetic acid (ultrasound/Fe²⁺-CH₃COOH-H₂O₂) system[J]. Industrial & Engineering Chemistry Research, 2013, 52(26):9038-9047.
[25] ZENG X Y, XIAO X Y, CHEN J Y, et al. Electron-hole interactions in choline-phosphotungstic acid boosting molecular oxygen activation for fuel desulfurization[J]. Applied Catalysis B:Environmental, 2019, 248(5):573-586.
[26] LAM V, LI G C, SONG C J, et al. A review of electrochemical desulfurization technologies for fossil fuels[J]. Fuel Processing Technology, 2012, 98:30-38.
[27] TANG X D, HU T, LI J J, et al. Desulfurization of kerosene by the electrochemical oxidation and extraction process[J]. Energy & Fuels, 2015, 29(4):2097-2103.