低共熔溶剂在车用燃料脱硫中的研究进展

doi:10.16085/j.issn.1000-6613.2018-0011

摘要/Abstract

摘要： 低共熔溶剂作为近十年来迅速发展的一类新型绿色溶剂，不仅具备离子液体的优点，而且原料价廉易得、合成条件简单、萃取脱硫效果好，已成为继离子液体用于车用燃料脱硫研究之后又一新的研究热点。本文根据合成低共熔溶剂的盐与氢键供体（或水合盐）的不同，对用于车用燃料脱硫的低共熔溶剂进行了分类总结，简述了低共熔溶剂的物化性质，介绍了低共熔溶剂用于车用燃料脱硫的方法及研究进展，对比了低共熔溶剂对不同含硫化合物的脱除效果，归纳了低共熔溶剂的萃取脱硫和氧化萃取脱硫机理。最后针对低共熔溶剂用于车用燃料脱硫中存在的选择性低、循环再生等关键问题，指出了其研究发展方向应是通过开发具有萃取脱硫高选择性的低共熔溶剂以及寻找新型绿色环保的低共熔溶剂脱硫方法来实现深度脱硫。

关键词: 低共熔溶剂, 车用燃料, 脱硫, 机理

Abstract: Deep eutectic solvents are novel environment friendly solvents that have developed rapidly in the past ten years. They not only have the advantages of ionic liquids, but also are low-cost, easy to obtain and synthesize, and are good in extraction desulfurization, which have become a new research hotspot in the desulfurization of vehicle fuel after the ionic liquids. In this paper, the deep eutectic solvents used in the vehicle fuel desulfurization were classified based on the difference of the quaternary ammonium salt and hydrogen bond donor (or hydrated salt). The physicochemical properties of eutectic solvent were briefly described. The desulfurization method and research progress of the deep eutectic solvents used for desulfurization of vehicle fuel were introduced. The removal efficiencies of deep eutectic solvent on different sulfur compounds were compared, and the mechanism of extraction desulfurization and oxidation extraction were summarized. Finally, in view of the key problems such as low selectivity and regeneration in desulfurization process, it is proposed that one of the prospective research issues is to find new DESs with high selectivity or give recommendation for new green desulfurization method to achieve deep desulfurization.

Key words: deep eutectic solvents, vehicle fuel, desulfurization, mechanism

中图分类号:

TE624.5

唐晓东, 张晓普, 李晶晶, 王治宇, 杨柳, 王春. 低共熔溶剂在车用燃料脱硫中的研究进展[J]. 化工进展, 2018, 37(11): 4197-4204.

TANG Xiaodong, ZHANG Xiaopu, LI Jingjing, WANG Zhiyu, YANG Liu, WANG Chun. Research progress of deep eutectic solvents in desulfurization of vehicle fuel[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4197-4204.

参考文献

[1] 唐晓东, 张永汾, 李晶晶, 等. FCC汽油烷基化脱硫催化剂新进展[J]. 现代化工, 2014, 34(8):41-44. TANG X D, ZHANG Y F, LI J J, et al. Progress in alkylation catalysts for FCC gasoline desulfurization[J]. Modern Chemical Industry, 2014, 34(8):41-44.
[2] SRIVASTAVA V C. ChemInform abstract:an evaluation of desulfurization technologies for sulfur removal from liquid fuels[J]. RSC Advances, 2012, 2(3):759-783.
[3] 安高军, 周同娜, 柴永明, 等. 轻质油品非加氢脱硫技术[J]. 化学进展, 2007(9):1331-1344. AN G J, ZHOU T N, CHAI Y M, et al. Nonhydrodesulfurization technologies of light oil[J]. Progress in Chemistry, 2007(9):1331-1344.
[4] MA X L, VELU S, KIM J H, et al. Deep desulfurization of gasoline by selective adsorption over solid adsorbents and impact of analytical methods on ppm-level sulfur quantification for fuel cell applications[J]. Applied Catalysis B:Environmental, 2005, 56(1):137-147.
[5] MAGHSOUDI S, VOSSOUGHI M, KHEIROLOMOOM A, et al. Biodesulfurization of hydrocarbons and diesel fuels by Rhodococcus sp. strain P32C1[J]. Biochemical Engineering Journal, 2001, 8(2):151-156.
[6] TANG X D, HU T, LI J J, et al. Desulfurization of kerosene by electrochemical oxidation and extraction process[J]. Energy & Fuels, 2015, 29(4):2097-2103.
[7] 曾丹林, 胡义, 王可苗, 等. 燃料油萃取脱硫技术研究进展[J]. 石油炼制与化工, 2012, 43(5):98-102. ZENG D L, HU Y, WANG K M, et al. Research advance in desulfurization of transportation fuels by extraction process[J]. Petroleum Processing and Petrochemicals, 2012, 43(5):98-102.
[8] LI C P, LI D, ZOU S S, et al. Extraction desulfurization process of fuels with ammonium-based deep eutectic solvents[J]. Green Chemistry, 2013, 15(10):2793-2799.
[9] DOCHERTY K M, KULPA C F. Toxicity and antimicrobial activity of imidazolium and pyridinium ionic liquids[J]. Green Chemistry, 2005, 7(4):185-189.
[10] PHAM T P, CHO C W, YUN Y S. Environmental fate and toxicity of ionic liquids:a review[J]. Water Research, 2010, 44(2):352-372.
[11] IBRAHIM M H, HAYYAN M, HASHIM M A, et al. The role of ionic liquids in desulfurization of fuels:a review[J]. Renewable & Sustainable Energy Reviews, 2017, 76:1534-1549.
[12] 龚凯, 华一新, 徐存英, 等. Betaine·HCl-6EG-nNiCl₂·6H₂O低共熔离子液体的黏度和电导率[J]. 化工学报, 2016, 67(4):1090-1097. GONG K, HUA Y X, XU C Y, et al. Viscosity and electrical conductivity of betaine·HCl-6EG-nNiCl₂·6H₂O deep eutectic ionic liquids[J]. CIESC Journal, 2016, 67(4):1090-1097.
[13] SMITH E L, ABBOTT A P, RYDER K S. Deep eutectic solvents(DESs) and their applications[J]. Chemical Reviews, 2014, 114(21):11060-11082.
[14] ABOOD H M, ABBOTT A P, BALLANTYNE A D, et al. Do all ionic liquids need organic cations? Characterisation of[AlCl₂·nAmide]⁺ AlCl₄^- and comparison with imidazolium based systems[J]. Chemical Communications, 2011, 47(12):3523-3525.
[15] ABBOTT A P, CAPPER G, DAVIES D L, et al. Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing quaternary ammonium salts with functional side chains[J]. Chemical Communications, 2001, 19(19):2010-2011.
[16] ABBOTT A P, BOOTHBY D, CAPPER G, et al. Deep eutectic solvents formed between choline chloride and carboxylic acids:versatile alternatives to ionic liquids[J]. Journal of the American Chemical Society, 2004, 126(29):9142-9147.
[17] ABBOTT A P, CAPPER G, DAVIES D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chemical Communications, 2003, 9(1):70-71.
[18] LO W H, YANG H Y, WEI G T. One-pot desulfurization of light oils by chemical oxidation and solvent extraction with room temperature ionic liquids[J]. Green Chemistry, 2003, 5(5):639-642.
[19] HE L N, LI H M, ZHU W S, et al. Deep oxidative desulfurization of fuels using peroxophosphomolybdate catalysts in ionic liquids[J]. Industrial & Engineering Chemistry Research, 2008, 47(18):6890-6895.
[20] GUI J Z, LIU D, SUN Z L, et al. Deep oxidative desulfurization with task-specific ionic liquids:an experimental and computational study[J]. Journal of Molecular Catalysis A:Chemical, 2010, 331(1):64-70.
[21] KULKARNI P S, AFONSO C A M. Cheminform abstract:deep desulfurization of diesel fuel using ionic liquids:current status and future challenges[J]. Cheminform, 2010, 12(7):1139-1149.
[22] DING Y X, ZHU W S, LI H M, et al. Catalytic oxidative desulfurization with a hexatungstate/aqueous H₂O₂/ionic liquid emulsion system[J]. Green Chemistry, 2011, 13(5):1210-1216.
[23] 唐晓东, 袁娇阳, 李晶晶, 等. 吡啶离子液体催化作用下的FCC汽油烷基化脱硫[J]. 燃料化学学报, 2015, 43(4):442-448. TANG X D, YUAN J Y, LI J J, et al. Alkylation de sulfurization of FCC gasoline catalyze d by pyridine ionic liquid[J]. Journal of Fuel Chemistry and Technology, 2015, 43(4):442-448.
[24] ZHAO H, BAKER G A. Oxidative desulfurization of fuels using ionic liquids:a review[J]. Frontiers of Chemical Science & Engineering, 2015, 9(3):262-279.
[25] GAO H S, LUO M F, XING J M, et al. Desulfurization of fuel by extraction with pyridinium-based ionic liquids[J]. Industrial & Engineering Chemistry Research, 2008, 47(21):8384-8388.
[26] JIANG Y Q, ZHU W S, LI H M, et al. Oxidative desulfurization of fuels catalyzed by fenton-like ionic liquids at room temperature[J]. Chemsuschem, 2011, 4(3):399-403.
[27] ABBOTT A P, CULLIS P M, GIBSON M J, et al. Extraction of glycerol from biodiesel into a eutectic based ionic liquid[J]. Green Chemistry, 2007, 9(8):868-872.
[28] HAYYAN M, MJALLI F S, HASHIM M A, et al. A novel technique for separating glycerine from palm oil-based biodiesel using ionic liquids[J]. Fuel Processing Technology, 2010, 91(1):116-120.
[29] PANG K, HOU Y C, WU W Z, et al. Efficient separation of phenols from oils via forming deep eutectic solvents[J]. Green Chemistry, 2012, 14(9):2398-2401.
[30] GUO W J, HOU Y C, WU W Z, et al. Separation of phenol from model oils with quaternary ammonium salts via forming deep eutectic solvents[J]. Green Chemistry, 2013, 15(1):226-229.
[31] FRANCISCO M, BRUINHORST A V D, KROON M C. New natural and renewable low transition temperature mixtures (LTTMs):screening as solvents for lignocellulosic biomass processing[J]. Green Chemistry, 2012, 14(8):2153-2157.
[32] LI X Y, HOU M Q, HAN B X, et al. Solubility of CO₂ in a choline chloride + urea eutectic mixture[J]. Journal of Chemical & Engineering Data, 2014, 53(2):548-550.
[33] ZAID H F M, CHONG F K, MUTALIB M I A. Extractive deep desulfurization of diesel using choline chloride-glycerol eutectic-based ionic liquid as a green solvent[J]. Fuel, 2017, 192:10-17.
[34] 李佳慧, 胡嘉, 赵荣祥, 等. 氯化胆碱/草酸型低共熔溶剂氧化脱除模拟油硫化物[J]. 燃料化学学报, 2014, 42(7):870-876. LI J H, HU J, ZHAO R X, et al. Oxidative de sulfurization of mode l oil with choline chloride/oxalic acid as a eutectic solvent[J]. Journal of Fuel Chemistry and Technology, 2014, 42(7):870-876.
[35] LÜ H Y, LI P C, DENG C L, et al. Deep catalytic oxidative desulfurization(ODS) of dibenzothiophene(DBT) with oxalate-based deep eutectic solvents(DESs)[J]. Chemical Communications, 2015, 51(53):10703-10706.
[36] 毛春峰, 赵荣祥, 李秀萍. 氯化胆碱/草酸低共熔溶剂高效脱除模拟油中硫[J]. 化学工程, 2017, 45(5):6-10. MAO C F, ZHAO R X, LI X P. High removal rate of sulfur in model oil by ChCl/H₂C₂O₄ deep eutectic solvents[J]. Chemical Engineering(China), 2017, 45(5):6-10.
[37] ZHU W S, WANG C, LI H P, et al. One-pot extraction combined with metal-free photochemical aerobic oxidative desulfurization in deep eutectic solvent[J]. Green Chemistry, 2015, 17(4):2464-2472.
[38] LI J J, XIAO H, TANG X D, et al. Green carboxylic acid-based deep eutectic solvents as solvents for extractive desulfurization[J]. Energy & Fuels, 2016, 30(7):5411-5418.
[39] RAHMA W S A, MJALLI F S, AL-WAHAIBI T, et al. Polymeric-based deep eutectic solvents for effective extractive desulfurization of liquid fuel at ambient conditions[J]. Chemical Engineering Research & Design, 2017, 120:271-283.
[40] 侯良培, 赵荣祥, 李秀萍. 酸性低共熔溶剂四乙基氯化铵/三氟乙酸高效催化氧化脱除模拟油中的硫化物[J]. 化工学报, 2017, 68(4):1614-1621. HOU L P, ZHAO R X, LI X P. Highly efficient catalytic oxidation desulfurization from model oil based on acid deep eutectic solvents tetraethylammonium chloride/trifluoroacetic acid[J]. CIESC Journal, 2017, 68(4):1614-1621.
[41] WANG X, JIANG W, ZHU W S, et al. A simple and cost-effective extractive desulfurization process with novel deep eutectic solvents[J]. RSC Advances, 2016, 6(36):30345-30352.
[42] 侯良培, 赵荣祥, 李秀萍, 等. 甲基咪唑盐酸盐/草酸型低共熔溶剂的制备及其在模拟油中氧化脱硫中的应用[J]. 化工学报, 2016, 67(9):3972-3980. HOU L P, ZHAO R X, LI X P, et al. Preparation of methylimidazole hydrochloride/oxalic acid type deep eutectic solvent and its application in oxidative desulfurization of model oil[J]. CIESC Journal, 2016, 67(9):3972-3980.
[43] GANO Z S, MJALLI F S, AL-WAHAIBI T, et al. The novel application of hydrated metal halide(SnCl₂·2H₂O):based deep eutectic solvent for the extractive desulfurization of liquid fuels[J]. International Journal of Chemical Engineering and Applications, 2015, 6(5):367-371.
[44] 韦露, 樊友军. 低共熔溶剂及其应用研究进展[J]. 化学通报, 2011, 74(4):333-339. WEI L, FAN Y J. Progress of deep eutectic solvents and their applications[J]. Chemistry, 2011, 74(4):333-339.
[45] ABBOTT A P, BARRON J C, RYDER K S, et al. Eutectic-based ionic liquids with metal-containing anions and cations[J]. Chemistry, 2007, 13(22):6495-6501.
[46] TANG X D, ZHANG Y F, LI J J, et al. Deep extractive desulfurization with arenium ion deep eutectic solvents[J]. Industrial & Engineering Chemistry Research, 2015, 54(16):4625-4632.
[47] D'AGOSTINO C, HARRIS R C, ABBOTT A P, et al. Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by ¹H pulsed field gradient NMR spectroscopy[J]. Physical Chemistry Chemical Physics, 2011, 13(48):21383-21391.
[48] SIRVÏÖ J A, HEISKANEN J P. Synthesis of alkaline-soluble cellulose methyl carbamate using a reactive deep eutectic solvent[J]. ChemSusChem, 2016, 10(2):455-460.
[49] GARCÍA G, APARICIO S, ULLAH R, et al. Deep eutectic solvents:physicochemical properties and gas separation applications[J]. Energy Fuels, 2015, 29(4):2616-2644.
[50] ZHANG Q H, VIGIER K D O, ROYER S, et al. Deep eutectic solvents:syntheses, properties and applications[J]. Chemical Society Reviews, 2012, 41(21):7108-7146.
[51] PAIVA A, CRAVEIRO R, AROSO I, et al. Natural deep eutectic solvents——solvents for the 21st century[J]. ACS Sustainable Chemistry & Engineering, 2014, 2(5):1063-1071.
[52] 胡丽华, 陈砺, 方泳华, 等. 低共熔溶剂的分子结构及物性估算的研究进展[J]. 化学试剂, 2017, 39(9):937-941. HU L H, CHEN L, FANG Y H, et al. Molecular structure and physical property estimation of deep eutectic solvents (DESs)[J]. Chemical Reagents, 2017, 39(9):937-941.
[53] 李永锐. DMF+NH₄SCN液液萃取分离苯和正庚烷[D]. 哈尔滨:哈尔滨工程大学, 2013. LI Y R. Separation of benzene from n-heptane by extraction with (DMF+NH₄SCN)[D]. Harbin:Harbin Engineering University, 2013.
[54] 唐晓东, 刘亮, 税蕾蕾. 直馏柴油催化氧化脱硫均相催化剂的制备与评价[J]. 化工学报, 2005, 56(4):642-645. TANG X D, LIU L, SHUI L L, et al. Preparation and evaluation of desulfurization catalysts for homogeneous catalytic oxidation of straight-run diesel[J]. Journal of Chemical Industry and Engineering(China), 2005, 56(4):642-645.
[55] 唐晓东, 税蕾蕾, 刘亮. 直馏柴油NOx-空气催化氧化脱硫研究[J]. 催化学报, 2004, 25(10):789-792. TANG X D, SHUI L L, LIU L. Catalytic oxidative desulfurization of straight-run diesel by using NOx and air as oxidants[J]. Chinese Journal of Catalysis, 2004, 25(10):789-792.
[56] TANG X D, HU T, LI J J, et al. Deep desulfurization of condensate gasoline by electrochemical oxidation and solvent extraction[J]. RSC Advances, 2015, 5(66):53455-53461.
[57] GAO H S, LUO M F, XING J M, et al. Desulfurization of fuel by extraction with pyridinium-based ionic liquids[J]. Industrial & Engineering Chemistry Research, 2008, 21(47):8384-8388.
[58] WANG X M, HAN M J, WAN H, et al. Study on extraction of thiophene from model gasoline with Brönsted acidic ionic liquids[J]. Frontiers of Chemical Science & Engineering, 2011, 5(1):107-112.
[59] MEHDIZADEH A, AHMADI A N, FATEMINASSAB F, et al. Application of alkyl sulfate and nitrate imidazolium based ionic liquids in deep desulfurization of model diesel fuels[C]//Congress on Ionic Liquids. 2013.
[60] CEDEÑO-CAERO L, GOMEZ-BERNAL H, FRAUSTRO-CUEVAS A, et al. Oxidative desulfurization of synthetic diesel using supported catalysts:part Ⅲ. Support effect on vanadium-based catalysts[J]. Catalysis Today, 2008, 133(1):244-254.
[61] OTSUKI S, NONAKA T, TAKASHIMA N, et al. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction[J]. Energy & Fuels, 2000, 14(6):750-753.