C6H11NO/nCF3SO3H型低共熔溶剂氧化脱除模拟油中的二苯并噻吩

doi:10.16085/j.issn.1000-6613.2019-1027

摘要/Abstract

摘要：

通过简单加热并搅拌己内酰胺（C₆H₁₁NO）和三氟甲磺酸（CF₃SO₃H）的混合物合成了C₆H₁₁NO/nCF₃SO₃H（n=0.25，0.5，1）型酸性低共熔溶剂。利用红外光谱（FTIR）和氢谱（¹HNMR）确定了C₆H₁₁NO/nCF₃SO₃H的结构特征。以C₆H₁₁NO/0.5CF₃SO₃H低共熔溶剂和H₂O₂组成萃取-氧化脱硫系统，并将其应用于脱除模拟油中的二苯并噻吩（DBT）。研究n(CF₃SO₃H)∶n(C₆H₁₁NO)、反应温度、O/S、C₆H₁₁NO/0.5CF₃SO₃H的加入量和不同类型的硫化物对脱硫效果的影响。实验结果表明，在模拟油体积为5mL、n(CF₃SO₃H)∶n(C₆H₁₁NO)=0.5、反应温度为60℃、 O/S=6、C₆H₁₁NO/0.5CF₃SO₃H的加入量为1.0mL的最佳反应条件下，C₆H₁₁NO/0.5CF₃SO₃H对DBT、4,6-DMDBT、BT和真实油的脱硫率分别达99.4%、98.6%、83.6%和61.6%。红外表征分析了DBT与DESs之间存在相互作用，这种作用促进了氧化脱硫的进程。催化剂5次循环反应以后，其脱硫率仍高达91.9%，表明C₆H₁₁NO/0.5CF₃SO₃H低共熔溶剂具有较高的脱硫性能和稳定性。

关键词: C₆H₁₁NO/0.5CF₃SO₃H, 低共熔溶剂, 氧化, 萃取, 二苯并噻吩

Abstract:

Deep eutectic solvents C₆H₁₁NO/nCF₃SO₃H(n=0.25,0.5,1) were synthesized by simply heating and stirring the mixture of caprolactam(C₆H₁₁NO) and trifluoromethanesulfonic acid(CF₃SO₃H). The structural characteristics of C₆H₁₁NO/nCF₃SO₃H were determined by infrared spectroscopy(FTIR) and hydrogen spectroscopy(¹HNMR). An extraction-oxidation desulfurization system was composed of C₆H₁₁NO/0.5CF₃SO₃H deep eutectic solvent and H₂O₂, and it was applied to remove dibenzothiophene(DBT) in model oil. The effects of n(CF₃SO₃H)∶n(C₆H₁₁NO), reaction temperature, O/S, dosage of C₆H₁₁NO/0.5CF₃SO₃H and different types of sulfides on desulfurization rate were studied. The experimental results indicated that under the optimum conditions of V(oil) 5mL, n(CF₃SO₃H)∶n(C₆H₁₁NO)=0.5, reaction temperature 60℃, O/S=6 and V(DESs) 1.0mL, the desulfurization rates of DBT, 4,6-DMDBT, BT and real oil were 99.4%, 98.6%, 83.6% and 61.6%, respectively. The stability of deep eutectic solvent was studied by infrared spectroscopy of recovered C₆H₁₁NO/0.5CF₃SO₃H. The interaction between DBT and DESs was analyzed by infrared spectroscopy of DBT, DESs and DBT-DESs. This interaction promoted the process of oxidative desulfurization. After five recycling runs, its desulfurization rate was still as high as 91.9%, indicating that C₆H₁₁NO/0.5CF₃SO₃H had high catalytic desulfurization activity and stability.

Key words: C₆H₁₁NO/0.5CF₃SO₃H, deep eutectic solvents, oxidation, extraction, dibenzothiophene

中图分类号:

TE624

刘昊然, 王韵淇, 李秀萍, 赵荣祥. C₆H₁₁NO/nCF₃SO₃H型低共熔溶剂氧化脱除模拟油中的二苯并噻吩[J]. 化工进展, 2020, 39(5): 1632-1640.

Haoran LIU, Yunqi WANG, Xiuping LI, Rongxiang ZHAO. Oxidative removal of dibenzothiophene from model oil by C₆H₁₁NO/nCF₃SO₃H deep eutectic solvents[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1632-1640.

参考文献

1	MARTINEZ-PALOU R, LUQUE R. Applications of ionic liquids in the removal of contaminants from refinery feedstocks: an industrial perspective[J]. Energy & Environmental Science, 2014, 7(8): 2414-2447.
2	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.
3	LI F T, LIU R H, WEN J H, et al. Desulfurization of dibenzothiophene by chemical oxidation and solvent extraction with Me₃NCH₂C₆H₅Cl·2ZnCl₂ ionic liquid[J]. Green Chemistry, 2009, 11(6): 883-888.
4	LI F T, LIU Y, SUN Z M, et al. Photocatalytic oxidative desulfurization of dibenzothiophene under simulated sunlight irradiation with mixed-phase Fe₂O₃ prepared by solution combustion[J]. Catalysis Science & Technology, 2012, 2(7): 1455-1462.
5	LI C P, ZHANG J J, LI Z, et al. Extraction desulfurization of fuels with ‘metal ions’ based deep eutectic solvents (MDESs)[J]. Green Chemistry, 2016, 18(13): 3789-3795.
6	DING R D, YUN Z U, ZHOU C H, et al. Insight into the correlation between the effective adsorption sites and adsorption desulfurization performance of CuNaY zeolite[J]. Journal of Fuel Chemistry & Technology, 2018, 46(4):451-458.
7	TIAN F P, SHEN Q C, FU Z K, et al. Enhanced adsorption desulfurization performance over hierarchically structured zeolite Y[J]. Fuel Processing Technology, 2014, 128: 176-182.
8	ZHANG Y, LI G, KONG L H, et al. Deep oxidative desulfurization catalyzed by Ti-based metal-organic frameworks[J]. Fuel, 2018, 219: 103-110.
9	BAZYARI A, KHODADADI A A, MAMAGHANI A H, et al. Microporous titania-silica nanocomposite catalyst-adsorbent for ultra-deep oxidative desulfurization[J]. Applied Catalysis B: Environmental, 2016, 180: 65-77.
10	JA'FARI M, EBRAHIMI S L, KHOSRAVI-NIKOU M R. Ultrasound-assisted oxidative desulfurization and denitrogenation of liquid hydrocarbon fuels: a critical review[J]. Ultrasonics Sonochemistry, 2018, 40:955-968.
11	JIANG W, DONG L, LIU W, et al. Designing multifunctional SO₃H-based polyoxometalate catalysts for oxidative desulfurization in acid deep eutectic solvents[J]. RSC Advances, 2017, 7(87): 55318-55325.
12	GU T N, ZHANG M L, TAN T, et al. Deep eutectic solvents as novel extraction media for phenolic compounds from model oil[J]. Chemical Communications, 2014, 50(79): 11749-11752.
13	ABBOTT A P, CAPPER G, DAVIES D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chemical Communications, 2003(1): 70-71.
14	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.
15	HAO L W, WANG M R, SHAN W J, et al. L-proline-based deep eutectic solvents (DESs) for deep catalytic oxidative desulfurization (ODS) of diesel[J]. Journal of hazardous materials, 2017, 339: 216-222.
16	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.
17	LIU W, JIANG W, ZHU W Q, et al. Oxidative desulfurization of fuels promoted by choline chloride-based deep eutectic solvents[J]. Journal of Molecular Catalysis A: Chemical, 2016, 424: 261-268.
18	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.
19	YIN J M, WANG J P, LI Z, et al. Deep desulfurization of fuels based on an oxidation/extraction process with acidic deep eutectic solvents[J]. Green Chemistry, 2015, 17(9): 4552-4559.
20	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.
21	CHEN X C, GUO H S, ABDELTAWAB A A, et al. Br?nsted-lewis acidic ionic liquids and application in oxidative desulfurization of diesel fuel[J]. Energy & Fuels, 2015, 29(5): 2998-3003.
22	HAO L W, SU T, HAO D M, et al. Oxidative desulfurization of diesel fuel with caprolactam-based acidic deep eutectic solvents: tailoring the reactivity of DESs by adjusting the composition[J]. Chinese Journal of Catalysis, 2018, 39(9): 1552-1559.
23	MAO C F, ZHAO R X, LI X P, et al. Trifluoromethanesulfonic acid-based DESs as extractants and catalysts for removal of DBT from model oil[J]. RSC Advances, 2017, 7(21): 12805-12811.
24	ARAUJO C F, COUTINHO J A P, NOLASCO M M, et al. Inelastic neutron scattering study of reline: shedding light on the hydrogen bonding network of deep eutectic solvents[J]. Physical Chemistry Chemical Physics, 2017, 19(27): 17998-18009.
25	胡晶晶, 赵地顺, 李静静, 等. 己内酰胺功能化离子液体的合成及其催化酯化性能的研究[J]. 有机化学, 2015, 35(8): 1773-1780.
25	HU J J, ZHAO D S, LI J J, et al. Synthesis and catalytic esterification performance of caprolactam task-specific ionic liquids[J]. Chinese Journal of Organic Chemistry, 2015, 35(8): 1773-1780.
26	LIU P, HAO J W, LIANG S J, et al. Choline chloride and itaconic acid-based deep eutectic solvent as an efficient and reusable medium for the preparation of 13-aryl-5H-dibenzo [b, i] xanthene-5, 7, 12, 14 (13H)-tetraones[J]. Monatshefte für Chemie-Chemical Monthly, 2016, 147(4): 801-808.
27	Lü H Y, WANG S N, DENG C L, et al. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid[J]. Journal of Hazardous Materials, 2014, 279: 220-225.
28	DONG Y X, NIE Y, ZHOU Q. Highly efficient oxidative desulfurization of fuels by Lewis acidic ionic liquids based on iron chloride[J]. Chemical Engineering & Technology, 2013, 36(3): 435-442.
29	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.
29	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.
30	ASUMANA C, YU G R, LI X, et al. Extractive desulfurization of fuel oils with low-viscosity dicyanamide-based ionic liquids[J]. Green Chemistry, 2010, 12(11): 2030-2037.
31	ZHENG D, ZHU W S, XUN S H, et al. Deep oxidative desulfurization of dibenzothiophene using low-temperature-mediated titanium dioxide catalyst in ionic liquids[J]. Fuel, 2015, 159: 446-453.
32	EDE S R, KUNDU S. Microwave synthesis of SnWO₄nanoassemblies on DNA scaffold: a novel material for high performance supercapacitor and as catalyst for butanol oxidation[J]. ACS Sustainable Chemistry & Engineering, 2015, 3(9): 2321-2336.
33	ZHANG C, PAN X Y, WANG F, et al. Extraction-oxidation desulfurization by pyridinium-based task-specific ionic liquids[J]. Fuel, 2012, 102: 580-584.
34	CHEN X C, SONG D D, ASUMANA C, et al. Deep oxidative desulfurization of diesel fuels by Lewis acidic ionic liquids based on 1-n-butyl-3-methylimidazolium metal chloride[J]. Journal of Molecular Catalysis A: Chemical, 2012, 359: 8-13.
35	GAO H S, GUO C, XING J M, et al. Extraction and oxidative desulfurization of diesel fuel catalyzed by a Br?nsted acidic ionic liquid at room temperature[J]. Green Chemistry, 2010, 12(7): 1220-1224.
36	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(1/2): 16-22.
37	DAI B L, WU P W, ZHU W S, et al. Heterogenization of homogenous oxidative desulfurization reaction on graphene-like boron nitride with a peroxomolybdate ionic liquid[J]. RSC Advances, 2016, 6(1): 140-147.
38	ZHU Y F, ZHU M Y, KANG L H, et al. Phosphotungstic acid supported on mesoporous graphitic carbon nitride as catalyst for oxidative desulfurization of fuel[J]. Industrial & Engineering Chemistry Research, 2015, 54(7): 2040-2047
39	杨永坛, 王征, 杨海鹰, 等. 气相色谱法测定催化柴油中硫化物类型分布及数据对比[J]. 分析化学, 2005, 33(11): 1517-1521.
39	YANG Y T, WANG Z, YANG H Y, et al. Gas chromatographic determination of sulfide type distribution in catalytic diesel and comparison of data[J]. Chinese Journal of Analytical Chemistry, 2005, 33(11): 1517-1521.
40	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): 1232-1239.
41	LIU W, LI T H, YU G J, et al. One-pot oxidative desulfurization of fuels using dual-acidic deep eutectic solvents[J]. Fuel, 2020, 265: 116967.
42	YAO T, YAO S, PAN C H, et al. Deep extraction desulfurization with a novel guanidinium-based strong magnetic room-temperature ionic liquid[J]. Energy & Fuels, 2016, 30(6): 4740-4749.
43	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.
44	ZHANG B Y, JIANG Z X, LI J, et al. Catalytic oxidation of thiophene and its derivatives via dual activation for ultra-deep desulfurization of fuels[J]. Journal of Catalysis, 2012, 287: 5-12.
45	WANG S N, LI P C, HAO L W, et al. Oxidative desulfurization of model diesel using a Fenton-like catalyst in the ionic liquid [Dmim]BF₄[J]. Chemical Engineering & Technology, 2017, 40(3): 555-560.
46	王鑫博, 李秀萍, 赵荣祥. EMIES/p-TsOH型低共熔溶剂的合成及其氧化脱硫性能的研究[J]. 燃料化学学报, 2019, 47(1): 104-112.
46	WANG X B, LI X P, ZHAO R X. Synthesis of EMIES/p-TsOH type deep eutectic solvent and its oxidative desulfurization performance[J]. Journal of Fuel Chemistry and Technology, 2019, 47(1): 104-112.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[7]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[8]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[9]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[10]	杨寒月, 孔令真, 陈家庆, 孙欢, 宋家恺, 王思诚, 孔标. 微气泡型下向流管式气液接触器脱碳性能[J]. 化工进展, 2023, 42(S1): 197-204.
[11]	杨建平. 降低HPPO装置反应系统原料消耗的PSE[J]. 化工进展, 2023, 42(S1): 21-32.
[12]	王福安. 300kt/a环氧丙烷工艺反应器降耗减排分析[J]. 化工进展, 2023, 42(S1): 213-218.
[13]	马伊, 曹世伟, 王家骏, 林立群, 邢延, 曹腾良, 卢峰, 赵振伦, 张志军. 低共熔溶剂回收废旧锂离子电池正极材料的研究进展[J]. 化工进展, 2023, 42(S1): 219-232.
[14]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[15]	廖志新, 罗涛, 王红, 孔佳骏, 申海平, 管翠诗, 王翠红, 佘玉成. 溶剂脱沥青技术应用与进展[J]. 化工进展, 2023, 42(9): 4573-4586.

C₆H₁₁NO/nCF₃SO₃H型低共熔溶剂氧化脱除模拟油中的二苯并噻吩

Oxidative removal of dibenzothiophene from model oil by C₆H₁₁NO/nCF₃SO₃H deep eutectic solvents

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价