Application of deep eutectic solvents in the removal of organic sulfur compounds from fuel

doi:10.16085/j.issn.1000-6613.2018-1114

Abstract

Abstract:

The extractive desulfurization of deep eutectic solvents (DESs) has provided a new green method for the deep desulfurization of fuel due to its simple operation, mild conditions, low cost and high desulfurization efficiency. This article summarizes the progress in the past five years on applying DESs in the removal of organic sulfur compounds from fuel, including direct extractive desulfurization and oxidative-extractive desulfurization. Firstly, the desulfurization results of different DESs are summarized. For example, the extraction efficiency of dibenzothiophene is 100% after three extraction stages by tetrabutyl ammonium bromide/polyethylene glycol; the removal efficiency of dibenzothiophene can reach 100% for oxidative desulfurization with choline chloride/acetic acid as an extractant. The desulfurization of DESs can meet the requirement of ultra-low sulfur. The factors influencing the desulfurization efficiencies of DESs, such as the structures of DESs, the temperature and time of desulfurization, ratio of DESs to oil, types and concentrations of sulfides, and oxidants are also analyzed. Then, the recovery methods of DESs are summarized, and the problems in the recovery process are pointed out. The mechanisms of desulfurization are also discussed. Finally, the problems of DESs desulfurization are pointed out and the prospect of DESs in the desulfurization of fuels is reviewed.

Key words: deep eutectic solvents, fuel, extractive desulfurization, oxidative-extractive desulfurization

摘要：

深共融溶剂（deep eutectic solvents，DESs）萃取脱硫技术具有操作简易、条件温和、成本低、脱硫效果好等优点，为燃油中有机硫化物的绿色深度脱除开辟了一条新的途径。本文综述了近5年DESs在燃油脱除有机硫化物中的最新研究成果，主要从直接萃取脱硫和氧化/萃取脱硫两方面对DESs脱硫进行综述。首先对不同DESs的脱硫效果进行了归纳总结，如以四丁基溴化铵/聚乙二醇直接萃取脱硫，3次萃取后，二苯并噻吩的脱除率可达100%；以氯化胆碱/乙酸为萃取剂氧化萃取脱硫，对二苯并噻吩模拟油的氧化萃取脱硫率也可达100%，可满足超低硫要求。同时对影响DESs脱硫效果的因素，如DESs的结构、脱硫的温度、时间、剂油比、硫化物的种类及浓度、氧化剂等进行了分析。然后对DESs的回收方法进行了总结，指出了回收过程中面临的问题并讨论了不同DESs的萃取脱硫机理。最后指出DESs脱硫面临的问题并展望了DESs在燃油脱硫中未来的发展前景。

关键词: 深共融溶剂, 燃油, 萃取脱硫, 氧化/萃取脱硫

CLC Number:

TE624

Yingna CUI,Ming BAO,Changping LI. Application of deep eutectic solvents in the removal of organic sulfur compounds from fuel[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1297-1307.

崔颖娜,包明,李长平. 深共融溶剂在燃油脱除有机硫化物中的应用[J]. 化工进展, 2019, 38(03): 1297-1307.

Figures/Tables 6

序号	DESs	萃取条件	单次脱硫效果	多次脱硫效果	回收再循环利用	多次重复利用
1	TBAC/PEG^[8] (摩尔比1∶2)	m _DES∶m _oil=1∶1、25℃、30min、硫初始浓度1600mg/L	对BT模拟油，脱硫率为70.44%	4次萃取后，脱硫率99.48%	4次回收循环使用后，脱硫率基本不变	经过6次重复利用后，深共融溶剂趋于饱和状态，失去萃取能力
2	TBAC/PEG/FeCl₃ ^[9] (摩尔比4∶1∶0.05)	m _DES:m _oil=1∶1、25℃、30min、硫初始浓度1600 mg/L	对DBT模拟油，脱硫率为89.53%	2次萃取后，脱硫率100%	5次回收循环使用后，脱硫率基本不变	第5次使用后深共融溶剂的萃取率低于50%
3	[CH₃(CH₂)₃]₄PBr/FeCl₃ ^[10](摩尔比1∶2)	DES质量分数0.525、50℃、115min、硫初始浓度500μg/g	对DBT和T的模拟油，脱硫率分别为65%和48%，对商业柴油脱硫率为32%	6次萃取后，商业柴油的硫浓度降至40μg/g 以下	5次回收循环使用后，脱硫率基本不变	—
4	[CH₃(CH₂)₃]₄PBr/ SnCl₂ ^.2H₂O^[11] (摩尔比1∶1)	DESs质量分数0.5、30℃、100min、硫初始浓度500 μg/g	对DBT和T的模拟油，脱硫率分别为69.57%和47.28%	5次萃取后，DBT和T的萃取率分别为97%和80%	—	第2次重复利用时，对模拟油中DBT和T的脱硫率分别降至38%和12%
5	TBAB/IM^[12] (摩尔比1∶1)	DES质量分数0.5、30°C、95min、硫初始浓度500μg/g	对DBT和T的模拟油，脱硫率分别为70%和47%，对商业柴油的脱硫率为47%	4次萃取后，模拟油中DBT和T的浓度分别降至10μg/g和40μg/g以下，5次萃取后，商业柴油硫浓度降至15μg/g以下	5次回收循环使用后，脱硫率基本不变	—
6	TBAB/PEG-600^[13] (摩尔比1∶2)	V _DES∶V _oil=1∶1、25℃、30min、硫初始浓度500μg/g	对DBT和T的模拟油，脱硫率分别为82.40%和62.16%	3次萃取后，对DBT和T萃取率分别为100%和95.15%	5次回收循环使用后，脱硫率基本不变	5次重复利用后，对模拟油中DBT和T的脱硫率分别降至31.72%和9.09%
7	AlCl₃-氯化石蜡-52-甲苯^[14](摩尔比1∶6∶18)	DESs 6%、 293K、10 min、硫初始浓度500μg/g	对3-MT、BT、DBT模拟油的脱硫率分别为99.81%、99.65%和89.64%，可使真实燃油的硫含量从682.05μg/g降至48.37μg/g	—	—	—
8	AlCl₃/CH₃CONH₂ ^[15] (摩尔比1.8∶1)	DESs 6%、50℃、 40min、硫初始浓度1000μg/g	模拟油中3-MT、BT、DBT 的转化率分别为97.31%、98.21%和 87.39%；在真实燃油中，硫含量可从580μg/g降至17.9μg/g	—	—	—
9	TBAB/HCOOH^[16] (摩尔比1∶1)	m _DES∶m _oi=1∶0.5、30℃、40 min、硫初始浓度500μg/g	对BT、DBT、T模拟油的脱硫率分别为81.75%、80.47%、72%，对FCC汽油和柴油的脱硫率分别为40.94%和35.27%	3次萃取后，对BT、DBT、T模拟油的脱硫率分别为98.32%、98.24%、97.6%；4次萃取后， FCC汽油和柴油的脱硫率分别为83.61%和70.21%	—	4次重复利用后，对BT、DBT、T模拟油的脱硫率分别为25.09%、24.14%、23.96%
10	[BPY]Br/Mal^[17] (摩尔比1∶1)	m _DES∶m _oil=1∶2、40℃、30 min、硫初始浓度500μg/g	对FCC汽油中硫化物的脱硫率为94.14%	—	—	—
11	TEtA/Pr^[18] (摩尔比1∶3)	m _DES=1.75g、V _oil=5mL、30℃、10min、硫初始浓度DBT 500mg/L、BT、4,6-DMDBT、RSH 250mg/L	对模拟油的脱硫率为51.6%	4次萃取后，模拟油中的硫的浓度可从500mg/L降至10mg/L	5次回收循环使用后，脱硫率基本不变	5次重复利用后，硫的分配系数K _N从2.14降至1.96
12	MIM/Pr^[19] (摩尔比1∶1)	m _DES= 1.75g、V _oil=5mL、30℃、10min、硫初始浓度DBT 500mg/L、BT、4,6-DMDBT、RSH 250mg/L	硫的分配系数K _N为2.31，脱硫率为53.6%	5次萃取后，可得到无硫燃油	5次回收循环使用后，脱硫率基本不变	—
13	[C₁₂DMEA]Cl/FeCl₃ ^[20] (摩尔比1∶1)	m _DES=1g、V _oil=5mL，30^oC、10min、硫初始浓度500mg/L	对DBT的模拟油，脱硫率为52.9%	5次萃取后，脱硫率可达99.3%	2次回收循环使用后，脱硫率从52.9%降至52.5%	—
14	TBAC/EG^[21] (摩尔比1∶2)	m _DES∶m _oil =1∶1、30℃、20 min、硫初始浓度1000 μg/g	对2-MT和BT两种硫化物混合的模拟油的脱硫率为64.3%	5次萃取后，脱硫率达99.5%	6次回收循环使用后，脱硫率基本不变	—
15	TBAB/Sul^[22] (1∶7)	m _DES:m _oil=1∶1、25℃、6h、T在正庚烷中的含量为10%	单次脱硫率为35.07%	5次萃取后，脱硫率可达98%	4次回收循环使用后，脱硫率基本不变	—
16	TBPB∶DMF^[23] (1∶3)	m _DES∶m _oil =1∶1、30℃、30 min、硫初始浓度500mg/L	对DBT模拟油的脱硫率为82.1%	3次萃取后，硫浓度可降至10mg/L以下	5次回收循环使用后，脱硫率基本不变	5次重复利用后，脱硫率仅为5.4%，基本失去萃取能力

序号	DESs	萃取条件	单次脱硫效果	多次脱硫效果	回收再循环利用	多次重复利用
1	TBAC/PEG^[8] (摩尔比1∶2)	m _DES∶m _oil=1∶1、25℃、30min、硫初始浓度1600mg/L	对BT模拟油，脱硫率为70.44%	4次萃取后，脱硫率99.48%	4次回收循环使用后，脱硫率基本不变	经过6次重复利用后，深共融溶剂趋于饱和状态，失去萃取能力
2	TBAC/PEG/FeCl₃ ^[9] (摩尔比4∶1∶0.05)	m _DES:m _oil=1∶1、25℃、30min、硫初始浓度1600 mg/L	对DBT模拟油，脱硫率为89.53%	2次萃取后，脱硫率100%	5次回收循环使用后，脱硫率基本不变	第5次使用后深共融溶剂的萃取率低于50%
3	[CH₃(CH₂)₃]₄PBr/FeCl₃ ^[10](摩尔比1∶2)	DES质量分数0.525、50℃、115min、硫初始浓度500μg/g	对DBT和T的模拟油，脱硫率分别为65%和48%，对商业柴油脱硫率为32%	6次萃取后，商业柴油的硫浓度降至40μg/g 以下	5次回收循环使用后，脱硫率基本不变	—
4	[CH₃(CH₂)₃]₄PBr/ SnCl₂ ^.2H₂O^[11] (摩尔比1∶1)	DESs质量分数0.5、30℃、100min、硫初始浓度500 μg/g	对DBT和T的模拟油，脱硫率分别为69.57%和47.28%	5次萃取后，DBT和T的萃取率分别为97%和80%	—	第2次重复利用时，对模拟油中DBT和T的脱硫率分别降至38%和12%
5	TBAB/IM^[12] (摩尔比1∶1)	DES质量分数0.5、30°C、95min、硫初始浓度500μg/g	对DBT和T的模拟油，脱硫率分别为70%和47%，对商业柴油的脱硫率为47%	4次萃取后，模拟油中DBT和T的浓度分别降至10μg/g和40μg/g以下，5次萃取后，商业柴油硫浓度降至15μg/g以下	5次回收循环使用后，脱硫率基本不变	—
6	TBAB/PEG-600^[13] (摩尔比1∶2)	V _DES∶V _oil=1∶1、25℃、30min、硫初始浓度500μg/g	对DBT和T的模拟油，脱硫率分别为82.40%和62.16%	3次萃取后，对DBT和T萃取率分别为100%和95.15%	5次回收循环使用后，脱硫率基本不变	5次重复利用后，对模拟油中DBT和T的脱硫率分别降至31.72%和9.09%
7	AlCl₃-氯化石蜡-52-甲苯^[14](摩尔比1∶6∶18)	DESs 6%、 293K、10 min、硫初始浓度500μg/g	对3-MT、BT、DBT模拟油的脱硫率分别为99.81%、99.65%和89.64%，可使真实燃油的硫含量从682.05μg/g降至48.37μg/g	—	—	—
8	AlCl₃/CH₃CONH₂ ^[15] (摩尔比1.8∶1)	DESs 6%、50℃、 40min、硫初始浓度1000μg/g	模拟油中3-MT、BT、DBT 的转化率分别为97.31%、98.21%和 87.39%；在真实燃油中，硫含量可从580μg/g降至17.9μg/g	—	—	—
9	TBAB/HCOOH^[16] (摩尔比1∶1)	m _DES∶m _oi=1∶0.5、30℃、40 min、硫初始浓度500μg/g	对BT、DBT、T模拟油的脱硫率分别为81.75%、80.47%、72%，对FCC汽油和柴油的脱硫率分别为40.94%和35.27%	3次萃取后，对BT、DBT、T模拟油的脱硫率分别为98.32%、98.24%、97.6%；4次萃取后， FCC汽油和柴油的脱硫率分别为83.61%和70.21%	—	4次重复利用后，对BT、DBT、T模拟油的脱硫率分别为25.09%、24.14%、23.96%
10	[BPY]Br/Mal^[17] (摩尔比1∶1)	m _DES∶m _oil=1∶2、40℃、30 min、硫初始浓度500μg/g	对FCC汽油中硫化物的脱硫率为94.14%	—	—	—
11	TEtA/Pr^[18] (摩尔比1∶3)	m _DES=1.75g、V _oil=5mL、30℃、10min、硫初始浓度DBT 500mg/L、BT、4,6-DMDBT、RSH 250mg/L	对模拟油的脱硫率为51.6%	4次萃取后，模拟油中的硫的浓度可从500mg/L降至10mg/L	5次回收循环使用后，脱硫率基本不变	5次重复利用后，硫的分配系数K _N从2.14降至1.96
12	MIM/Pr^[19] (摩尔比1∶1)	m _DES= 1.75g、V _oil=5mL、30℃、10min、硫初始浓度DBT 500mg/L、BT、4,6-DMDBT、RSH 250mg/L	硫的分配系数K _N为2.31，脱硫率为53.6%	5次萃取后，可得到无硫燃油	5次回收循环使用后，脱硫率基本不变	—
13	[C₁₂DMEA]Cl/FeCl₃ ^[20] (摩尔比1∶1)	m _DES=1g、V _oil=5mL，30^oC、10min、硫初始浓度500mg/L	对DBT的模拟油，脱硫率为52.9%	5次萃取后，脱硫率可达99.3%	2次回收循环使用后，脱硫率从52.9%降至52.5%	—
14	TBAC/EG^[21] (摩尔比1∶2)	m _DES∶m _oil =1∶1、30℃、20 min、硫初始浓度1000 μg/g	对2-MT和BT两种硫化物混合的模拟油的脱硫率为64.3%	5次萃取后，脱硫率达99.5%	6次回收循环使用后，脱硫率基本不变	—
15	TBAB/Sul^[22] (1∶7)	m _DES:m _oil=1∶1、25℃、6h、T在正庚烷中的含量为10%	单次脱硫率为35.07%	5次萃取后，脱硫率可达98%	4次回收循环使用后，脱硫率基本不变	—
16	TBPB∶DMF^[23] (1∶3)	m _DES∶m _oil =1∶1、30℃、30 min、硫初始浓度500mg/L	对DBT模拟油的脱硫率为82.1%	3次萃取后，硫浓度可降至10mg/L以下	5次回收循环使用后，脱硫率基本不变	5次重复利用后，脱硫率仅为5.4%，基本失去萃取能力

序号	DESs	氧化剂	萃取条件	脱硫效果	回收再循环利用
1	ChCl/p-TsOH^[26] (摩尔比1∶2)	H₂O₂	m _DES∶m _oil∶m $H 2 O 2$ =0.5∶1∶0.05、25℃、30min、硫初始浓度1600mg/L	对BT模拟油，脱硫率99.99%，对真实燃油的脱硫率为97.25%	4次回收循环使用后，对BT模拟油脱硫仍可达98.87%
2	TBAC/OXA^[27] (摩尔比1∶2)	H₂O₂	V _DES=2mL、V _oil=10mL、n(H₂O₂)∶n(DBT) = 5、 50℃、3h、硫初始浓度500mg/L	对DBT模拟油，脱硫率为91%	4次回收循环使用后，脱硫率基本不变
3	L-Pro/p-TsOH^[28] (摩尔比1∶2)	H₂O₂	V _DES=2mL、V _oil=10mL、n(H₂O₂)∶n(DBT) = 5、 60℃、2h、硫初始浓度500mg/L	对DBT模拟油，脱硫率为99%	6次回收循环使用后，脱硫率基本不变
4	ChCl/CH₃COOH^[29] (摩尔比1∶2)	O₂	V _DES=3mL、V _oil=15mL、V _(aldehyde)=250μL、V _(air) =5mL/min、30°C、3h、250W高压汞灯、硫初始浓度500mg/L	对模拟油中BT、DBT、4,6-DMDBT的最高脱硫率分别为100%，98.6%和68.6%	^—①
5	[HMIM]Cl/H₂C₂O₄ ^[30](摩尔比1∶1)	H₂O₂	V _DES=1.25mL、V _oil=5mL、 n(H₂O₂)∶n(S)＝12、40℃、140min、硫初始浓度500mg/L	对DBT模拟油，脱硫率为92.2%。	7次回收循环使用后，脱硫率基本不变
6	ChCl/H₂C₂O₄ ^[31] (摩尔比1∶1)	H₂O₂	V _DES = 1mL、V _oil = 5mL、V _H2O2=0.3mL、40℃、160min、硫质量浓度为500mg/L	对DBT模拟油，脱硫率为93. 4%	5 次回收循环使用后，脱硫率基本不变
7	CH₃CONH₂/ZnCl₂ ^[32] (摩尔比1∶0.4)	H₂O₂	V _oil =5mL、DES/oil=1∶3(V/V)、n(H₂O₂)∶n(S)＝8、70℃、200min、硫质量分数为500μg/g	对DBT模拟油，脱硫率为87.12%	5次回收循环使用后，脱硫率基本不变
8	TEAC/TFA^[33] (摩尔比1∶1)	H₂O₂	V _DES=1.25mL、V _oil=5mL、n(H₂O₂)∶n(S)＝6、40℃、140min、硫质量分数为500μg/g	对DBT、BT和T的脱硫率分别为95.4%，56.2%和23.4%	5次回收循环使用后，脱硫率基本不变
9	[C4Pyr]Cl/ /p-TsOH^[34] (摩尔比1∶0.2)	H₂O₂	V _DES= 1.00mL、V _oil= 5mL、n(H₂O₂)∶n(DBT)= 6、50℃、硫质量分数为500μg/g	对DBT、4,6-DMDBT和BT的脱硫率分别为98.2%、96.0%、40.2%	5次回收循环使用后，对DBT模拟油的脱硫率为95.1%
10	C₆H₅CH₂CH₂COOH/ZnCl₂ ^[35] (摩尔比1∶0.5)	H₂O₂	V _oil =5mL、DES∶oil=0.25∶1（V/V）、n(H₂O₂)/n(S)＝6、50℃、80min、硫质量分数为500μg/g	对DBT、BT、4,6-DMDBT的模拟油的脱硫率分别为99.23%，96.12%和98.4%	5次回收循环使用后，脱硫率基本不变
11	Pr/ZnCl₂ ^[36] (摩尔比1∶0.5)	H₂O₂	V _oil = 5mL、DES/oil=0.15∶1（V/V）、n(H₂O₂)/n(S)＝4、30℃、180min、硫的初始浓度500mg/L	对DBT、4,6-DMDBT的模拟油和汽油的脱硫率分别为99.42%，98.80%和66.67%	5次回收循环使用后，对DBT模拟油脱硫率为96.31%
12	ChCl/2PEG^[37] (摩尔比1∶2)	H₂O₂	磷钨酸（HPW）为催化剂、n(HPW)=0.0052mmol、V _oil=5mL、V _DES=0.5 ml、n(H₂O₂)/n(S)＝3、50℃、3h、硫的初始浓度500mg/L	对DBT模拟油的脱硫率为99.1%	4次回收循环使用后，脱硫率基本不变
13	ChCl/2Ac^[38] (摩尔比1∶2)	H₂O₂	[PSTEtA]₃PW₁₂O₄₀为催化剂、V _oil=5mL、m(catalyst)= 0.025g、n(H₂O₂)/n(S)＝3、40℃、2.5h	对DBT模拟油的脱硫率为可达100%	—
14	ChCl/Gl^[39] (摩尔比1∶2)	H₂O₂	光催化剂Cu-Fe/TiO₂ 2.0% 、V _DES∶V _Oxidizedoil=1∶5、n(H₂O₂)/n(S)=4、室温、20min、硫初始浓度为100mg/L	对DBTO₂的脱硫率为97.06%，2次萃取后，DBTO₂的浓度降至0	3次回收循环使用后，对DBTO₂的脱硫率为88.34%
15	CoCl₂/ChCl/2PEG-200^[40] (摩尔比1∶1∶2)	KHSO₅	m _oil =6g、m _oil=2g、PMS溶液0.9g、20℃、60min、硫初始浓度为500mg/L	对DBT模拟油的脱硫率接近100%	7次回收循环使用后，脱硫率略有降低，降低5%
16	ChCl/p-TsOH^[41] (摩尔比1∶2)	H₂O₂	m _DES∶m _oil =1∶1、m(H₂O₂)∶m(DBT)=10∶1、50℃、60min、硫初始浓度为6000μg/g	对DBT模拟油的脱硫率为99.1%，对真实燃油的脱硫率可达67.7%	—

序号	DESs	氧化剂	萃取条件	脱硫效果	回收再循环利用
1	ChCl/p-TsOH^[26] (摩尔比1∶2)	H₂O₂	m _DES∶m _oil∶m $H 2 O 2$ =0.5∶1∶0.05、25℃、30min、硫初始浓度1600mg/L	对BT模拟油，脱硫率99.99%，对真实燃油的脱硫率为97.25%	4次回收循环使用后，对BT模拟油脱硫仍可达98.87%
2	TBAC/OXA^[27] (摩尔比1∶2)	H₂O₂	V _DES=2mL、V _oil=10mL、n(H₂O₂)∶n(DBT) = 5、 50℃、3h、硫初始浓度500mg/L	对DBT模拟油，脱硫率为91%	4次回收循环使用后，脱硫率基本不变
3	L-Pro/p-TsOH^[28] (摩尔比1∶2)	H₂O₂	V _DES=2mL、V _oil=10mL、n(H₂O₂)∶n(DBT) = 5、 60℃、2h、硫初始浓度500mg/L	对DBT模拟油，脱硫率为99%	6次回收循环使用后，脱硫率基本不变
4	ChCl/CH₃COOH^[29] (摩尔比1∶2)	O₂	V _DES=3mL、V _oil=15mL、V _(aldehyde)=250μL、V _(air) =5mL/min、30°C、3h、250W高压汞灯、硫初始浓度500mg/L	对模拟油中BT、DBT、4,6-DMDBT的最高脱硫率分别为100%，98.6%和68.6%	^—①
5	[HMIM]Cl/H₂C₂O₄ ^[30](摩尔比1∶1)	H₂O₂	V _DES=1.25mL、V _oil=5mL、 n(H₂O₂)∶n(S)＝12、40℃、140min、硫初始浓度500mg/L	对DBT模拟油，脱硫率为92.2%。	7次回收循环使用后，脱硫率基本不变
6	ChCl/H₂C₂O₄ ^[31] (摩尔比1∶1)	H₂O₂	V _DES = 1mL、V _oil = 5mL、V _H2O2=0.3mL、40℃、160min、硫质量浓度为500mg/L	对DBT模拟油，脱硫率为93. 4%	5 次回收循环使用后，脱硫率基本不变
7	CH₃CONH₂/ZnCl₂ ^[32] (摩尔比1∶0.4)	H₂O₂	V _oil =5mL、DES/oil=1∶3(V/V)、n(H₂O₂)∶n(S)＝8、70℃、200min、硫质量分数为500μg/g	对DBT模拟油，脱硫率为87.12%	5次回收循环使用后，脱硫率基本不变
8	TEAC/TFA^[33] (摩尔比1∶1)	H₂O₂	V _DES=1.25mL、V _oil=5mL、n(H₂O₂)∶n(S)＝6、40℃、140min、硫质量分数为500μg/g	对DBT、BT和T的脱硫率分别为95.4%，56.2%和23.4%	5次回收循环使用后，脱硫率基本不变
9	[C4Pyr]Cl/ /p-TsOH^[34] (摩尔比1∶0.2)	H₂O₂	V _DES= 1.00mL、V _oil= 5mL、n(H₂O₂)∶n(DBT)= 6、50℃、硫质量分数为500μg/g	对DBT、4,6-DMDBT和BT的脱硫率分别为98.2%、96.0%、40.2%	5次回收循环使用后，对DBT模拟油的脱硫率为95.1%
10	C₆H₅CH₂CH₂COOH/ZnCl₂ ^[35] (摩尔比1∶0.5)	H₂O₂	V _oil =5mL、DES∶oil=0.25∶1（V/V）、n(H₂O₂)/n(S)＝6、50℃、80min、硫质量分数为500μg/g	对DBT、BT、4,6-DMDBT的模拟油的脱硫率分别为99.23%，96.12%和98.4%	5次回收循环使用后，脱硫率基本不变
11	Pr/ZnCl₂ ^[36] (摩尔比1∶0.5)	H₂O₂	V _oil = 5mL、DES/oil=0.15∶1（V/V）、n(H₂O₂)/n(S)＝4、30℃、180min、硫的初始浓度500mg/L	对DBT、4,6-DMDBT的模拟油和汽油的脱硫率分别为99.42%，98.80%和66.67%	5次回收循环使用后，对DBT模拟油脱硫率为96.31%
12	ChCl/2PEG^[37] (摩尔比1∶2)	H₂O₂	磷钨酸（HPW）为催化剂、n(HPW)=0.0052mmol、V _oil=5mL、V _DES=0.5 ml、n(H₂O₂)/n(S)＝3、50℃、3h、硫的初始浓度500mg/L	对DBT模拟油的脱硫率为99.1%	4次回收循环使用后，脱硫率基本不变
13	ChCl/2Ac^[38] (摩尔比1∶2)	H₂O₂	[PSTEtA]₃PW₁₂O₄₀为催化剂、V _oil=5mL、m(catalyst)= 0.025g、n(H₂O₂)/n(S)＝3、40℃、2.5h	对DBT模拟油的脱硫率为可达100%	—
14	ChCl/Gl^[39] (摩尔比1∶2)	H₂O₂	光催化剂Cu-Fe/TiO₂ 2.0% 、V _DES∶V _Oxidizedoil=1∶5、n(H₂O₂)/n(S)=4、室温、20min、硫初始浓度为100mg/L	对DBTO₂的脱硫率为97.06%，2次萃取后，DBTO₂的浓度降至0	3次回收循环使用后，对DBTO₂的脱硫率为88.34%
15	CoCl₂/ChCl/2PEG-200^[40] (摩尔比1∶1∶2)	KHSO₅	m _oil =6g、m _oil=2g、PMS溶液0.9g、20℃、60min、硫初始浓度为500mg/L	对DBT模拟油的脱硫率接近100%	7次回收循环使用后，脱硫率略有降低，降低5%
16	ChCl/p-TsOH^[41] (摩尔比1∶2)	H₂O₂	m _DES∶m _oil =1∶1、m(H₂O₂)∶m(DBT)=10∶1、50℃、60min、硫初始浓度为6000μg/g	对DBT模拟油的脱硫率为99.1%，对真实燃油的脱硫率可达67.7%	—

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