Katasonova2021 Article ExtractionMethodsForRemovingSu1

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Extraction Methods for Removing Sulfur and Its Compounds from Crude Oil and
Petroleum Products
Article in Russian Journal of Applied Chemistry · April 2021

DOI: 10.1134/S1070427221040017
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ISSN 1070-4272, Russian Journal of Applied Chemistry, 2021, Vol. 94, No. 4, pp. 411–436. © Pleiades Publishing, Ltd., 2021.
Russian Text © The Author(s), 2021, published in Zhurnal Prikladnoi Khimii, 2021, Vol. 94, No. 4, pp. 411−439.
REVIEWS
Extraction Methods for Removing Sulfur and Its Compounds

from Crude Oil and Petroleum Products
O. N. Katasonovaa,*, E. Yu. Savoninaa, and T. A. Maryutinaa
a Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
*e-mail: katasonova_ol@mail.ru
Received December 21, 2020; revised March 11 2021; accepted March 26, 2021
Abstract—Sulfur is present in crude oil and petroleum products in the form of various compounds: mercaptans,
hydrogen sulfide, sulfides, disulfides, thiophene derivatives, high-molecular-mass heterocyclic compounds,
etc. The content of elemental sulfur in petroleum feedstock is low (up to 0.1%). Sulfur negatively affects the
service and transportation properties of oil; therefore, the content of sulfur compounds in petroleum products
and commercial oil is strictly limited. Numerous methods are used today for removing sulfur compounds from
petroleum feedstock, such as hydrotreating, bio- and oxidative desulfurization, extraction, including supercritical
fluid extraction, adsorption, alkylation, etc. This review deals with the use of extraction methods for treating
petroleum feedstock to remove various sulfur-containing compounds. Particular attention is paid to papers dealing
with the use of cheap and available polar organic solvents and inorganic chemicals for removing sulfur and its
compounds both from model solutions and from crude oils and petroleum fractions. Also, search for new “green”
solvents such as ionic liquids and eutectic mixtures, allowing removal of sulfur compounds from crude oil, shows
promise. As a rule, complete removal of sulfur-containing compounds from oil samples by extraction requires a
multistep extraction process.
Keywords: extraction, polar organic solvents, ionic liquids, eutectic solvents, sulfur compounds, desulfurization
of petroleum products
DOI: 10.1134/S1070427221040017
INTRODUCTION world tends to increase. The world market’s price of

high-sulfur crudes is considerably lower than that of
A topical problem of the modern petroleum industry is their low-sulfur analogs; in addition, requirements to
the development of new technologies for desulfurization the quality of petroleum products become more and
of crude oil and petroleum products and subsequent use more stringent. The presence of sulfur compounds
of the separated concentrates of sulfur compounds for negatively affect the environmental, transportation,
producing various items (forage, fertilizers, solvents, and service properties of crude oil and petroleum
paints, drugs, fungicides, plastics, car tires, detergents, products. Aggressive components of sulfur-containing
additives, etc.). oil compounds, namely, mercaptan sulfur and hydrogen
Depending on the oil field, the extracted crudes differ sulfide, cause equipment corrosion and tarring in the
in the speciation and content of sulfur: from fractions of course of oil refining, decrease the fuel stability, and
percent (light low-sulfur crudes from Northwest Siberia, impart specific odor to petroleum products. Sulfides,
sulfur content below 0.6%) to 6% (heavy high-sulfur disulfides, thiophene derivatives, and high-molecular-
crudes from Ural and Volga fields). The highest sulfur mass sulfur compounds, compared to hydrogen sulfide
content (14%) was found in crude oil from the Rozel and mercaptans, are more inert, and their content in fuel
Point field (Utah, the United States) [1]. fractions can reach 80% [2, 3].
The extraction of high-sulfur and high-viscosity The combustion of sulfur compounds present in
crude oils in various oil-producing regions of the liquid fuel leads to the formation of sulfur oxide, to
411
412 KATASONOVA et al.
air pollution, and to a decrease in the fuel performance extraction cycles accompanied by the solvent loss with
and operation characteristics of engines. Therefore, the a low raffinate yield.
sulfur content in many petroleum products is strictly The number of papers dealing with the extraction
limited. According to the Euro-5 standard for diesel fuel, using not only “classical” solvents but also ionic liquids,
adopted in Europe, the sulfur content of the fuel should eutectic mixtures, and supercritical fluids increased in
not exceed 0.001%.1 The content and speciation of sulfur the past two decades [18–26]. The use of the latter three
in various oil fractions vary depending on the boiling extraction methods for removing sulfur compounds
point of the corresponding fractions [4]. Aliphatic sulfur from crude oil and petroleum products is yet at the
present in <350°C distillates is virtually absent in gasoil research step.
and tar fractions, in which aromatic sulfur (thiophene This review is aimed as analyzing and summarizing
and its derivatives) prevails. Compounds containing data on extraction methods for removing sulfur
aliphatic sulfur are removed from oil more readily than compounds from crude oil and petroleum products.
aromatic sulfur compounds [5]. Achievements in the field of desulfurization of crude
The processes used today for sulfur removal include oil and petroleum fractions with polar organic solvents,
hydrodesulfurization, extraction, adsorption, oxidative ionic liquids, and deep eutectic solvents, reached in the
desulfurization, alkylation, and removal of sulfur past 20 years, are noted.
compounds using biopreparations or supercritical water,
but none of them is versatile [5–15]. EXTRACTION OF SULFUR COMPOUNDS WITH
Extractive desulfurization is based on higher POLAR ORGANIC SOLVENTS
solubility of sulfur compounds, compared to
hydrocarbons, in an appropriate polar solvent [16]. Most of the published research papers deal with
The procedure for removing sulfur and its compounds the removal of sulfur and its compounds from model
by extraction is attractive and cheap because of mild solutions and from preliminarily separated diesel and
process conditions (high temperatures and pressures gasoil fractions (Table 1). Desulfurization of heavy and
are not applied) and no chemical action on the feed. high-sulfur crude oils and of their heavy fractions is a
The extraction choice is governed by the type of the challenging problem because of their high viscosity and
sulfur-containing compound to be removed and by high boiling point, and also of high content of complex
the physicochemical characteristics of the petroleum heteroatomic compounds [5].
products. The extraction efficiency will be limited by Thiophenes and their derivatives are extracted from
the solubility of sulfur compounds in the extractant. In petroleum feedstock with aprotic solvents such as
addition, the two liquid phases should be immiscible acetonitrile, dimethylformamide, dimethylacetamide,
and should have low viscosity to ensure efficient mixing N-methylpyrrolidone, and dimethyl sulfoxide. These
and mass exchange. The extractant should be nontoxic solvents exhibit low selectivity, high ability to dissolve
and cheap; it should exhibit anticorrosive properties and aromatic sulfur compounds, and ability to form stable
be thermally and chemically stable. The boiling points π-complexes with them [27]. The most widely used
of the solvent and sulfur compounds extracted from extractant is N-methylpyrrolidone, because it surpasses
petroleum feedstock should be different to ensure the the majority of other solvents in capacity [28–34].
possibility of the solvent regeneration by distillation and However, the yield of the raffinate fraction in this case
its reuse [5, 16, 17]. is relatively low. For example, as noted in [28], in the
The practical use of the extraction technology for course of three-step crossflow extraction treatment of
sulfur removal from crude oil is complicated by the light vacuum gasoil using N-methylpyrrolidone at 2 : 1
fact that the range of available selective extractants weight ratio, the sulfur content of the raffinate decreases
or their mixtures is narrow. As a rule, the degree of from 1.65 to 0.35 wt % at the final product yield of
desulfurization of real oil samples does not exceed 39.6%.
50%, and complete oil desulfurization requires several In some papers, the problem of hydrocarbon loss
––––––––––––––– is solved by adding a co/antisolvent or varying the
1 Directive 2009/30/EC of the European Parliament and of the Council extraction temperature [29, 30]. The addition of water
of 23 April 2009. http://data.europa.eu/eli/dir/2009/30/2016-06-10 or a nonpolar solvent allows the solvent selectivity and
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021
Table 1. Extraction of sulfur compounds from model solutions and real petroleum feedstock samples with polar organic solvents and inorganic reagents
Sulfur compound Sample Extractant Conditionsa Degree of extraction References

Total sulfur Light cycle oil Acetonitrile, 50°С, Vs:Vf = 2.5:1, 30 min Acetonitrile: 38% (raffinate [27]
(2157 mg·L–1) dimethylformamide, yield 48.5%).
N-methylpyrrolidone + 5% Dimethylformamide: 60.8%
H2O for each solvent (raffinate yield 43.4%).
N-Methylpyrrolidone: 62.6%
(raffinate yield 41.7%)
Total sulfur Vacuum gasoil N-Methylpyrrolidone 40°С, Vs:Vf = 2:1, 20 min 91.61% (raffinate yield [28]
(271.6–458.3°С) 39.6%), 3 extraction steps
Total sulfur Gasoils N-Methylpyrrolidone + 3, Batch extraction: 45°С, Batch extraction: 42.6– [29]
(0.268–1360 mg·L–1) 5, 7% Н2О Vs:Vf = 1:1 or 1.5:1. 67.9% (raffinate yield 56–
Dynamic extraction Vs:Vf 77.5%). Dynamic extraction
= 1.4:1, content H2O 4%. 76.5% (raffinate yield 63.3%)
Feed and solvent flow rates
5 and 7 mL·min–1
Total sulfur Atmospheric Solvent mixtures: 40°С, Vs : Vf =1:1 and 1.5 N-Methylpyrrolidone + [30]
gasoil (299–351°С, N-Methylpyrrolidone : 1. At nonpolar solvent to 1% Н2О — 26%,
11700 mg·kg–1) + 1% Н2О, phenol + feed weight ratio of 0.3 : 1 N-Methylpyrrolidone +
5% Н2О, 1% Н2О + heptane — 30.7%,
N-Methylpyrrolidone + N-Methylpyrrolidone +

+ 1% Н2О + heptane, 1% Н2О + Nefras 80/120 —
N-Methylpyrrolidone + 32.3%
+ 1% Н2О + Nefras
80/120, dimethyl sulfoxide
+ Nefras 80/120
Total sulfur Hydrodewaxed Dimethylformamide, 40°С, Vs:Vf = Hydrodewaxed fraction [31]
EXTRACTION METHODS FOR REMOVING SULFUR
fraction of atmospheric N-methylpyrrolidone + 2:1(N-methylpyrrolidone) of atmospheric gasoil

gasoil (240–392°С, 1% Н2О (N-methylpyrrolidone):
24 mg·kg–1), 80.4% (raffinate yield
straight-run fraction 86.2%).
of atmospheric Straight-run fraction
gasoil (205–373°С, of atmospheric gasoil
9890 mg·kg–1) (dimethylformamide): 37.7%
(raffinate yield 79.5%)
413
Table 1. (Contd.) 414

Total sulfur Visbreaking gasoil Phenol + 10% Н2О, Gasoil was separated into 1 : 72% (raffinate yield [32]
(160–340°С, 1.853 wt N-methylpyrrolidone + two fractions: 80.4%),
%) 1% Н2О (1) s.b.–234°С, 45°С, Vs:Vf 2: 76% (raffinate yield 64%),
= 2:1 (phenol), 5 extraction steps
(2) 234°С–e.b.
40°С, Vs:Vf = 1:1
(N-Methylpyrrolidone)
Total sulfur Light and heavy N-Methylpyrrolidone, 40°С, Vs:Vf = 2.58:1; Multistep countercurrent ex- [33]
vacuum gasoil (1.65 N-methylpyrrolidone 2.97:1 for light gasoil and traction using a rotating disc
and 1.68 wt %) + benzene reforming Vs:Vn.s:Vf = 2.95 : 0.47 : 1; contactor : 86.3–90.3% (raf-
raffinate (as 3.28 : 0.86 : 1 for heavy finate yield 45.9–52.5%) for
nonpolar solvent), gasoil light gasoil,
dimethylformamide 91.8–93.8% at similar raf-
finate yield for heavy gasoil
Thiophenes Model solution in Dimethylformamide, 50°С, Vs : Vf = 2 : 1, N-Methylpyrrolidone: 97% [34]

isooctane (500 mg·L–1) N-methylpyrrolidone, 1000 rpm–1, 60 min
ethylene glycol
KATASONOVA et al.
Benzothiophene, 3-methyl- Model solution Dimethylformamide, 45°С, Vs : Vf = 1 : 1, 25 min N-Methylpyrrolidone > di- [35]
benzothiophene, dibenzo- I in hexadecane, dimethylacetamide, methylacetamide > dimeth-
thiophene, 4-methyldiben- II in dodecane, dimethyl sulfoxide, ylformamide > dimethyl
zothiophene, 4,6-dimethyl- butyl benzene, N-methylpyrrolidone sulfoxide
dibenzothiophene methylnaphthalene Dimethylformamide:
66.8, 18.8, and 14.4% benzothiophene ≈ diben-
zothiophene > 4-methyl-
dibenzothiophene > 3-meth-
ylbenzothiophene ≈ 4,6-di-
methyldibenzothiophene >
2-N-octylthiophene >>
1-dodecanethiol For model
mixture II: 12.44–70.34%.
Real and mixed gasoil sam-
ples 38.8–54.4%

Table 1. (Contd.)

Total sulfur Прямогонный газойль Acetonitrile, furfural, 55°С, Vs : Vf = 1 : 1, 30 min Countercurrent extraction: [36]
(до 221°С, 1.3 wt %) dimethylformamide, dimethylformamide 71.5%
dimethyl sulfoxide, (raffinate yield 74.3%)
dimethylacetamide
Total sulfur Diesel fuel (415 mg·L– Methanol, ethanol, 29°С, Vs : Vf = 1 : 1 Dimethylformamide: 88%, [37]
1) dimethylformamide, (Dimethylformamide), 30 2 extraction steps
N-methylpyrrolidone, min
dimethyl sulfoxide,
acetonitrile, polyethylene
glycol-400, ethylene
glycol
Total sulfur Diesel fuel Dimethylformamide 120°С, Vs : Vf = 3 : 1, 30 83.5% (raffinate yield [38]
(176–420°С, 2 wt %) min 41.4%), for 2 extraction steps
Total sulfur Light visbreaking Dimethylformamide 40°С, Vs : Vf = 0.5 : 1 and Light visbreaking gasoil [39]
gasoil (175–282°С), 0.4 : 1 19.3% (raffinate yield
0.83 wt %. 80.2%), 5 extraction steps.
Light decelerated Light decelerated coking

coking gasoil (180– gasoil 23.2% (raffinate yield
280°С), 0.69 wt % 82.6%)
Sulfides, thiophenes Diesel fuel (0.22 wt %, Dimethylformamide, 25°C, 30 min More than 90% in 2 [40]
200–360°C) dimethyl sulfoxide + extraction steps
CdCl2, CuCl2, CoCl2,
MnCl2, CrCl3, Cu(TFA)2,

Co(TFA), Mn(TFA)2
Total sulfur, sulfides, Crude oil from Dimethylformamide Vs : Vf = 1 : 1 12% of total, 14% of sulfide, [41]
thiophenes Arkhangelskoe field of 11% of thiophene sulfur
Volga–Ural Oil and Gas
Province
415

Total sulfur Atmospheric gasoil Dimethylformamide 40°С, Vs : Vf = 1 : 1 60% (raffinate yield 66.5%), [42]
(299–351°С) and light за 3 extraction steps
visbreaking gasoil
(180–300°С), 70 : 30,
12700 mg·kg–1
Thiophene, dibenzothio- Model solution of Dimethylformamide, also 29°C, Vs : Vf = 1 : 1, 90.2% of thiophene, 97.2% [43]
phene, 4,6-dimethyldiben- sulfur compounds in in the presence of KI, 1000 rpm, 30 min of dibenzothiophene, 77% of
zothiophene n-octane (50, 150, KOH, NaOH 4,6-dimethyldibenzothiophene
300 mg·L–1)
Total sulfur Light cycle oil Acetonitrile 25°C, Vs : Vf = 2.5 : 1, 30 Decrease in sulfur content [44]
(0.47 wt %, 193– min from 0.47 to 0.31 wt %
383°С) (raffinate yield 25.6%)
Total sulfur Light cycle oil Acetonitrile, 30°С, Vs : Vf = 3 : 1 для Acetonitrile: 84.1% [45]
dimethylformamide Dimethylformamideа и 5 : 1 (raffinate yield 19.64%),
для Acetonitrileа, 30 min Dimethylformamide: 66.65%
raffinate yield 39.4%)
KATASONOVA et al.
Дибензотиофен Light cycle oil (Ural) Acetonitrile, in mixture 40°С, Vs : Vf = 1.5 : 1, Acetonitrile: 75.2% (raffinate [46]
with methanol and Н2О 1000 rpm, 30 min yield 43%), Acetonitrile
+ 4% methanol: 75.5%
(raffinate yield 44%),
Acetonitrile + 4% Н2О :
57.3% (raffinate yield 63%)
Total sulfur Light vacuum gasoil Acetonitrile, Acetonitrile– 25°C, Vs : Vf = Acetonitrile: 56.8% (raffinate [47]
(1.57 wt %) hexane 2 : 1 (acetonitrile) yield 70%), for 2 extraction
and 2.6 : 0.56 : 1 steps.
(Acetonitrile : hexane), Acetonitrile : hexane: 28%
15 min (raffinate yield 90%)
Total sulfur Gasoil (catalytic Sulfolane 50°С, Vs : Vf = 3 : 1 with 65.43% [48]
cracking), Tк = 150°С, stirring at 700 rpm, 15 min

800 mg·kg–1
Table 1. (Contd.)

Total sulfur Gasoil (catalytic Sulfolane, furfural 50°С, Vs : Vf = 1 : 1 Sulfolane: 196 mg kg–1 [49]
cracking), 760 mg·kg–1, (furfural) or 4 : 1 (74.2%), in 6 steps, up to
Tb = 155°С (sulfolane), 700 rpm, 83 mg kg–1 (89.1%)
30 min
Сульфиды, тиофены Diesel fraction Acetonitrile, 40°С, Vs : Vf = 2 : 1, in the Phenol + 3% H2O : 80.2% [50]
recovered from South dimethylformamide, case of using hexane 3 : 1 (raffinate yield 48.3%);
Uzbekistan crudes dimethylacetamide, methyl phenol + 8% H2O : 58.9%
(2.02 wt %, sulfide Cellosolve, furfuryl (raffinate yield 71.6%)
sulfur 1.42 wt %) alcohol, tetrahydrofurfuryl Countercurrent extraction:
alcohol, phenol. phenol + 3% H2O : 100%;
Dimethylformamide/ phenol + 8% H2O : 97.4%
tetrahydrofurfuryl alcohol (raffinate yield 64.8%)
(50/50), furfuryl alcohol/
phenol (50/50). In mixture
with hexane (1 : 1), in the
presence of 3% H2O
Total sulfur Diesel fraction Phenol : H2O : hexane 50°C, phenol with 8 wt % Countercurrent extraction: [51, 52]
recovered from South system H2O at the weight ratio to decrease in the sulfur content
Uzbekistan crudes the feed of 3 : 1 (or volume from 2.02 to 0.38 wt % (raf-

(2.02 wt %, sulfide ratio of 2.35 : 1) and of finate yield about 73%), 7
sulfur 1.42 wt %) hexane to feed weight ratio extraction steps
of 0.5 : 1
Total sulfur Superviscous Tetrahydrofuran, 25°С, Vs : Vf = 1 : 1 SVC: dimethylformamide : [53]

crude (SVC) from dimethylformamide, 1500 rpm, 30 min H2O (10 : 1) 18.6%. Devo-
Ashal’chinskoe field pyridine, acetonitrile, their nian crude: methanol 13.3%
(4.29 wt %) and aqueous and alcoholic

Devonian crude from solutions, methanol,
ethanol, acetone,
Romashkinskoe field
NaOH, mineral acids
(1.50 wt %)
417

Benzothiophene, Model solution in Polyethylene glycol-200 Troom, Vs : Vf = 1 : 1, 5 min 69% of benzothiophene, 76% [54]
dibenzothiophene, heptane (500 mg L–1) of dibenzothiophene, 43% of
dimethyldibenzothiophene dimethyldibenzothiophene
In 3 extraction steps the total
sulfur concentration was re-
duced from 500 to 10 mg L–1
Dibenzothiophene Model solution of Methanol, benzyl alcohol, 25°С, Vs : Vf = 1 : 1, 30 min Полиethylene glycol-400: [55]
dibenzothiophene in 2-phenylethanol, ethylene 99.99%
octane, 300 mg kg–1 glycol, tetraethylene
glycol, glycerol, and
polyethylene glycol-400
Thiophene, dibenzo- Model solution of Polyethylene 30°С, Vs : Vf = 1 : 1, 15 min Methoxypolyethylene gly- [56]
thiophene, sulfur compounds glycol-200, 400, 600, col-500: 59.7% of thiophene,
4,6-dimethyldibenzo- in octane + toluene methoxypolyethylene 70.7% of benzothiophene,
thiophene (effect of aromatic glycol-500, polyethylene 76.1% of dibenzothiophene,
hydrocarbons) glycol-500 dimethyl ether 56.7% of 4,6-dimethyldiben-
zothiophene
(1000 mg L–1)
Polyethylene glycol-500
dimethyl ether: 64.1% of
thiophene, 76.4% of benzo-
KATASONOVA et al.
thiophene, 80.6% of dibenzo-

thiophene, 63.2% of 4,6-di-
methyldibenzothiophene
Benzothiophene, Model solution in 4,7,10-Trioxatridecane- 25°С, Vs : Vf = 0.5, 20 min 67% of benzothiophene, [57]
dibenzothiophene, heptane and pentane 1,13-diаmine 74% of dibenzothiophene,
dimethyldibenzothiophene (500 mg kg–1) and 53% of
dimethyldibenzothiophene
Total sulfur Furnace gasoil (257– Methanol, furfuryl, 80°С, Vs : Vf = 2 : 1 Furfural. Furnace gasoil: [58]
390°C, 0.47 wt %), ethylene glycol, 81% (raffinate yield 80.8%).
hydrotreated diesel fuel 40% NaOH in methanol Diesel fraction: 86%
(222–375°C, 0.2 wt %) (raffinate yield 86.9%)

Table 1. (Contd.)

Total sulfur (mainly Crudes from Tyumen Ethanol, acetone Refluxing in a round- Tyumen crude: ethanol up [59]
sulfide) field, Khanty–Mansi bottomed flask on a water to 68%, acetone 10.8% of
autonomous okrug bath. Crude oil weighed sulfur.
(1.73 wt %) and from portion 1 ± 0.2 g with 0.5 Demkinskoe crude: ethanol
Demkinskoe field, L of ethanol for 2 h, then 72%, acetone 18.5% of sulfur
Tatarstan (3.96 wt %) 200 mL of acetone for 1 h
Dibenzothiophene Model solution of Dimethylacetamide, 30°С, Vs : Vf = 1 : 1 92.5% of dibenzothiophene [60]
dibenzothiophene and dimethylformamide, 100 rpm, 15 min, dimeth-
benzothiophene in sulfolane ylacetamide : dimethyl-
octane (1000 mg L–1) formamide : sulfolane =
3 :1 : 1
Total sulfur Gasoil (648 mg L–1) Dimethylformamide, 30°С, N-Methylpyrrolidone : [61]

acetonitrile, N-Methylpyrrolidone : dimethylformamide :
dimethyl sulfoxide, dimethylformamide : ethylene glyco: 99.1%, 3
N-methylpyrrolidone, ethylene glycol (2 : 1 : 1), extraction steps
ethylene glycol Vs: Vf = 1 : 2, 500 Вт, 5 min,
200 об·min–1
Total sulfur Diesel fraction Dimethyl 50°С, Vs : Vf = 1.1 : 1 N-Methylpyrrolidone + [62, 63]

(straight-run) (212– sulfoxide, furfuryl, 10% ethylene glycol: 73.7%
343°C), 1.56 wt % N-Methylpyrrolidone + (raffinate yield 68.6%), 6
10% ethylene glycol, extraction steps
Dimethylformamide +
10% ethylene glycol
Hydrogen sulfide, light Model solution of 5% NaOH 65°С, Vs : Vf = 20 : 1, 40 Purification to 5 mg L–1, [64]
mercaptans ethyl mercaptan in min, 2 steps ~100%

n-dodecane (370 mg
L–1)
Tengiz crude (Tengiz
field, Kazakhstan,
0.52 wt %)
419

Thiophenol, Model solution of Methanol, ethanol, 25°С, Vs : Vf = 1 : 1, 90 min 15% NaOH: 100% of [65]
dodecanethiol, thiophene, sulfur compounds in dimethylformamide, thiophenol; 50% NaOH +
dibenzothiophene, heptane and octane acetonitrile, ethanol (1 : 2): 100% of
dimethyl sulfide (50 mg L–1 of each polyethylene glycol, dodecanethiol
sulfur compound) N-methylpyrrolidone,
dimethylacetamide,
monoethanolamine,
diethylene glycol, NaOH
Total sulfur Heavy crude (Al NaOH 40°C, 56.89% [66]
Khalfaya field, Iraq, Vs:Vf = 1:1, 500 rpm, 60
5.8 wt %) min
Hydrogen sulfide; Model solution of 25% aqueous ammonia, 40–50°C, Vs:Vf = 1:1, Batch extraction: 42% in one [67]
methyl, ethyl, and propyl propyl mercaptan 15% aqueous NaOH 1200 rpm, 1 min extraction step, 97% in five
mercaptans in petroleum ether extraction steps. Dynamic
(300 mg L–1), extraction 87%
butane–butylene
fraction (13 mg L–1),
propane–butane
fraction (hydrogen
KATASONOVA et al.
sulfide 4231 mg L–1,

mercaptan sulfur
1064 mg L–1)
Thiophenes, Model solution of H2O and aqueous solutions 10% НСl, 50°С, Vs:Vf = 50% of thiophene, 28.2% of [68]
benzothiophenes, sulfur compounds in of HCl, H2SO4, HNO3, 2:1, 1000 rpm, 60 min benzothiophenes, 26.8% of
dibenzothiophenes isooctane (500 mg·L–1) CH3COOH, NaOH, dibenzothiophene
NH4OH and NaCl
a Vs : Vf: solvent-to-feed ratio.

EXTRACTION METHODS FOR REMOVING SULFUR 421
the raffinate yield to be increased, but in many cases of commercial solvents for removing sulfur compounds
leads to a decrease in the degree of sulfur removal from from model solutions, real gasoil fractions, and their
petroleum feedstock. mixtures was made in [35–37]. For example, according
Addition of 3, 5, and 7% water as a modifier to to [35], the extractants can be ranked in a similar order
N-methylpyrrolidone in extraction treatment of gasoline with respect to the performance in sulfur removal
fractions obtained by atmospheric distillation, catalytic from model and real solutions: N-methylpyrrolidone >
cracking, and coking increased the raffinate yield by dimethylacetamide > dimethylformamide > dimethyl
17–65%, but the total sulfur content of the raffinate sulfoxide, but the degrees of extraction decrease in
fraction increased by 19–42.5%. Addition of 3% water going from model to real solutions. Dimethylformamide
to N-methylpyrrolidone allowed the phase separation in appeared to be advantageous with respect to the ratio
desulfurization of light gasoil from catalytic cracking of the degree of extraction of sulfur compounds
[29]. from the feed to the raffinate yield, and its low
boiling point, compared to N-methylpyrrolidone and
To solve the problem of hydrocarbon loss in
dimethylacetamide, reduces expenditures for the solvent
treatment of atmospheric gasoil, Kameshkov et al. [30]
regeneration by distillation. Dimethylformamide
suggested using extraction systems containing, along
extracts sulfur compounds from model mixtures in the
with N-methylpyrrolidone + 1% water, also nonpolar
following order: benzothiophene ≈ dibenzothiophene >
solvents such as heptane or saturated Nefras (naphtha
4-methyldibenzothiophene > 3-methylbenzothiophene ≈
solvent) 80/120. Nonpolar solvents are selective to
4,6-dimethyldibenzothiophene > 2-n-octylthiophene >>
saturated hydrocarbons and favor their transfer to the
1-dodecanethiol.
raffinate phase. However, to improve the raffinate
quality, it is necessary to increase the ratio of the polar Kumar et al. [36] introduced the solvent performance
solvent to the feed. factor and suggested for it a calculation formula
including two main parameters: degree of removal
To avoid the formation of homogeneous azeotropes of sulfur compounds and raffinate yield. With respect
of N-methylpyrrolidone with arenes and heteroatomic to the degree of removal of sulfur compounds from
components, which can complicate the subsequent solvent straight-run gasoil, the extractants can be ranked in
regeneration, the petroleum products (hydrodewaxed the following order: furfural > dimethylformamide >
and straight-run atmospheric gasoil fractions, light dimethylacetamide > dimethyl sulfoxide > acetonitrile.
visbreaking gasoil) were preliminarily separated into The degree of extraction of sulfur compounds with
light (160–250°С) and heavy (250–340°С) fractions; dimethylformamide, dimethylacetamide, and furfural is
the latter was extracted with N-methylpyrrolidone [31, considerably higher (37.7–41.5%) than with acetonitrile
32]. and dimethyl sulfoxide (9.2–20.8%), and furfural extracts
After multistep countercurrent extraction treatment the maximal amount of sulfur from petroleum products.
of light vacuum gasoil with N-methylpyrrolidone using However, the raffinate yield with dimethylformamide,
a rotating disc contactor at 40°С and different extractant- dimethylacetamide, and furfural is lower (72.5–
to-feed weight ratios, the sulfur content of the raffinate 82.5%) than with dimethyl sulfoxide and acetonitrile
was <0.5 wt %, which meets the requirements to the (87.5–88.5%). Dimethylformamide, furfural, and
ship fuel quality. The extraction of heavy vacuum gasoil dimethylacetamide are comparable in the performance
with N-methylpyrrolidone in the presence of a nonpolar factor, but furfural is poorly resistant to oxidation and
solvent, benzene reforming raffinate, yielded a ship fuel heat, and the boiling point of dimethylformamide is lower
component with 0.57 wt % sulfur content [33]. than that of dimethylacetamide. N-Methylpyrrolidone
The use of dimethylformamide for removing sulfur and dimethyl sulfoxide, despite high extraction ability,
compounds from petroleum feedstock is economically have boiling points that are often close to those of
more feasible than the use of N-methylpyrrolidone. the extracted sulfur compounds, making impossible
Dimethylformamide is cheap, has a lower boiling separation of the solvent and concentrate of sulfur
point, and is characterized by acceptable ratio of the compounds by distillation [37].
extractant capacity and final product yield [35–43]. Toteva et al. [38] described the use of cosolvents,
Comparative analysis of the efficiency of using a series water and pentane. The addition of 5% water to

dimethylformamide at the 1 : 3 ratio of light gasoil and to dimethylformamide and N-methylpyrrolidone, which
solvent allowed the total sulfur content to be decreased is confirmed in a number of papers [44–53]. However,
from 0.63 to 0.21% and the raffinate yield to be increased. low values of the acetonitrile boiling point and viscosity
However, Gaile et al. [39] indicate that the presence of allow using it in excess relative to the petroleum product
water favors the dimethylformamide hydrolysis, which, and reducing the power consumption for its regeneration
in turn, leads to the equipment corrosion and complicates [18]. In treatment of light cycle oil, the total sulfur
the flowsheet. The five-step countercurrent extraction content was decreased from 0.47 to 0.31 wt % at the
scheme that they suggested, involving extraction with extractant : feed ratio increased to 2.5 : 1; the raffinate
anhydrous dimethylformamide at 40°С and the weight yield was 26.5% [44]. Toteva [45] reported that, at the
ratios of the extractant to visbreaking and decelerated acetonitrile : light cycle oil ratio of 5 : 1, the degree
coking gasoils of 0.5 : 1 and 0.4 : 1 allowed reduction of extraction of sulfur compounds from the petroleum
of the dimethylformamide volume required for the product was 84.1% at 20% yield of the raffinate fraction.
treatment, ensured acceptable (80.2–82.6%) yield of Addition of 1% water improves the final product yield
the final product, and allowed the content of sulfur and favors efficient phase separation, but the degree of
compounds to be decreased from 0.83 and 0.69 wt % in extraction of sulfur compounds from the gasoil fraction
the feed to 0.67 and 0.53 wt % in the raffinate. decreases to 55.6%. In [46], addition of even minor
The use of modified extractants allowed amount of water (4%) at the solvent : light cycle oil
desulfurization of petroleum products. Kobotaeva et al. ratio of 1.5 : 1 at 40°С allowed the raffinate yield to
[40] studied the removal of sulfur compounds from be increased from 43 to 63%; however, the content of
diesel fuels by extraction with dimethylformamide and benzothiophenes in the petroleum feedstock increased
dimethyl sulfoxide containing metal (Cd, Co, Mn, Cu, in this case by 23.8%.
Cr) chlorides and trifluoroacetates (TFA). They suggest Vereshchagin et al. [47] reported that a decrease
that the metal cation is coordinated to the carbonyl in the sulfur content of the raffinate of light vacuum
group of dimethylformamide via oxygen atom, which gasoil (192–539°С) from the AVT-6 installation
enhances the properties of the acceptor center localized (Kirishinefteorgsintez Production Association) to
on the nitrogen atom and favors more complete the level of 1 wt % (in accordance with modern
extraction of sulfur compounds from diesel fuel requirements to low-viscosity ship fuels) became
samples. The efficiency of using dimethylformamide possible at the acetonitrile to feed weight ratio of 2 : 1 in
and dimethyl sulfoxide modified with metal chlorides two extraction steps at the raffinate yield of up to 70%.
and trifluoroacetates can be accounted for on the basis However, preliminary experiments showed that addition
of Pearson’s concept of hard and soft acids and bases, of a nonpolar solvent at the ratio acetonitrile : hexane :
according to which soft acids interact preferentially with gasoil = 2.6 : 0.56 : 1 favored an increase in the yield and
soft bases, and hard acids, with hard basis. Among the a decrease in the sulfur content of the raffinate relative to
metal chlorides used, CdCl2 can be classed with soft the use of pure acetonitrile in 2 : 1 and 3 : 1 ratios.
Lewis acids; CoCl2 and CuCl2, with acids of intermediate Sulfolane is a polar aprotic solvent and is used in
hardness; and MnCl2 and CrCl3, as hard acids. The some industrial installations. Sulfolane is miscible both
degree of extraction of sulfur compounds with systems with water and with hydrocarbons, which led to its wide
based on dimethylformamide as a hard base and metal use as a solvent for treatment of hydrocarbon mixtures.
salts increases in the following order: CdCl2 < CuCl2 < In petroleum chemistry, sulfolane is used as a reagent
CoCl2 < MnCl2 = CrCl3 < Cu(TFA)2 < < Co(TFA)2 < for extractive recovery of aromatic compounds to obtain
Mn(TFA)2. Sulfur compounds are removed from diesel high-octane gasolines. Adzamic et al. [48, 49] suggested
fuel with 0.22 wt % sulfur content under mild conditions sulfolane as an extractant for removing aromatic
(25°С, atmospheric pressure) in 30 min. After one or compounds from the gasoline fraction. From catalytic
two extraction steps, the diesel fuel contained only trace cracking gasoil, 89.1 wt % of sulfur was removed by
amounts of sulfur compounds. six-step extraction at 50°С and the solvent : feed ratio
Acetonitrile compared to dimethylformamide and of 4 : 1.
N-methylpyrrolidone is characterized by lower selectivity, Proton-donor solvents such as phenol, methyl
lower capacity, and increased raffinate yield compared Cellosolve, tetrahydrofurfuryl alcohol, furfuryl
alcohol, ethylene glycol, and polyethylene glycols are electron density on the sulfur atom and steric structure
effective for extractive removal of sulfide sulfur [50– of the sulfur-containing molecule. The extraction
59]. Gaile et al. published several papers dealing with efficiency with polyethylene glycol is independent
desulfurization of petroleum fractions (obtained by of temperature and initial sulfur content of the crude
processing high-sulfur crudes from South Uzbekistan oil. Low viscosity of polyethylene glycol-200 favors
with high nitrogen content and prevalence of sulfides) efficient mass exchange; the equilibrium is reached in
using various extractants [50–52]. To increase the less than 3 min in all the experiments. Polyethylene
raffinate yield, they used phenol containing 8 wt % glycol was reused in five cycles and then regenerated by
water and a nonpolar solvent, hexane, for efficient phase adsorption using activated carbon [54].
separation. The seven-step countercurrent extraction of
Li et al. [55] tested a series of alcohols for removing
the diesel fraction containing 2.02 wt % sulfur, including
dibenzothiophene from n-octane. They showed that an
1.42 wt % sulfide sulfur, with phenol containing 8 wt %
increase in the number of hydroxyl groups in alcohols
water at the extractant to feed ratio of 3 : 1 (at 50°С)
positively influenced the efficiency of the extraction
gave raffinate in 64.8 wt % yield with 0.23 wt % sulfur
of sulfur compounds; it varied in the following
content. Under the same conditions, in the presence of
order: polyethylene glycol-400 > 2-phenylethanol >
an additional nonpolar solvent, hexane, at its weight
tetraethylene glycol > benzyl alcohol > methanol >
ratio to the feed of 0.5 : 1, the raffinate yield increased
to 72.6 wt %, and the sulfur content of the raffinate was ethylene glycol > glycerol. 99.99% of dibenzothiophene
0.38 wt % [51]. was removed in one extraction step at 1 : 1 ratio of the
model solution to the extractant at 25°С in 30 min.
In [53], the extraction of sulfur compounds from
crude oils was performed in the flow-through mode Gao et al. [56] describe the advantages of using
using centrifugal contactors. The efficiency of using modified polyethylene glycol compared to their classical
various organic extractants for the sulfur removal from analogs. The use of methoxypolyethylene glycol-500 and
crudes of Ashal’chinskoe and Romashkinskoe fields dimethyl ether of polyethylene glycol-500 increased the
was evaluated. A methanol solution showed the highest selectivity and efficiency of the extraction of thiophene
performance in sulfur removal from the Romashkinskoe compounds from model solutions in octane (containing
crude in centrifugal contactors (the degree of removal up to 25% toluene as an aromatic hydrocarbon),
of sulfur compounds from the crude was 13.3%), and a compared to polyethylene glycols-200, 400, and 600. The
dimethylformamide–water solution was the most effec- extraction activity of modified polyethylene glycols is
tive for the Ashal’chinskoe crude (18.6%). Additional determined by bonding between the active oxygen atom
pretreatment consisting in ultrasonic and/or magnetic and aromatic hydrogen atom of thiophenes, on the one
treatment of crude oil in combination with its oxidation hand, and by similarity of the C–O–C group in modified
and heating increased the efficiency of removing sulfur polyethylene glycols and C–S–C group in thiophene
compounds from crude oil samples by 20–40%. derivatives, on the other hand. The degree of extraction
Organic solvents, as a rule, are toxic, volatile, and of thiophene, benzothiophene, dibenzothiophene,
readily inflammable; therefore, a number of studies and 4,6-dimethyldibenzothiophene from octane with
[54, 55] deal with the search for “green” solvents modified polyethylene glycols was 64.1, 76.4, 80.6,
such as water-soluble polyethylene glycols, which and 63.2%, respectively. 4,7,10-Trioxatridecane-1,13-
are proton-donor solvents. Polyethylene glycols are diamine, a solvent with a polyethylene glycol fragment and
characterized by low viscosity (dynamic viscosity 58– two amino groups, allows extraction of benzothiophene,
85 MPa s at 20°C) and high boiling point (>150°С). dibenzothiophene, and dimethyldibenzothiophene from
The use of polyethylene glycol-200 allowed the heptane with 67, 74, and 53% efficiency, respectively.
dibenzothiophene content of a model solution to be The distribution ratio of dibenzothiophene in the system
decreased by 98% from 512 to 10 mg L–1 in three with 4,7,10-trioxatridecane-1,13-diamine was higher
extraction cycles. The efficiency of the extraction of by 3.66 than in the systems with polyethylene glycols
various thiophene derivatives decreased in the order and was close to that in the systems with polyethylene
dibenzothiophene (76%) > benzothiophene (69%) > glycol dimethyl ether and acid-containing ionic liquids.
dimethyldibenzothiophene (43%), depending on the A decrease in the dibenzothiophene concentration in
octane from 500 to 20 mg L–1 became possible after ease of implementation. Sodium hydroxide efficiently
three extraction steps [57]. takes up hydrogen sulfide and light mercaptans from
Some authors state that, on mixing dissimilar organic petroleum products, but is inefficient in removal of
solvents, the selectivity and solvency of the extraction heavy mercaptans and polycyclic sulfur compounds,
mixture can be brought to the optimum levels. A 3 : 1 : which are weak acids and are poorly soluble in water.
1 mixture of dimethylacetamide, dimethylformamide, Researchers from the Volga Research Institute of
and tetramethyl sulfone at the extractant to feed (model Hydrocarbon Resources developed a two-step procedure
gasoline) ratio of 1 : 1 at 30°С extracts 92.5% of diben- for demercaptization of Tengiz crude oil [64]. The use
zothiophenes in one extraction step and 99.1% of total of a 5% NaOH solution at the extractant to crude oil
sulfur in five steps. The solvents after three extraction ratio of 20 : 1 and 65°С allows the content of ethyl and
cycles were regenerated by the adsorption method [60]. methyl mercaptans in the hydrocarbon feedstock to be
99.1% of sulfur was extracted from the gasoline fraction reduced to the level no higher than 5 mg L–1 with the
with a 2 : 1 : 1 mixture of N-methylpyrrolidone, dimeth- subsequent catalytic regeneration of the alkali solution
ylformamide, and ethylene glycol at the extractant to by oxidation of mercaptides with atmospheric oxygen
feed ratio of 1 : 2 at 30°С in 5 min under the conditions to disulfides. The regenerated alkali is returned to the
of microwave irradiation (500 W) [61]. process cycle, and the mixture of by-products, dialkyl
The dimethylformamide + ethylene glycol (10 wt %) disulfides, is suggested for use for producing dimethyl
system surpasses the N-methylpyrrolidone + ethylene disulfide (a coking inhibitor in pyrolysis of gaseous
glycol system in the raffinate yield (69.8%) and purity feedstock), thiophene, and elemental sulfur on a Claus
of the straight-run diesel fuel fraction (the degree of installation.
removal of sulfur compounds is 79.5%), but requires 2 The results of [65] confirm the selectivity of alkali and
times more extraction steps at the same solvent-to-feed alcoholic alkali solutions in the removal of mercaptans.
volume ratio [62, 63]. For example, a 15% NaOH solution quantitatively
Mokhtar et al. [37] studied the effect of some extracts thiophenol from a model mixture consisting of
cosolvents such as ethylene glycol, polyethylene glycol, various sulfur compounds (thiophenol, dodecanethiol,
acetonitrile, and N-methylpyrrolidone on the selectivity thiophene, dibenzothiophene, dimethyl sulfide) in
and capacity of dimethylformamide in extraction of sulfur heptane and octane. The subsequent extraction with a
compounds from diesel fuel. The results show that, as 50% NaOH solution in ethanol leads to 100% recovery
the concentration of ethylene and polyethylene glycols of dodecanethiol. Alkali treatment also allowed removal
in dimethylformamide is increased to 2000 mg L–1, the of up to 56.7% of sulfur compounds from the heavy
degree of extraction of sulfur compounds decreases crude of the Al Khalfaya field (South Iraq) with 5.8 wt %
from 67.1 to 56.7%. Similar degrees of sulfur sulfur content [66].
extraction from petroleum feedstock, 58.6 and 51.9%, When using an aqueous ammonia solution of no less
were reached with N-methylpyrrolidone–acetonitrile than 25 wt % concentration as an extractant in alkali
and dimethylformamide–acetonitrile mixtures. As demercaptization, oxidative catalytic regeneration of the
compared to pure dimethylformamide, the use of spent alkali becomes unnecessary [67]. Ammonia reacts
the 1 : 1 dimethylformamide–N-methylpyrrolidone with hydrogen sulfide and light mercaptans to form
mixture allowed the degree of sulfur removal from the ammonium salts (sulfides, hydrosulfides, mercaptides),
diesel fraction to be increased to 70%. However, the which readily decompose to the initial ammonia,
addition of N-methylpyrrolidone to dimethylformamide hydrogen sulfide, and mercaptans by hydrolysis on
complicated the solvent regeneration and led to large heating (boiling) the spent aqueous ammonia solutions.
loss of the diesel fuel. This is one of competitive advantages of the suggested
treatment process over the use of NaOH. 42% of
EXTRACTION WITH AQUEOUS SOLUTIONS mercaptans were removed from a model solution with
OF ACIDS AND BASES aqueous ammonia in one cycle of batch extraction and
virtually 100%, in five cycles. The use of dynamic
Alkali treatment is an attractive desulfurization extraction in the countercurrent mode allows removal of
procedure because of the cheapness of chemicals and 87% of mercaptans.
In [68], thiophene, benzothiophene, and Much attention is paid to ionic liquids with the
dibenzothiophene were extracted from a model melting point lower than room temperature. Ideal ionic
fuel with aqueous solutions of HCl, H2SO4, HNO3, liquids are characterized by high capacity and selectivity
CH3COOH, NH4OH, NaOH, and NaCl of different to sulfur compounds, low values of cross solubility,
concentrations. Among the solutions tested, 10% HCl at viscosity, and vapor pressure, good thermal stability,
the extractant to model fuel ratio of 2 : 1 and 50°C shows electrical conductivity, and high rate of phase separation
the highest performance in the removal of thiophenes after mixing; the majority of the known ionic liquids
(50%). However, the degree of removal of benzo- and are, as a rule, nonflammable and low-toxic [20, 22, 71].
dibenzothiophene from the model fuel was lower: 28.2 However, commercial use of ionic liquids is restricted by
and 26.8%, respectively. From two gasoline samples their high cost, presence of impurities in the synthesized
under the same conditions, the HCl solution extracted ionic liquid samples, and low distribution ratios of
89.2 and 29.17% of sulfur compounds. sulfur compounds. In addition, ionic liquids containing
Treatment of petroleum feedstock with sulfuric acid halide anions are toxic, readily hydrolyzable, and highly
consists in the conversion of mercaptans to disulfides viscous, which largely limits their commercial use [21].
and sulfur dioxide and of thiophenes to thiophenesul- In 2001, Bösmann et al. [72] used for the first time
fonic acids and sulfur oxides. Disulfides, sulfides, tet- ionic liquids for removing sulfur compounds from fuel
rahydrothiophenes, and sulfones readily dissolve in fractions. Kobotaeva and Skorokhodova [73] removed
sulfuric acid. Prior to acid treatment, hydrogen sulfide sulfur compounds from the straight-run diesel fraction
is removed by washing with an alkali solution or by oxi- from Omsk Oil Refinery (200–360°С, total sulfur content
dation with oxygen to elemental sulfur. Treatment with 0.349 wt %) by extraction with imidazole-containing
sulfuric acid is accompanied by the loss of products, po- ionic liquids, straight and containing transition metal
lymerization, and formation of acid tars [69]. halides and trifluoroacetates. The extraction removal of
sulfur compounds from diesel fuel using ionic liquids
EXTRACTION WITH IONIC LIQUIDS without metal salts allowed the total sulfur content of
diesel fuel to be reduced from 0.34 to 0.2–0.14 wt %, and
Ionic liquids were used as an alternative to organic the addition of metal trifluoroacetates to ionic liquids
solvents for desulfurization of oil fractions. Ionic liquids based on butylimidazole allowed the sulfur content to be
are salts with the melting point lower than the boiling reduced to 0.06–0.05 wt %.
point of water, i.e., lower than 100°С [11]. Wang et al. [74] believe that metal salts exhibiting
Ionic liquids consist of organic cations (imidazolium, electron-acceptor properties ensure additional
pyridinium, isoquinolinium, ammonium, phosphonium, complexation with sulfur compounds via lone electron
sulfonium) and inorganic or organic anions ([Cl]–, [NO3]– pairs of sulfur atoms and unoccupied orbitals of
, [BF4]–, [РF6]–, [ЅbF6]–, [СF3ЅО3]–, [(СF3ЅО2)2N]–, the transition metal ions, with the electron-acceptor
[СН3СОO]–, [Аl2Сl7]–, [Me2PO4]–, [(CN)2N]–). The properties of transition metal trifluoroacetates being
physicochemical properties of ionic liquids depend on the stronger than those of the halides. The degree of
combination of the cation and anion. Correspondingly, removal of sulfur compounds from a gasoline fraction
the extractant properties can be optimized by varying (total sulfur content 740 μg mL–1) in extraction with
the two constituents of the ionic liquids. Intermolecular an ionic liquid of Lewis acid type, consisting of 1H-3-
interactions of ionic liquids including hydrogen bonding methylimidazolium chloride and copper(I) chloride,
and van der Waals, π–π, and ion pair interactions are [HMIM]Cl/[CuCl], was 23.2% at the extractant to fuel
considerably more complex compared to classical ratio of 1 : 1. The use of an ionic liquid based on 1-butyl-
solvents and influence the selectivity and capacity of 3-methylimidazolium chloride and copper chloride,
ionic liquids [70]. More than a thousand of different [BMIM][Cu2Cl3], at the extractant to fuel ratio of 1 : 5
ionic liquids are known today. Numerous papers have allowed removal of 23.4 and 21.6% of thiophenes from a
been published on the extraction of sulfur compounds model solution and a gasoline fraction with 680 mg L–1
from model solutions, but only relatively few papers, on sulfur content, respectively [75].
their extraction from real diesel and gasoline fractions Chu et al. [76] compared the performance of ionic
with ionic liquids [19–22, 70–92]. liquids containing tetrafluoroborate anion and substituted
imidazolium or pyridinium cation (substituents: С4H9, The influence of the cation size in an ionic liquid
С8H17, С6Н5) in desulfurization of two diesel fraction on the efficiency of the extraction of sulfur compounds
samples. An increase in the length of the alkyl group was also examined in [80, 81]. The authors state that,
enhanced the extraction ability of the ionic liquid. The with an increase in the cation size (increase in the alkyl
imidazole-based ionic liquids ensure higher degree of group length), the Coulomb interaction between the
extraction than the pyridine-based ionic liquids do, ionic liquid cation and anion becomes weaker, whereas
presumably because of the structural similarity of the the π–π interaction of the unsaturated bonds in sulfur
thiophene (in extracted sulfur compounds) and imidazole compounds with the imidazole ring of the ionic liquid
rings. The degree of sulfur removal from diesel fuel is increases. The alkyl group is an electron-donor group,
insufficiently high: 29.96 and 39.76% with 1-octyl-3- and an increase in the length of the alkyl-substituted
methylimidazolium tetrafluoroborate [C8MIM][BF4] at group favors an increase in the electron density in the
the extractant to fuel ratio of 1 : 1. aromatic ring of the extractant and positively influences
the extraction. For example, the use of 1-hexyl-3-
Extraction from the gasoline fraction was performed
(2-methoxycarbonyl)-3-imidazolium dicyanamide
using dicationic ionic liquids based on imidazole
[C2COOCH3IМC6H13][N(CN)2] allowed removal of up
and pyridine [77]. The ionic liquid based on 1-ethyl-
to 62% of dibenzothiophene from n-dodecane, whereas
3-methylimidazolium hydrosulfate, [С2(MIM)2]
with 1-ethyl-3-(2-methoxycarbonyl)-3-imidazolium
[(HSO4)2], showed the highest performance in removal
dicyanamide [C2COOCH3IМC2H5][N(CN)2] the degree
of sulfur compounds. The degree of sulfur removal
of removal was as low as 34%. An increase in the
from the gasoline fraction reached 79.72% at 30°С
anion size leads to an additional increase in the sulfur
and extractant to gasoline weight ratio of 2 : 1 in one
distribution ratio.
extraction step at a contact time of 30 min. After five
extraction cycles, the sulfur content of the gasoline Dharaskar [82] considered the selectivity
samples was reduced to the level lower than 10 μg g–1. The of ionic liquids, 1-butyl-3-methylimidazolium
dicationic ionic liquids, compared to the monocationic hexafluorophosphate [BMIM][PF6] and tetrafluoroborate
[BMIM][BF4], to the main sulfur compounds present in
analogs, have higher π-electron density in the aromatic
fuel fractions. The degrees of extraction of thiols and
ring, which leads to stronger π−π interaction of cations
sulfides were low. As for aromatic compounds, they could
with aromatic sulfur compounds and, correspondingly,
be ranked in the following order: dibenzothiophene >
to more efficient removal of sulfur from petroleum
benzothiophene > thiophene > 2-methylthiophene,
feedstock.
correlating with a decrease in the electron density on the
A different trend was observed in [78]: The use of sulfur atom. The probable mechanism of the extraction
pyridine-containing ionic liquids as extractants allowed of sulfur compounds with these ionic liquids consists in
removal of up to 94.3% of dibenzothiophenes from the formation of liquid clathrates and in π–π interaction
poly-α-olefin (Synfluid PAO 6) compared to imidazole of the imidazole ring of the extractant with aromatic
ionic liquids, with which the degree of removal of sulfur compounds. Removal of sulfur compounds from
sulfur compounds from the model solution was 90.2%. diesel fuel and gasoline samples is complicated by the
Similar results were reported by Player et al. [79]. presence of different homologs in which the steric effect
They found that the degree of extraction of thiophene of the alkyl group in aromatic rings leads to a decrease in
and dibenzothiophene from a model solution decreased the degree of removal, and also of other impurities that
with a decrease in the size of ions in the ionic liquid: of can inhibit the desulfurization. Furthermore, aliphatic
cations in the series pyridine > imidazole > pyrrolidine and alicyclic sulfur compounds present in real samples
and of anions in the series bis(trifluoromethanesulfonyl) are not aromatic and are weakly polar; they cannot
imide [NTf2]– > trifluoromethanesulfonate [OTf]– > form π–π bonds with ionic liquids and therefore are not
hexafluorophosphate [PF6]– > tetrafluoroborate [BF4]–. extracted. The sulfur content of the gasoline fraction
The positive correlation between the ion volume and decreases by 80 and 72.2%, and that of the diesel
extraction efficiency can be attributed to an increase fraction, by 57.1 and 53.6% in extraction with [BMIM]
in the area of the van der Waals contact between ionic [BF4] and [BMIM][PF6], respectively (four extraction
liquid components and a sulfur compound. cycles, fuel to extractant ratio 5 : 1, 30 min, 30°C.
Imidazole and benzimidazole ionic liquids with with a decrease in the length of the alkyl chain in
polyethylene glycol and allyl or benzyl double functional the pyridinium ring, and also in going from a model
groups were suggested for removing dibenzo- and mixture of thiophenes (45.5%) to real samples (38.1%).
4,6-dimethyldibenzothiophenes from dodecane [83]. Liu et al. [85] found that, among eight tested acid
The experiments have shown that the efficiency of ionic liquids, the extractant based on the imidazole
the extraction of sulfur compounds mainly depends ring and p-toluenesulfonate anion showed the highest
on the cation of the ionic liquid, whereas the anions performance in the extraction of dibenzothiophene
(dicyanamide [N(CN)2] > bis(trifluoromethanesulfonyl) from model solutions and diesel fraction. The
imide [NTf2] > thiocyanate [SCN] > tetrafluoroborate dibenzothiophene extraction decreased with an increase
[BF4]) only slightly influence the degree of removal of in the number of methyl groups in its homologs.
sulfur compounds from the model solution. The longer The use of 1-(4-sulfo)butyl-3-methylimidazolium
is the ether chain in the imidazolium cation, the lower p-toluenesulfonate [(CH2)4SO3HMIМ][Tos] allowed
is the viscosity of the ionic liquid and the higher is the total sulfur content of a diesel fuel sample to be
the efficiency of the extraction of sulfur compounds. decreased in 25 min from 438 to 45 mg L–1 in five
Electrostatic interactions of the ether oxygen atoms with extraction steps at 80°С and the fuel to extractant ratio
aromatic sulfur compounds will also favor the extraction of 4 : 1.
efficiency. The results obtained for N-benzylimidazole 1-Butyl-3-methylimidazolium dicyanamide
ionic liquids are comparable with the results obtained surpasses in the extraction ability 1-ethyl-3-
with N-allyl-substituted ionic liquids. The extractants methylimidazolium dicyanamide and allows removal of
based on N-allylbenzimidazole ensured higher degrees 18.63 and 32.82% of sulfur from the gasoline and diesel
of extraction of sulfur compounds from dodecane than fractions, respectively, in one step and up to 56.51 and
the corresponding imidazole-based ionic liquids did (69 69.54%, in six steps, at the extractant to fuel ratio of 1 :
against 59% for dibenzothiophene; 52 against 29% for 1. The desulfurization of the fuel fractions is attributed
4,6-dimethyldibenzothiophene). Benzimidazole ionic to the formation of a double π–π bonding of the aromatic
liquids ensure enhanced π–π interaction with heterocyclic ring of sulfur compounds with the imidazolium cation
compounds due to larger planar aromatic π-electron ring and dicyanamide anion [86].
systems. An increase in the number of n-ether groups in Chen et al. [87] demonstrated the advantage of dou-
benzimidazole negatively affects the dibenzothiophene ble π–π bonding by the example of ionic liquids con-
extraction efficiency but does not correlate with the sisting of the same 3-butyl-4-methylthiazolium cation
4,6-dimethyldibenzothiophene extraction efficiency. and different anions: dicyanamide [DCA], thiocyanate
Chinese researchers [84, 85] studied the behavior [SCN], hexafluorophosphate [PF6], and tetrafluorobo-
of ionic liquids containing various combinations of rate [BF4]. 64% of dibenzothiophenes and 45% of thio-
cations and anions. They state that both components phenes were removed from a model fuel with 3-butyl-
contribute to the capacity and selectivity of the 4-methylthiazolium dicyanamide [BMTH][DCA] at the
ionic liquid, whereas the anion is responsible for the extractant to model solution ratio of 1 : 1 and 25°C in
extractant hydrophobicity/hydrophilicity, melting point, 20 min. The sulfur content of gasoline and diesel fuel
thermal and electrochemical stability, and viscosity. was decreased from 558 to 20 mg L–1 in five extraction
Wang et al. [84] performed extraction from a model cycles and from 547 to 8 mg L–1 in four extraction cy-
solution and a real fuel with ionic liquids based on cles, respectively. 1-Butyl-3-methylimidazolium acetate
N-butylpyridinium [BPy] and N-ethylpyridinium ([BMIM][Ac]) was chosen as the most effective extract-
[EPy] cations and nitrate, tetrafluoroborate, and ant for removing n-butyl mercaptan from hexane. 95.8%
acetate anions. The degree of extraction of sulfur of the mercaptan (decrease from 200 to 8.34 mg L–1)
compounds decreased in the order N-butylpyridinium was removed at room temperature and weight ratio of
tetrafluoroborate [BPy][BF4] > N-butylpyridinium the ionic liquid to the model solution of 1 : 20 after one
nitrate [BPy][NO3] > N-butylpyridinium acetate [BPy] extraction cycle (11 h) [88].
[Ac] > N-ethylpyridinium tetrafluoroborate [EPy] Protonic ionic liquids are a new type of extractants.
[BF4] > N-ethylpyridinium nitrate [EPy][NO3] > They can be readily synthesized by proton exchange
N-ethylpyridinium acetate [EPy][Ac] in accordance between Brønsted acids and bases. They are cheap,
environmentally friendly, and highly soluble in anion (Fo) decreased in the following order: [DBU]
water and polar solvents and have low viscosity. (82.55%) > [NFM] (61.03%) > [HMIM] (43.95%) >
Wang et al. [89] synthesized and studied ionic liquids [NMM] (32.95%). Close degrees of extraction of
based on cations of amines: tris(3,6-dioxaheptyl) benzo- (84–81%) and dibenzothiophene (85–81%)
amine [TDA], triethylamine [TEA], tripropylamine at varied anion are attributed to relatively small size
[TPA], tripentylamine [TPEA], and on anions of of the anion compared to the cation. The degree of
aliphatic and aromatic acids: formic [Fo], acetic [Ac], extraction of dibenzothiophene decreases in the order
propionic [Pr], benzoic [BA], salicylic [SA], lactic 1,8-diazabicyclo[5.4.0]undec-7-ene acetate [DBU]
[LA], and glycolic [GA]. The extractant performance [Ac] > 1,8-diazabicyclo[5.4.0]undec-7-ene propionate
increased in the order triethylammonium formate [DBU][Pr] > 1,8-diazabicyclo[5.4.0]undec-7-ene
[TEA][Fo] < tripropylammonium formate [TPA][Fo] < butyrate [DBU][Bu] > 1,8-diazabicyclo[5.4.0]undec-
tripentylammonium formate [TPEA][Fo]; however, 7-ene formate [DBU][Fo] > 1,8-diazabicyclo[5.4.0]
with an increase in the alkyl chain length, the mutual undec-7-ene phenolate [DBU][Ph]; for benzothiophene,
solubility of the extraction system components increased the trend is as follows: [DBU][Pr] > [DBU]
also. High degree of sulfur removal from dodecane with [Ac] > [DBU][Bu] > [DBU][Fo] > [DBU][Ph]. For
tris(3,6-dioxaheptyl)ammonium formate [ТDА][Fo] is 4,6-dimethyldibenzothiophene, because of the steric
probably due to interaction of the active oxygen atoms effect, the degrees of extraction from the model solution
in ethylene glycol units with hydrogen atoms of the are lower, from 67.62 to 53.57%, and decrease in the
aromatic ring of the sulfur compounds. The solubility order [DBU][Ph] > [DBU][Pr] > [DBU][Bu] > [DBU]
of the TDA-based ionic liquids in the model solution [Ac] > [DBU][Fo]. After three extraction cycles at the
is considerably lower than that of the ionic liquids [DBU][Pr] to model fuel ratio of 1 : 1, the degree of
based on the other amines, which may be due to strong removal of dibenzothiophene, benzothiophene, and
hydrophilic properties of the ethylene glycol rings in 4,6-dimethyldibenzothiophene was 98.33, 98.67, and
ТDА. The TDA-based ionic liquids with aliphatic acid 94.26%, respectively. The extractant was regenerated
anions ensure higher distribution ratios than those with by stripping with cyclohexane.
aromatic acid anions do, but are, at the same time, more In [91], bis(2-ethylhexyl) hydrogen phosphate was
soluble in the model fuel, which leads to significant used as an extractant for removing thiophene compounds
extractant loss. The solubility in the model fuel decreases from five crude oil samples. The maximal degree of
in the order tris(3,6-dioxaheptyl)ammonium propionate removal was 53%; the extraction mixture was heated
[ТDА][Pr] > tris(3,6-dioxaheptyl)ammonium acetate for approximately 1 h at 250°C with continuous stirring
[ТDА][Ас] > tris(3,6-dioxaheptyl)ammonium formate (700 rpm); the ionic liquid concentration was 2 vol %.
[ТDА][Fo]. The degree of extraction of sulfur
The efficiency of the extraction with ionic liquids
compounds from dodecane with ionic liquids based on
increases if sulfur compounds are preliminarily oxidized
ТDА and hydroxy acids (LA, GA) is lower than that
to the corresponding sulfoxides and sulfones, because
with other ionic liquids. 72.68% of thiophene, 76.31%
oxidized sulfur compounds have considerably higher
of benzothiophene, and 83.94% of dibenzothiophene
distribution ratios [92].
were extracted with tris(3,6-dioxaheptyl)ammonium
salicylate [TDA][Sa] at the fuel to extractant ratio of 1 : Ionic liquids are regenerated, as a rule, by distillation
1 and 25°С in 5 min. The ionic liquids were regenerated within the range of thermal stability of the extractant
by stripping with petroleum ether. The efficiency of and by stripping of water-soluble ionic liquids with
the extraction of benzo- and dibenzothiophenes from water [19, 20].
octane was studied for nine protonic ionic liquids
with the cations of 1,8-diazabicyclo[5.4.0]undec-7- DEEP EUTECTIC SOLVENTS
ene [DBU], N,N-dimethylethanolamine [DMEOA],
N-methylimidazole [MIM], N-methylmorpholine Deep eutectic solvents are a new class of solvents and
[NMM], and N-formylmorpholine [NFM] and anions of are being actively studied today. Deep eutectic solvents
formic [Fo], acetic [Ac], propionic [Pr], and n-butyric have properties similar to those of ionic liquids but are
[Bu] acids and phenol [Ph] [90]. The degree of extraction still less toxic and less expensive and are biodegradable.
of sulfur compounds depending on the cation at the same Deep eutectic solvents consist of two and more
Table 2. Classification of eutectic solvents [23, 24, 95]

Type Formula M; Z
I Cat+ X−·zMClx (quaternary ammonium salt + metal chloride) М: Zn, Sn, Fe, Al, Ga, In, Сu, Ag,
Cd, La, Y
II Cat+ X–·zMClx·yH2O (quaternary ammonium salt + metal chloride hydrate) М: Cr, Co, Cu, Ni, Fe, La, Ca, Mg
III Cat+ X–·zRZ (quaternary ammonium salt + hydrogen bond dono) Z: CONH2, COOH, OH
IV MClx+ RZ = MClx–1+·RZ + MClx+1 metal chloride + hydrogen bond donor) M: Al, Zn; Z: CONH2, OH
components capable of forming a eutectic mixture with Sn–diphenylcarbazide) to the model fuel of 1 : 25 in
the melting point considerably lower than that of each 10 min at 35°С in one extraction cycle. The authors
separate component [93]. state that the extraction mechanism is associated both
Deep eutectic solvents based on a mixture of with the π–π interaction between the phenyl rings of
quaternary ammonium salts and zinc chloride were the complexing agent and thiophene components and
discovered by Abbott et al. [94, 95]. Four types of deep with the π-complexation of tin(II) with the electron pair
eutectic solvents are known (Table 2) [23, 95]. of sulfur compounds. An extractant based on choline
Deep eutectic solvents of type III are the most stud- chloride and propionic acid (1 : 3) was suggested for
ied and consist of two major components: a hydrogen removing benzothiophene from octane [99]. 64.9% of
bond acceptor and a hydrogen bond donor. A choline sulfur was removed at 37°С under the conditions of
salt, quaternary ammonium and phosphonium, and ter- ultrasonic treatment in 10 min at the extractant to model
tiary sulfonium salts are used as hydrogen bond accep- solution ratio of 1 : 3 in one extraction step.
tors. Polyhydric alcohols (glycerol, ethylene glycol, pol- Jha et al. [100] synthesized and studied three eutec-
yethylene glycol), aromatic compounds (benzoic acid), tic solvents based on diethylene glycol as a hydrogen
organic acids (citric, oxalic, malonic, etc.), and amides bond donor and tetrabutylammonium bromide, choline
(urea) can act as hydrogen bond donors [23, 24, 95]. chloride, and methyltriphenylphosphonium bromide as
The physicochemical properties of deep eutectic acceptors. All the three eutectic solvents ensure similar
solvents can vary depending on the eutectic mixture degree of thiophene removal from heptane (68%). This
composition. The use of an eutectic solvent based on fact suggests that sulfur present in thiophene interacts
choline chloride and phenol (1 : 4) at the extractant only with the oxygen atoms of diethylene glycol. For
to model solution ratio of 2.5 : 1 and 40°С allowed 2-methylthiophene and dibenzothiophene, the degree
removal of up to 91.5, 95.4, and 99.2% of thiophenes, of removal from the model fuel depends to a greater
benzothiophenes, and dibenzothiophenes, respectively, extent on the hydrogen bond acceptor and decreases
from heptane. Deep eutectic solvents can be regenerated in the order tetrabutylammonium bromide > methyl-
by extraction with diethyl ether; the extraction capacity triphenylphosphonium bromide > choline chloride. At
did not decrease even after 15 extraction–regeneration the extractant to model solution ratio of 0.1 and 30°С,
cycles [96]. 90% of thiophene was removed from a tetrabutylammonium chloride : diethylene glycol (1 : 4)
solution simulating a gasoline fraction with the choline extracts up to 91.77% of dibenzothiophene and 86.24%
chloride–glycerol (1 : 3) system at the extractant to of 2-methylthiophene from heptane in 60 min.
fuel volume ratio of 1 : 1 in five extraction steps [97]. Lee et al. [101] studied the relationship between the
Shirazinia et al. [98] synthesized and studied a series structures of extractant components and physicochemical
of metal complex eutectic solvents based on choline properties of the extractant: melting point, viscosity,
chloride and various metal chlorides (FeCl3, FeCl2, density, polarity, extraction ability, solubility, and
CuCl2, SnCl2, and ZnCl2) with diphenylguanidine and selectivity to thiophenes, benzothiophenes, and
1,5-diphenylcarbazide as complexing agents. 95.2% dibenzothiophenes. They tested 28 different eutectic
of dibenzothiophene, 94.5% of 3-methylthiophene, solvents consisting of seven tetraalkylammonium
and 92.1% of thiophene were extracted from octane at bromides (alkyl from С2 to С8) and four alkanediols
the weight ratio of the extractant (choline chloride + (С2–С5). Among hydrogen bond acceptors with up to
four carbon atoms in the chain, the efficiency of the spectively. The effect of various types of glycols on the
removal of sulfur compounds from model mixtures extraction of sulfur compounds was also studied. The
increased with a decrease in the length of alkyl chains maximal extraction of sulfur from the model fuel was
in the acceptor and with an increase in the chain length reached on introducing 50% polyethylene glycol-400:
in the donor. However, in going to acceptors with 91.47 and 80.89% for dibenzothiophene and thiophene,
more than four carbon atoms in the chain, the trend respectively. Flow-through extraction in a borosilicate
became opposite: The efficiency of the removal of channel 600 mm long and 0.5 mm i.d. allowed removal
benzo- and dibenzothiophenes increased when using of up to 95.65% of thiophene and 98.78% of dibenzo-
longer-chain acceptors and shorter-chain donors. The thiophene from a solution simulating diesel fuel with
structure of the hydrogen bond acceptor influences the polyethylene glycol-200 : tetrabutylammonium bromide
removal efficiency of benzo- and dibenzothiophenes (1 : 2) extractant in four cycles; the equilibrium in the
more strongly compared to thiophenes. Despite the extraction system was attained in a time as short as 40
fact that the maximal sulfur removal became possible s [104]. 88% of dibenzothiophene was removed from a
with tetraheptyl- and tetraoctylammonium bromide model solution in four extraction cycles using methyltri-
in combination with ethylene glycol (1 : 4), the phenylphosphonium bromide and tetraethylene glycol
extractant based on tetraethylammonium bromide and (1 : 4) at the extractant to model solution volume ratio of
1,4-butanediol (1 : 4) was chosen as optimum, taking into 1 : 1 and 20°С [105]. The use of the tetrabutylphospho-
account its low solubility in model solution, possibility nium bromide : sulfolane (1 : 4) system as an extractant
of regeneration with water, and cost. This extractant allowed the content of thiophene and dibenzothiophene
allowed the sulfur content of the model solution to be in their individual heptane solutions to be reduced by
decreased from 1500 to <10 mg L–1 in five steps. up to 67 and 86%, respectively. From a mixed solution
Lima et al. [102] synthesized 16 eutectic solvents simulating the gasoline fraction with the sulfur concen-
based on quaternary ammonium and phosphonium salts tration of 4599 mg L–1, sulfur compounds were removed
with different polyethylene glycols. As they found, the quantitatively in four extraction steps at the extractant to
efficiency of the extraction of thiophenes and benzo- fuel ratio of 1 : 1 and 25°С in 15 min [106].
thiophenes depends not only on the length of the alkyl Dharaskar et al. [107] used trihexyl(tetradecyl)
chain in the quaternary ammonium salt, but also on phosphonium tetrafluoroborate ([HTTP][BF4]) as an
the molecular mass of polyethylene glycol and varies extractant for removing dibenzothiophene, thiophene,
in the following order: ethylene glycol < tetraethylene benzothiophene, and their homologs from samples
glycol < polyethylene glycol-200 < polyethylene gly- of diesel and gasoline fractions. The sulfur content
col-300 < polyethylene glycol-400 ≈ polyethylene gly- was reduced from 180 to 40.5 mg L–1 (by 77.5%) in
col-600. Up to 65% of thiophene and 85% of benzothio- diesel fuel and from 75 to 12.5 mg L–1 (by 83.33%)
phene can be removed from a model solution with an in gasoline after five extraction steps at the [THTDP]
extractant based on tetrabutylammonium chloride and [BF4] to fuel weight ratio of 1 : 1 and 30°C. The authors
polyethylene glycol-400 (1 : 2). The extractant was re- note that the extractants based on phosphonium cation
generated by washing with water. In the process, ben- are the most effective for removing dibenzothiophene
zothiophene precipitated and thiophene passed into the from liquid fuels; the degree of sulfur extraction
aqueous phase. At 1 : 1 volume ratio of tetrabutylam- can reach 92.6%. Trihexyl(tetradecyl)phosphonium
monium bromide and polyethylene glycol to a solution bis(trifluoromethanesulfonyl)imide (CyphosIL-109)
simulating the gasoline fraction, the degree of removal shows lower performance under similar conditions of
of dibenzothiophene and thiophene at room temperature multistep extraction: The degree of removal of sulfur
reached 82.40 and 62.16%, respectively. In the process, compounds was 69.44% for diesel fuel and 78.67% for
polyethylene glycol-600 was used as a hydrogen bond the gasoline fraction [108].
donor [103]. Addition of 10% emulsifiers (Triton Х-100 The extraction of thiophene and its derivatives from a
and sodium dodecyl sulfate) favoring an increase in the model solution and a crude oil sample was performed with
contact area available for the mass transfer to the eutec- eutectic solvents consisting of AlCl3, chloroparaffin-52,
tic solvent only slightly increased the degree of removal and six aromatic compounds (benzene, toluene,
of dibenzothiophene and thiophene: by 2 and 8%, re- o-xylene, p-xylene, ethylbenzene, chlorobenzene). The
degree of sulfur removal decreased in the order toluene > The extractant based on triethylamine, benzoic acid,
p-xylene > o-xylene > ethylbenzene > benzene > and its analogs was used for removing sulfur from
chlorobenzene, correlating with the electron-donor n-octane [113]. The physicochemical properties and
power of the benzene ring. The 6% eutectic solvent solubility of the eutectic solvent were controlled by
based on toluene allowed removal from heptane of up to introducing various functional groups into the aromatic
99.81% of thiophene, 99.65% of benzothiophene, and acid. The degree of removal of sulfur compounds from
89.64% of dibenzothiophene, respectively. The authors octane decreases in the order dibenzothiophene (81%) >
state the desulfurization mechanism is determined, on benzothiophene (76.5%) > thiophene (59%), which
the one hand, by π–π interaction of thiophene sulfur correlates with a decrease in their electron density.
with the aromatic ring of the extractant and, on the other The sulfur concentration was reduced in 10 min from
hand, by the complexation of the sulfur compound with 500 to <10 mg L–1 in three cycles of extraction with
the extractant anion. The sulfur content of the crude oil triethylamine : o-hydroxybenzoic acid at the extractant
sample was reduced from 682 to 48.4 mg L–1 [109]. to model solution weight ratio of 1.5 : 1 and 25°С. It
The extraction of thiophene and benzothiophene should be noted that the degree of the benzothiophene
from two samples of commercial diesel fuel with an removal was stable after 10 extraction cycles.
eutectic solvent containing tetraethylphosphonium A mixture of polyetheramine and formic acid (1 : 10)
bromide and FeCl3 in 2 : 1 and 1.5 : 1 molar ratios was allows removal of up to 72.16% of dibenzothiophene,
studied. The degree of desulfurization of diesel fuel did 63.96% of dibenzothiophene, and 53.01% of thiophene
not exceed 33% in one extraction step; in six steps, the from octane at the extractant to model solution ratio of 1 :
sulfur content was reduced from 286 to 40 mg L–1 [110]. 1 and 30°С in 15 min [114]. At the treatment conditions
Li et al. [111] suggested ternary extractants based on kept constant, the sulfur content of a real fuel sample was
tetrabutylammonium chloride, polyethylene glycol-200, reduced from 3205 to 1010 mg L–1 in five extraction steps.
and FeCl3 (4 : 1 : 0.05). As compared to the existing A natural eutectic solvent based on betaine as a
traditional binary eutectic solvents, the ternary systems hydrogen bond acceptor and levulinic acid as a donor
showed higher performance; along with hydrogen (1 : 7) allows removal of up to 27% of thiophene
bonding, metal ions in the extractant acted via formation from n-decane at room temperature and extractant
of coordination compounds. The degree of removal of to model solution ratio of 1 : 1 in 4 h [115]. The
dibenzothiophenes from octane was 89.5% in one cycle. use of binary reagents consisting of ionic liquids,
Li et al. [112] synthesized eutectic solvents based N-methylpyrrolidinium hydrosulfate [Hnmp][HSO4]
on tetrabutylammonium bromide and carboxylic acids and hydrophosphate [Hnmp][H2PO4], and an organic
(formic, acetic, propionic, oxalic, malonic, adipic) as solvent, dimethylformamide (1 : 1), not only enhances
hydrogen bond donors. Depending on the type of the the extraction efficiency but also decreases the extractant
sulfur compound extracted from the model solution, the cost [116]. Up to 95% of sulfur was removed from the
extraction ability of the eutectic solvents varies in the model solution and up to 69–71%, from real solutions
following order of acids: formic ≈ acetic > propionic > of gasoline fractions in five extraction steps at the
oxalic > malonic > adipic for thiophenes; formic > extractant to real sample ratio of 2 : 1 and 40°С.
propionic > acetic > oxalic > malonic > adipic for
benzothiophenes; propionic > acetic > oxalic > formic > SUPERCRITICAL FLUID EXTRACTION
malonic > adipic for dibenzothiophenes. The extractant
based on formic acid surpasses the other mixtures Water in the supercritical state (Tcr = 374°С, Pcr =
not only in the extraction capacity but also in the low 22.1 MPa) has unique properties: low viscosity and
values of cross solubility. In one extraction step, 40.94 dielectric permittivity, high density, and ability to
and 35.27% of sulfur compounds were removed from dissolve gases and nonpolar organic substances and to
the gasoline and diesel fractions, respectively, at the participate in redox reactions [117].
extractant to fuel ratio of 2 : 1. In four extraction cycles, As demonstrated in [25, 117, 118] by the example
83.61 and 70.21% of sulfur was removed from gasoline of the conversion of sulfur compounds, desulfurization
and diesel fuel. The authors assume that the main of crude oil and petroleum fractions occurs as a result
extraction mechanism is hydrogen bonding between of free-radical thermal cleavage of aliphatic C–S bonds.
sulfur compounds and eutectic solvent. Hydrogen sulfide is a final product of treating petroleum
feedstock. Supercritical water is inefficient in cleavage of petroleum feedstock using various extraction systems.
thiophene aromatic rings. The sulfur compounds can be The efficiency of the extraction treatment of crude oil and
ranked in the following order with respect to the reactivity petroleum products depends on the composition of the
under supercritical conditions: alkyl sulfides ~ aromatic extraction system used, speciation of sulfur compounds,
sulfides >> 3-methylthiophene > thiophene > benzo- and physicochemical features of the petroleum feedstock,
dibenzothiophene. Catalysts increase the rate and degree and process conditions. Polar organic solvents and
of removal of aromatic sulfur compounds from petroleum alkaline aqueous solutions are preferable in commercial
feedstock. implementation of the desulfurization of crude oil and its
Desulfurization of heavy crude (Saudi Aramco) fractions. As a rule, complete purification of petroleum
and two model mixtures, dihexyl sulfide and feedstock requires several extraction cycles.
dibenzothiophene in hexadecane, in supercritical water Numerous papers dealing with the synthesis and
was performed in the presence of catalysts: ZnO, MoO3, properties of new types of extractants, ionic liquids
and MoS2 nanoparticles [119]. Without catalysts, the and deep eutectic solvents, have been published in the
degree of removal of sulfur compounds from crude oil past years. The majority of the ionic liquids studied and
is as low as 6–7%, and addition of MoS2 nanoparticles eutectic solvents have advantages over classical solvents:
increases this parameter by a factor of 2, to 12%. The environmental friendliness, stability, high capacity and
dihexyl sulfide conversion in hexadecane was ~85% selectivity with respect to sulfur compounds, low values
and only slightly depended on the addition of catalysts. of the vapor pressure, viscosity, and solubility, diversity,
25% of dibenzothiophene was removed from the model and simple synthesis. Today practical use of the new
solution in the presence of ZnO catalyst. solvents for removing sulfur compounds from crude oil
The use of supercritical water allows performing and petroleum products is limited by their high cost and
desulfurization of heavy crudes and bitumens and by the need for more extensive experiments with real
favors a decrease in their viscosity [26, 119]. Yan et al. samples.
[120] used supercritical methanol (350°C, 13 MPa) in The use of supercritical fluid extraction for
an Ar atmosphere for converting 3-methylthiophene desulfurization of crude oil and petroleum fractions is
and diphenyl, dibenzyl, and di-n-hexyl sulfides. The noted.
conversion of dibenzyl and di-n-hexyl sulfides was Extraction technologies can be used for removing
100 and 65%, respectively, whereas the diphenyl sulfur-containing compounds from crude oil in
sulfide conversion was as low as 12%. Similar combination with other desulfurization methods, e.g.,
results were obtained using supercritical water + hydrodesulfurization or oxidative desulfurization.
formic acid. For 3-methylthiophene, separate cases
of elimination or substitution of methyl groups were
FUNDING
observed. Supercritical fluid extraction requires high
temperatures and pressures; therefore, it is expensive The study was financially supported by the Russian
and requires thorough process control. Today the use Foundation for Basic Research (project no. 18-03-00904). The
of supercritical fluid extraction does not allow reducing review of published data included in Extraction with Ionic
the sulfur content of petroleum feedstock to the level Liquids and Deep Eutectic Solvents sections was performed
prescribed by a number of modern requirements and within the framework of the government assignment for the
quality standards for the fuel. Most likely, the prospects Vernadsky Institute of Geochemistry and Analytical Chemistry,
of supercritical fluid extraction are associated with its Russian Academy of Sciences, no. 0137-2019-0020.
use in combination with other desulfurization methods
CONFLICT OF INTEREST
(hydrodesulfurization, oxidative desulfurization) rather
than as a separate technology. The authors declare that they have no conflict of interest.
CONCLUSIONS REFERENCES
In this review, we systematized the results of 1. Bol’shakov, G.F., Seraorganicheskie soedineniya nefti
extraction removal of sulfur-containing compounds from (Organic Sulfur Compounds of Curde Oil), Novosibirsk:
Nauka, 1986. Qaz, A.Q., Gao, S., and Chen, X., RSC Adv., 2014, vol. 4,
2. Shmal’, G., Zamrii, A., Viktorova, R., and Alieva, L., pp. 35302–35317.
Neftegaz. Vert., 2020, nos. 3–4, pp. 102–108. https://doi.org/10.1039/C4RA03478C
http://www.ngv.ru/magazines/article/neft-bez-sery-eto- 20. Ibrahim, M.H., Hayyan, M., Hashim, M.A., and
realnost/. Hayyan, A., Renew. Sustain. Energy Rev., 2017, vol. 76,
3. Saleh, T.A., Trends Environ. Anal. Chem., 2020, vol. 25, pp. 1534–1549.
ID e00080. https://doi.org/10.1016/j.rser.2016.11.194
https://doi.org/10.1016/j.teac.2020.e00080
21. Swapnil, D., Res. J. Chem. Sci., 2012, vol. 2, no. 8,
4. Song, C. and Ma, X., Appl. Catal. B, 2003, vol. 41, pp. 80–85. http://isca.me/rjcs/Archives/v2/i8/15.ISCA-
nos. 1–2, pp. 207–238. RJCS-2012-110.pdf.
https://doi.org/10.1016/S0926-3373(02)00212-6 22. Gaile, A.A., Klement’ev, V.N., and Vereshchagin, A.V.,
5. Javadli, R. and Klerk, A., Appl. Petrochem. Res., 2012, Russ. J. Appl. Chem., 2019, vol. 92, no. 4, pp. 453–475.
vol. 1, pp. 3–19. https://doi.org/10.1134/S1070427219040013
https://doi.org/10.1007/s13203-012-0006-6
23. Chandran, D., Khalid, M., Walvekar, R., Mubarak, N.M.,
6. Pawelec, B., Navarro, R.N., Campos-Martin, J.M., and Dharaskar, S., Wong, W.Y., and Gupta, T.C.S.M., J. Mol.
Fierro, J.L.G., Catal. Sci. Technol., 2011, vol. 1, pp. 23–42. Liq., 2019, vol. 275, pp. 312–322.
https://doi.org/10.1039/C0CY00049C https://doi.org/10.1016/j.molliq.2018.11.051
7. Aitani, A.M., Ali, M.F., and Al-Ali, H.H., Petrol. 24. Majid, M.F. and Mo, H.F., J. Mol. Liq., 2020, vol. 306,
Sci. Technol., 2000, vol. 18, nos. 5–6, pp. 537–553. ID 112870.
https://doi.org/10.1080/10916460008949859 https://doi.org/10.1016/j.molliq.2020.112870
8. Babich, I.V. and Moulijn, J.A., Fuel, 2003, vol. 82, 25. Qi, W., Li, Y., Liu, Z., Li, X., Jiang, Y., and Sun, H.,
pp. 607–631. Chem. Eng. Sci., 2020, vol. 228, ID 115979.
https://doi.org/10.1016/S0016-2361(02)00324-1 https://doi.org/10.1016/j.ces.2020.115979
9. Srivastava, V.C., RSC Adv., 2012, vol. 2, pp. 759–783. 26. Timko, M.T., Ghoniem, A.F., and Green, W.H.,
https://doi.org/10.1039/C1RA00309G J. Supercritical Fluids, 2015, vol. 96, pp. 114–123.
10. Song, C., Catal. Today, 2003, vol. 86, nos. 1–4, pp. 211–263. https://doi.org/10.1016/j.supflu.2014.09.015
https://doi.org/10.1016/S0920-5861(03)00412-7 27. Bedda, K., Hamada, B., Semikin, K.V., and
11. Al-Degs, Y.S., El-Sheikh, A.H., Al Bakain, R.Z., Kuzichkin, N. V., Petrol. Coal, 2019, vol. 61, no. 6,
Newman, A.P., and Al-Ghouti, M.A., Energy pp. 1352–1360.
Technol., 2016, vol. 4, no. 6, pp. 679–699. https://www.vurup.sk/wp-content/uploads/2019/11/PC-
https://doi.org/10.1002/ente.201500475 X-2019_Bedda-140.pdf.
12. Rang, H., Kann, J., and Oja, V., Oil Shale, 2006, vol. 23, 28. Vereshchagin, A.V., Gaile, A.A., Klement’ev, B.N., and
no. 2, pp. 164–176. Lazunenko, F.A., Izv. Sankt-Peterb. Gos. Tekhnol. Inst.
https://kirj.ee/public/oilshale/oil-2006-2-9.pdf. (Tekh. Univ.), 2017, no. 40, pp. 69–76.
13. Song, C. and Ma, X., Int. J. Green Energy, 2004, vol. 1, 29. Kumar, S., Srivastava, V.C., Raghuvanshi, R.,
no. 2, pp. 167–191. Nanoti, S.M., and Sudhir, M., Energy
https://doi.org/10.1081/GE-120038751 Fuels, 2015, vol. 29, no. 7, pp. 4634–4643.
14. Stanislaus, A., Marafi, A., and Rana, M.S., Catal. Today, https://doi.org/10.1021/acs.energyfuels.5b00834
2010, vol. 153, nos. 1–2, pp. 1–68. 30. Kameshkov, A.V., Gaile, A.A., Kuzichkin, N.V., and
https://doi.org/10.1016/j.cattod.2010.05.011 Khasanova, A.A., Neftepererab. Neftekhim., 2015, no. 12,
15. Fedyaeva, O.N. and Vostrikov, A.A., Vestn. Ross. Fonda pp. 3–6.
Fundam. Issled., 2017, no. 1 (93), pp. 114–122. 31. Kameshkov, A.V., Gaile, A.A., Kuzichkin, N.V., and
https://www.rfbr.ru/rffi /ru/bulletin/o_2039792#114. Spetsov, E.A., Neftepererab. Neftekhim., 2015, no. 10,
16. Kumar, S., Srivastava, V.C., and Nanoti, S.M., Sep. Purif. pp. 6–11.
Rev., 2017, vol. 46, no. 4, pp. 319–347. 32. Shishkin, S.N., Gaile, A. A., Bakaushina, D.A., and
https://doi.org/10.1080/15422119.2017.1288633 Kuzichkin, N.V., Russ. J. Appl. Chem., 2013, vol. 86,
17. Cusack, R.W., Fremeaux, P., and Otto, Y.N.V., Chem. no. 5, pp. 654–657.
Eng., 1991, vol. 98, no. 2, pp. 66–76. https://doi.org/10.1134/S1070427213050078
18. Gaile, A.A. and Klement’ev, V.N., Khim. Khim. Tekhnol., 33. Vereshchagin, A.V., Gaile, A.A., Klement’ev, B.N.,
2018, no. 46, pp. 39–45. Lazunenko, F.A., and Vorob’eva, A.R., Izv. Sankt-Peterb.
19. Abro, R., Abdeltawa, A.A., Al-Deyab, S.S., Yu, G., Gos. Tekhnol. Inst. (Tekh. Univ.), 2019, no. 49 (75),

pp. 32–35. 49. Adzamic, T., Sertić-Bionda, K., and Zoretić, Z., Nafta,
34. Saha, B., Sengupta, S., and Selvin, R., Sep. Sci. Technol., 2009, vol. 60, no. 9, pp. 485–490.
2019, vol. 55, no. 6, pp. 1123–1132. https://hrcak.srce.hr/index.php?show=clanak&id_
https://doi.org/10.1080/01496395.2019.1580292 clanak_jezik=65039
35. Kumar, S., Srivastava, V.C., Kumar, A., and Nanoti, S.M., 50. Gaile, A.A., Saifidinov, B.M., Kolesov, V.V., and
RSC Adv., 2016, vol. 6, pp. 25293–25301. Koldobskaya, L.L., Russ. J. Appl. Chem., 2010, vol. 83,
https://doi.org/10.1039/C5RA27757D no. 3, pp. 464–472.
36. Kumar, S., Srivastava, V.C., Nanoti, S.M., Nautiyal, B.R., https://doi.org/10.1134/S1070427210030171
and Siyaram, RSC Adv., 2014, no. 4, pp. 38830–38838. 51. Gaile, A.A., Saifidinov, B.M., Kolesov, V.V., and
https://doi.org/10.1039/C4RA05841K Koldobskaya, L.L., Russ. J. Appl. Chem., 2010, vol. 83,
37. Mokhtar, W.N.A.W., Bakar, W.A.W.A., Ali, R., and no. 3, pp. 473–476.
Kadir, A.A.A., J. Ind. Eng. Chem., 2015, vol. 30, pp. 274– https://doi.org/10.1134/S1070427210030183
280. 52. Gaile, A.A., Saifidinov, B.M., and Koldobskaya, L.L.,
https://doi.org/10.1016/j.jiec.2015.05.033 Neftepererab. Neftekhim., 2011, no. 3, pp. 11–15.
38. Toteva, V., Topalova, L., and Manolova, P., J. Univ. 53. Katasonova, O.N., Savonina, E.Y., and Maryutina, T.A.,
Chem. Technol. Metall., 2007, vol. 42, no. 1, pp. 17–20. J. Anal. Chem., 2020, vol. 75, pp. 148–153.
https://dl.uctm.edu/journal/node/j2007-1/02- https://doi.org/10.1134/S1061934820020070
Toteva-17-20.pdf 54. Kianpour, E. andAzizian, S., Fuel, 2014, vol. 137, pp. 36–40.
39. Gaile, A.A., Chistyakov, V.N., Koldobskaya, L.L., and https://doi.org/10.1016/j.fuel.2014.07.096
Kolesov, V.V., Neftepererab. Neftekhim., 2011, no. 12, 55. Li, Z., Yingna Cui, Y., Li, C., and Shen, Y., Sep. Purif.
pp. 23–27. Technol., 2019, vol. 219, pp. 9–15.
40. Kobotaeva, N.S., Skorokhodova, T.S., An- https://doi.org/10.1016/j.seppur.2019.03.003
drienko, O.S., Marakina, E.I., and Sa-
56. Gao, J., Zhu, S., Dai, Y., Xiong, C., Li, C., Yang, W., and
chkov, V.I., Appl. Sci., 2018, vol. 8, ID 1259.
Jiang, X., Fuel, 2018, vol. 233, pp. 704–713.
https://doi.org/10.3390/app8081259
https://doi.org/10.1016/j.fuel.2018.06.101
41. Lyapina, N.K., Marchenko, G.N., Parfenova, M.A.,
57. Moghadam, F.R., Kianpour, E., Azizian, S., Yarie, M.,
Galkin, E.G., Grishina, R.E., and Nugumanov, R.M.,
and Zolfigol, M.A., Royal Soc. Open Sci., 2020, vol. 7,
Bashk. Khim. Zh., 2007, vol. 14, no. 12, pp. 55–62
ID 200803.
42. Kameshkov, A.V., Gaile, A.A., Kuzichkin, N.V., and
Spetsov, E.A., Izv. Sankt-Peterb. Gos. Tekhnol. Inst. https://doi.org/10.1098/rsos.200803
(Tekh. Univ.), 2015, no. 32, pp. 72–74. 58. Petkov, P., Tasheva, J., and Stratiev, D., Petrol. Coal,
43. Mokhtar, W.N.A.W., Bakar, W.A.W.A., Rusmidah 2004, vol. 42, no. 2, pp. 13–18.
Ali, R., and Kadir, A.A.A., J. Taiwan Inst. Chem. Eng., https://www.vurup.sk/wp-content/uploads/dlm_
2014, vol. 45, pp. 1542–1548. uploads/2017/07/pc_petkov.pdf.
https://doi.org/10.1016/j.jtice.2014.03.017 59. Lyapina, N.K., Akhmetov, A.F., Krasil’nikova, Yu.V.,
44. Karonis, D., Pettas, P., Lois, C., and Bardakos, D., IOSR Parfenova, M.A., and Organyuk, Yu.V., Bashk. Khim.
J. Appl. Chem. (IOSR-JAC), 2019, vol. 12, no. 5, pp. 34– Zh., 2013, vol. 20, no. 4, pp. 105–107.
42. 60. Zhao, K., Cheng, Y., Liu, H., Yang, C., Qiu, L. Zeng, G.,
https://doi.org/10.9790/5736-1205013442 and He, H., RSC Adv., 2015, vol. 5, pp. 66013–66023.
https://doi.org/10.1039/c5ra12305d
45. Toteva, V., Oxid. Commun., 2010, vol. 33, no. 1, pp. 147–
155. 61. Mesdour, S., Boufades, D., Moussiden, A., and
https://scibulcom.net/en/article/ Hamada, B., Petrol. Sci. Technol., 2019, vol. 37, no. 15,
U57nM1kxkVMvTWlbpAJW. pp. 1755–1762.
46. Pasadakis, N., Karonis, D., and Mintza, A., Fuel Process. https://doi.org/10.1080/10916466.2019.1570259
Technol., 2011, vol. 92, no. 8, pp. 1568–1573. 62. Hassan, S.I., Sif El-Din, O.I., and Tawfik, S.M., J. Appl.
https://doi.org/10.1016/j.fuproc.2011.03.023 Sci. Res., 2009, vol. 5, pp. 515–521.
47. Vereshchagin, A.V., Gaile, A.A., Klement’ev, V.N., and http://www.aensiweb.com/old/jasr/jasr/2009/515-521.
Dolgov, S.A., Izv. Sankt-Peterb. Gos. Tekhnol. Inst. (Tekh. pdf.
Univ.), 2018, no. 45, pp. 37–42. 63. Abd El-Aty, D.M., Sif El-Din, O.I., Hassan, S.I.,
48. Adzamic, T., Sertić-Bionda, K., and Marcec-Rahelic, N., Tawfik, S.M., and Hanafi, S., Petrol. Sci. Technol., 2009,
Petrol. Sci. Technol., 2010, vol. 28, pp. 1936–1945. vol. 27, pp. 861–873.
https://doi.org/10.1080/10916460903330056 https://doi.org/10.1080/10916460802096279
64. Kopylov, A.Yu., Mazgarov, A.M., and Vil’danov, A.F., J. Environ. Chem. Eng., 2016, vol. 4, no. 4, pp. 4786–
Khim. Prom–st. Segodnya, 2010, no. 4, pp. 45–53. 4793.
65. Savonina, E.Yu., Katasonova, O.N., and Maryutina, T.A., https://doi.org/10.1016/j.jece.2016.11.011
Zavod. Lab., 2020, vol. 86, no. 3, pp. 5–10. 79. Player, L.C., Chan, B., Lui, M.Y., Masters, A.F., and
https://doi.org/10.26896/1028-6861-2020-86-3-5-10 Maschmeyer, T., ACS Sustain. Chem. Eng., 2019, vol. 7,
66. Abd Al-Khodor, Y.A. and Albayati, T.M., Process Safety pp. 4087–4093.
Environ. Prot., 2020, vol. 136, pp. 334–342. https://doi.org/10.1021/acssuschemeng.8b05585
https://doi.org/10.1016/j.psep.2020.01.036 80. Nie, Y., Li, C., Meng, H., and Wang, Z., Fuel
67. Akopyan, A.V., Andreev, B.V., Anisimov, A.V., Process. Technol., 2008, vol. 8, pp. 978–983.
Eseva, E.A., Tarakanova, A.V., Ustinov, A.S., https://doi.org/10.1016/j.fuproc.2008.04.003
Kleimenov, A.V., Kondrashev, D.O., Khrapov, D.V., and 81. Raj, J.J., Magaret, S., Pranesh, M., Lethesh, K.C.,
Esipenko, R.V., Russ. J. Appl. Chem., 2019, vol. 92, no. 6, Devi, W.C., and Mutalib, M.I.A., Sep. Purif. Technol.,
pp. 865–873. 2018, vol. 196, pp. 115–123.
https://doi.org/10.1134/S1070427210030183 https://doi.org/10.1016/j.seppur.2017.08.050
68. Saha, B. and Sengupta, S., Energy Fuels, 2017, vol. 31,
82. Dharaskar, S.A., Wasewar, K.L., Varma, M.N., and
pp. 996–1004.
Shende, D.Z., Int. J. Energy Technol. Policy, 2016,
https://doi.org/10.1021/acs.energyfuels.6b01842
vol. 12, no. 2, pp. 105–121.
69. Kharlampidi, Kh.E., Soros. Obraz. Zh., 2000, vol. 6, http://www.inderscience.com/offer.php?id=75659.
no. 7, pp. 42–46. 83. Butt, H.S., Lethesh, K.C., and Fiksdahl, A., Sep. Purif.
h t t p : / / w i n d o w. e d u . r u / r e s o u r c e / 4 6 4 / 2 1 4 6 4 / Technol., 2020, vol. 248, ID 116959.
files/0007_042.pdf. https://doi.org/10.1016/j.seppur.2020.116959
70. Paucar, N.E., Kiggins, P., Blad, B., De Jesus, K., Afrin, F.,
84. Wang, J., Zhao, D., Zhou, E., and Dong, Z., J. Fuel Chem.
Pashikanti, S., and Sharma, K., Environ. Chem. Lett.,
Technol., 2007, vol. 35, no. 3, pp. 293–296.
2021, pp. 1–24.
https://doi.org/10.1016/S1872-5813(07)60022-X
https://doi.org/10.1007/s10311-020-01135-1
85. Liu, D., Gui, J., Song, L., Zhang, X., and Sun, Z., Petrol.
71. Khalilov, A.B., Ibrahimova, M.J., Huseynov, H.J., and
Sci. Technol., 2008, vol. 26, pp. 973–982.
Abbasov, V.M., Khim. Inter. Ustoich. Razv., 2019, vol. 27,
https://doi.org/10.1080/10916460600695496
pp. 109–119.
https://doi.org/10.15372/KhUR2019117 86. Asumana, C., Haque, M.R., Yu, L., Wu, X., Chen, X., and
72. Bösmann, A., Datsevich, L., Jess, A., Lauter, A., Yu, G., Sep. Sci. Technol., 2013, vol. 48, pp. 2582–2588.
Schmitz, C., and Wasserscheid, P., Chem. Commun., https://doi.org/10.1080/01496395.2013.804559
2001, pp. 2494–2495. 87. Chen, X., Liu, G., Yuan, S., Asumana, C., Wang, W., and
https://doi.org/10.1039/B108411A Yu, G., Sep. Sci. Technol., 2012, vol. 47, pp. 819–826.
73. Kobotaeva, N.S. and Skorokhodova, T.S., Neftekhimiya, https://doi.org/10.1080/01496395.2011.637281
2020, vol. 60, no. 4, pp. 476–482. 88. Li, X., Zhang, J., Li, J., and Chen, B., Fuel, 2019, vol. 239,
https://doi.org/10.31857/S0028242120040061 pp. 502–510.
74. Wang, J.L., Zhao, D.S., and Li, K.X., Petrol. Sci. Technol., https://doi.org/10.1016/j.fuel.2018.11.052
2012, vol. 30, pp. 2417–2423. 89. Wang, O., Zhang, T., Zhang, S., Fan, Y., and Chen, B.,
https://doi.org/10.1080/10916466.2010.518194 Sep. Purif. Technol., 2020, vol. 231, ID 115923.
75. Huang, C., Chen, B., Zhang, J., Liu, Z., and Li, Y., https://doi.org/10.1016/j.seppur.2019.115923
Energy Fuels, 2004, vol. 18, pp. 1862–1864. 90. Ren, Z., Wei, L., Zhou, Z., Zhang, F., and Wei Liu, W.,
https://doi.org/10.1021/ef049879k Energy Fuels, 2018, vol. 32, no. 9, pp. 9172–9181.
76. Chu, X., Hu, Y., Li, J., Liang, Q., Liu, Y., Zhang, X., https://doi.org/10.1021/acs.energyfuels.8b01936
Peng, X., and Yue, W., Chin. J. Chem. Eng., 2008, vol. 16, 91. Attia, M., Farag, S., Jaffer, S.A., and Chaouki, J., J. Clean.
no. 6, pp. 881–884. Prod., 2020, vol. 275, ID 124177.
https://doi.org/10.1016/S1004-9541(09)60010-0 https://doi.org/10.1016/j.jclepro.2020.124177
77. Li, J., Lei, X.-J., Tang, X.-D., Zhang, X.-P., Wang, Z.-Y., 92. Rodríguez-Cabo, B., Rodríguez, H., Rodil, E., Arce, A.,
and Jiao, S., Energy Fuels, 2019, vol. 33, pp. 4079–4088. and Soto, A., Fuel, 2014, vol. 117, pp. 882–889.
https://doi.org/10.1021/acs.energyfuels.9b00307 https://doi.org/10.1016/j.fuel.2013.10.012
78. Al Kaisy, G.M.J., Mutalib, M.I.A., Bustam, M.A., 93. Chandran, D., Khalid, M., Walvekar, R., Mubarak, N.M.,
Leveque, J.-M., and Muhammad, N., Dharaskar, S., Wong, W.Y., and Gupta, T.C.S.M., J. Mol.

Liq., 2019, vol. 275, pp. 312–322. 108. Dharaskar, S., Sillanpaa, M., Wasewar, K., and
https://doi.org/10.1016/j.molliq.2018.11.051 Walvekar, R., Feasibility study of phosphonium ionic
94. Abbott, A.P., Capper, G., Davies, D.L., Munro, H.L., liquids as efficient solvent for sulfur extraction from
Rasheed, R.K., and Tambyrajah, V., Chem. Commun., liquid fuels, Proc. Int. Engineering Research Conf.–
2001, pp. 2010–2011. 12th EURECA 2019, AIP Conf. Proc. 2137, 020002-
https://doi.org/10.1039/b106357j 1–020002-10.
95. Smith, E.L., Abbott, A.P., and Ryder, K.S., Chem. Rev., https://doi.org/10.1063/1.5120978
2014, vol. 114, no. 21, pp. 11060–11082. 109. Tang, X., Zhang, Y., Li, J., Zhu, Y., Qing, D., and Deng, Y.,
https://doi.org/10.1021/cr300162p Ind. Eng. Chem. Res., 2015, vol. 54, pp. 4625−4632.
96. Makoś, pp. and Boczkaj, G., J. Mol. Liq., 2019, vol. 296, https://doi.org/10.1021/acs.iecr.5b00291
ID 111916. 110. Gano, Z.S., Mjalli, F.S., Al-Wahaibi, T., Al-Wahaibi, Y.,
https://doi.org/10.1016/j.molliq.2019.111916 and Al Nashef, I.M., Chem. Eng. Process., 2015, vol. 93,
97. Kučan, K.Z. and Rogošić, M., J. Chem. Technol. pp. 10–20.
Biotechnol., 2018, vol. 94, pp. 1282–1293. https://doi.org/10.1016/j.cep.2015.04.001
https://doi.org/10.1002/jctb.5885. 111. Li, С., Zhang, J., Li, Z., Yin, J., Cui, Y., Liu, Y., and
98. Shirazinia, S., Semnani, A., Nekoeinia, M., Shirani, M., Yang, G., Green Chem., 2016, vol. 18, pp. 3789–3795.
and Akbari, A., J. Mol. Liq., 2020, vol. 301, ID 112364. https://doi.org/10.1039/C6GC00366D
https://doi.org/10.1016/j.molliq.2019.112364 112. Li, J., Xiao, H., Tang, X., and Zhou, M., Energy Fuels,
99. Almashjary, K.H., Khalid, M., Dharaskar, S., Jagadish, P., 2016, vol. 30, no. 7, pp. 5411–5418.
Walvekar, R., and Gupta, T.C.S.M., Fuel, 2018, vol. 234, https://doi.org/10.1021/acs.energyfuels.6b00471
pp. 1388–1400. 113. Zhao, X., Zhu, G., Jiao, L., Yu, F., and Xie, C., Chem.
https://doi.org/10.1016/j.fuel.2018.08.005 Eur. J., 2018, vol. 24, pp. 11021–11032.
100. Jha, D., Haider, M.B., Kumar, R., and https://doi.org/10.1002/chem.201801631
Balathanigaimani, M.S., J. Environ. Chem. Eng., 2020, 114. Zhu, S., Cheng, H., Dai, Y., Gao, J., and Jiang, X., Energy
vol. 8, ID 104182. Fuels, 2020, vol. 34, no. 7, pp. 8186–8194.
https://doi.org/10.1016/j.jece.2020.104182 https://doi.org/10.1021/acs.energyfuels.0c01096
101. Lee, H., Kang, S., Jin, Y., Jung, D., Park, K., Li, K., 115. Hatab, F.A., Darwish, A.S., Lemaoui, T., Warrag, S.E.E.,
and Lee, J., Fuel, 2020, vol. 264, ID 116848. Benguerba, Y., Kroon, M.C., and Al Nashef, I.M.,
https://doi.org/10.1016/j.fuel.2019.116848 J. Chem. Eng. Data, 2020, vol. 65, no. 11, pp. 5443–
102. Lima, F., Gouvenaux, J., Branco, L.C., Silvestre, A.J.D., 5457.
and Marrucho, I.M., Fuel, 2018, vol. 234, pp. 414–421. https://doi.org/10.1021/acs.jced.0c00579
https://doi.org/10.1016/j.fuel.2018.07.043 116. Kiran, N., Abro, R., Abro, M., Shah, A.A., Jatoi, A.S.,
103. Mjalli, F.S., Rahma, W.S.A., Al-Wahaibi, T., and Bhutto, A.W., Qureshi, K., Sabzoi, N., Gao, S., and
Al-Hashmi, A.A., Chin. J. Chem. Eng., 2019. Yu, G., Chem. Papers, 2019, vol. 73, pp. 2757–2765.
https://doi.org/10.1016/j.cjche.2019.03.033 https://doi.org/10.1007/s11696-019-00828-4
104. Al-Azzawi, M., Mjalli, F.S., Al-Hashmi, A., Al- 117. Hosseinpour, M., Soltani, M., Noofeli, A., and
Wahaibi, T., and Abu-jdayil, B., Chem. Eng. Process.: Nathwani, J., Fuel, 2020, vol. 271, ID 117618.
Process Intens., 2019, vol. 140, pp. 43–51. https://doi.org/10.1016/j.fuel.2020.117618
https://doi.org/10.1016/j.cep.2019.04.012 118. Patwardhan, P.R., Timko, M.T., Class, C.A.,
105. Sudhir, N., Yadav, P., Nautiyal, B.R., Singh, R., Bonomi, R.E., Kida, Y., Hernandez, H.H., Tester, J.W.,
Rastogi, H., and Chauhan, H., Sep. Sci. Technol., 2020, and Green, W.H., Energy Fuels, 2013, vol. 27,
vol. 55, no. 3, pp. 554–563. pp. 6108−6117.
https://doi.org/10.1080/01496395.2019.1569061 https://doi.org/10.1021/ef401150w
106. Lima, F., Dave, M., Silvestre, A.J.D., Branco, L.C., and 119. Ates, A., Azimi, G., Choi, K.-H., Green, W.H., and
Marrucho, I.M., ACS Sustain. Chem. Eng., 2019, vol. 7, Timko, M.T., Appl. Catal. B, 2014, vol. 147, pp. 144–
pp. 11341–11349. 155.
https://doi.org/10.1021/acssuschemeng.9b00877 https://doi.org/10.1016/j.apcatb.2013.08.018
107. Dharaskar, S., Sillanpa, M., and Tadi, K.K., Environ. 120. Yan, T., Wu, L., Wang, L., Fu, F., and Fang, T., Energy
Sci. Pollut. Res., 2018, vol. 25, pp. 17156–17167. Fuels, 2020, vol. 34, pp. 2958−2968.
https://doi.org/10.1007/s11356-018-1789-5 https://doi.org/10.1021/acs.energyfuels.9b04148
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Extraction Methods for Removing Sulfur and Its Compounds

INTRODUCTION world tends to increase. The world market’s price of

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

fraction of atmospheric N-methylpyrrolidone + 2:1(N-methylpyrrolidone) of atmospheric gasoil

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

Thiophenes Model solution in Dimethylformamide, 50°С, Vs : Vf = 2 : 1, N-Methylpyrrolidone: 97% [34]

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

MnCl2, CrCl3, Cu(TFA)2,

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

Total sulfur Superviscous Tetrahydrofuran, 25°С, Vs : Vf = 1 : 1 SVC: dimethylformamide : [53]

(4.29 wt %) and aqueous and alcoholic

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

thiophene, 80.6% of dibenzo-

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

Total sulfur Gasoil (648 mg L–1) Dimethylformamide, 30°С, N-Methylpyrrolidone : [61]

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

mercaptans ethyl mercaptan in min, 2 steps ~100%

Sulfur compound Sample Extractant Conditionsa Degree of extraction References

sulﬁde 4231 mg L–1,

a Vs : Vf: solvent-to-feed ratio.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

Table 2. Classiﬁcation of eutectic solvents [23, 24, 95]

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 94 No. 4 2021

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