Desulfurization of Fuel Oils Using
Ionic Liquids
Guangren Yu
College of Chemical Engineering
Beijing University of Chemical Technology
Beijing 100029, P. R. China
Legislation on S-Limits in Fuel Oils
S-/N-content in fuel oils (gasoline, disel) <50ppm or less
2014/5/29
2
S-compounds in Fuel Oils
R SH
R NH2
R
S
S
R
N
S
N
S
S
R
R
N
N
S
S
R
N
H
N
S
R S
S R
Non-cyclic
thiol
thioether
disulphide
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S
N
N
Cyclic
thiophenes & their derivatives
3
Commercial Method: Hydrodesulfurization(HDS)
thiol
thioether
disulphide
300~400oC
H2
hydrocarbon
H2S
hydrocarbon
H2S
>10atm
H2
S
thiophene (TS)
dibenzothiophene (DBT)
their derivatives
2014/5/29
•cost
•technique
•alkene lost
4
Desulfurization Using Ionic Liquids (ILs)
Fuel oils
S
ILs
Oxidization
S
Extraction
Fuel oils
ILs
S
Oxidant
Cat.
S
O
O
A. Bösmann, Chem. Commun., 2001, 66:2494
B. W. Lo et al, Green chem.,2003, 5:639.
2014/5/29
5
Ionic Liquids
1-ethyl-3-methylimidazolium tetrafluoroborate, [emim][BF4]
J. S. Wilkes, et al., J. Chem. Soc. Chem. Commun., 13, 965 (1992).
Desirable properties:
•extremely low volatility
•remarkable ability in dissolving organic/inorganic compounds
•nonflammability
•easy alteration of cation and/or anion structure for specific
applications
•….
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6
Studies on Ionic Liquids in Many Applications
SEPARATION
gas separations
extractive distillation
extraction
membranes
ELECTROLYTES
fuel cells
sensors
batteries
supercaps
metal finishing
coating
LUBRICANTS & ADDITIVES
lubricants
fuel additives
ELECTROELASTIC MATERIALS
artificial muscles
robotics
ILs
HEAT STORAGE
thermal fluids
LIQUID CRYSTALS
displays
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ANALYTICS
MALDI-TOF-matrices
GC-head-space-solvents
protein-crystallization
SOLVENTS
bio-catalysis
organic reactions & catalysis
Nano-particle-synthesis
polymerization
7
1. Extractive Desulfurization
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8
TS Extraction from Model Oils
ILs
Model oil
Temp. (K)
[EPy][NO3]
[EPy][AC]
[BPy][BF4]
[BPy] [NO3]
[BPy] [AC]
[(CH2)4SO3HMIm][Tos]
[HPy][BF4]
[OPy][BF4]
[C43MPy][BF4]
[C63MPy][BF4]
[C83MPy][BF4]
n-heptane, xylol
n-heptane, xylol
n-heptane, xylol
n-heptane, xylol
n-heptane, xylol
i-octane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
[EPy][BF4]
n-heptane, xylol
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
323
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Nernst partition coefficient
mg(s)•Kg(IL)-1/mg(s)•Kg(oil)-1
IL : model oil
1:1
1:3
0.37
0.48
0.30
0.32
0.83
0.61
0.43
0.31
0.47
0.34
0.61
0.70
0.79
0.85
1.00
1.07
0.22
0.28
0.29
9
DBT Extraction from Model Oils
KN mg(s)Kg(IL)-1/mg(s)Kg(oil)-1
ILs
Model oil
Temp. (K)
1:1
[(CH2)4SO3HMIm][Tos]
[BMI][PF6]
[BMI][CF3SO3]
[BMI][BF4]
[EMI][BF4]
[BPy][BF4]
[HPy][BF4]
[OPy][BF4]
[BMI][BF4]
[BMI][OcSO4]
[EMI][EtSO4]
[MMI][Me2PO4]
[BMI][PF6]
[C43MPy][BF4]
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n-tetradcane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
n-dodecane
RT
333
333
333
323
RT
RT
RT
RT
RT
RT
RT
333
RT
1.08
0.77
1.42
1.79
0.7
1.9
0.8
0.7
0.9
2.08
IL : model oil
1:3
-
1:5
0.68
0.81
0.95
0.55
-
10
A Typical Reported Result: Model Oil
Multistage desulfurization of model diesel oil (500 ppm sulfur in ndodecane) by [BMIM]Cl/AlCl3 (0.35/0.65) at room temperature.
A. Bösmann, et al, Green Chemistry, 2001:2494.
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11
A Typical Reported Result: Diesel Fuel
A. Bösmann, et al, Green Chemistry, 2001:2494.
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12
A Summary for Reported Results
• 5~8 kinds of Ils (20~30 ILs)
• most studies were focused on MODEL oils; S-content
can be reduced to <10ppm after a few cycles
• only a very few studies reported the results of real oils; it
is, however, hard to reduce S-content to <50ppm
•REAL OILS IS DESIRED TO BE TESTED WIDELY AND
EXTRACTIVE DESULFURIZATION PERFORANCE OF
ILS IS DESIRED TO BE IMPROVED.
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13
Our ILs in Extractive Desulfurization
S
S
[EtMe2S]
N
F
N
N
C
S
F
-
[SCN]
N-
[BF4]
C
N
F
F
[DCA]
[BMTH]
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+
S
C
N
F
F
[PF6]
N
C
[DCA]
F
P-
F
NH
[EMI]
N
N
F
N
N
[BMI]
B- F
[S2]
1. F-free
2. Dual-function
3. Low viscosity
14
Our Oils Investigated
Model gasoline (S,500ppm)
hexane (85w%) + toluene(5w%) + TS
All ILs
Model diesel fuel (S,500ppm)
octane+ + droplets of DBT
FCC gasoline (S,350ppm)
FCC diesel fuel (S,380ppm)
[dcnm]-based Ils
&
[DCA]-based ILs
Coker diesel fuel (S,225ppm)
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15
Investigated Factors in Extractive Desulfurization
•Oil configuration
•ILs species
•Time
•Temperature
•IL:oil mass ratio
•Initial sulfur content
•Multiple-extraction
•Mutual-solubility
•IL regeneration
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16
Time: A Typical Result
360
[C2mim][N(CN)2]
[C4mim][N(CN)2]
300
270
240
Diesel fuel
[C2mim][N(CN)2]
[C4mim][N(CN)2]
350
S-content (ppm)
330
S-content (ppm)
400
Gasoline
300
250
210
0
5 10 15 20 25 30 35 40 45 50 55 60
Ti
( i )
200
0
5 10 15 20 25 30 35 40 45 50 55 60
Ti
( i )
S-content vs extraction time for the desulfurization of real oils
(gasoline and diesel fuel) with [BMI][N(CN)2] and [EMI][N(CN)2]
(temperature: 25°C; 1:1(w/w)IL:fuel)
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17
Temperature: A Typical Result
Gasoline
Diesel fuel
30
0.4
0.3
20
0.2
0.1
10
10
20
30
40
50
Extraction temperature ( oC)
0.0
60
S-Nernst Partition Coefficient
S-Extraction Efficiency (%)
0.5
As
The
temperature
desulfurization
increases,
there is a
gradual
decrease in
the
desulfurizat
ion
efficiency.
efficiency is
highest at
ambient
conditions,
i.e. 20 and
25°C.
S-extraction efficiency of real gasoline and diesel fuel with
[BMI][N(CN)2] at different extraction temperatures (initial S-content:
350ppm in gasoline and 380ppm in diesel fuel; mass ratio of
IL/fuel=1:1; extraction time: 20 min), along with S-Nernst partition
coefficients in mg(S)•kg(IL)-1/mg(S)•kg(fuel)-1
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18
IL/oil (w/w) Ratio: A Typical Result
Gasoline
Diesel fuel
S-Extraction Efficiency (%)
50
0.8
40
0.6
30
0.4
20
0.2
10
0.0
2:1
1:1
1:2
1:3
1:4
1:5
S-Nernst Partition Coefficient
1.0
The desulfurization for both gasoline
and diesel fuel is highest at 2:1 and
lowest at 1:5 mass ratio.
The extractive difference between
2:1 and 1:1 mass ratios are
inconspicuous;
e.g., for gasoline, 22.27% and
21.67% S-removal are realized at
2:1 and 1:1(w/w) IL:fuel, respectively.
The partition coefficients somewhat
depend on the IL:fuel mass ratio
Mass ratio of IL:oil (g/g)
S-extraction efficiency of [BMI][N(CN)2] for TS and DBT from model
oils at different mass ratios of IL:oil (initial S-content: 562ppm in
gasoline and 606ppm in diesel fuel; temperature: 25°C; extraction
time: 20 min), along with S-Nernst partition coefficients in
mg(S)•kg(IL)-1/mg(S)•kg(oil)-1
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19
Initial S-content: A Typical Result (Model Oil)
S-extraction efficiency (%)
TS
DBT
70
2.5
60
2.0
50
1.5
40
1.0
30
0.5
0
300
600
900
S-Nernst partition efficient
3.0
80
1200 1500 1800 2100
S-content (ppm)
S-extraction efficiency (%) of [BMI][N(CN)2] and S-Nernst partition
coefficients in mg(S)•kg(IL)-1/mg(S)•kg(oil)-1 (25°C; IL/oil=1:1, 20min)
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20
Multiple Extraction: A Typical Result
250
S-content in oil (ppm)
S-content in oil (ppm)
400
Gasoline
300
200
150
100
50
0
0
1
2
3
4
5
Extraction cycle
6
7
8
Diesel fuel
300
200
100
0
0
1
2
3
4
5
6
7
8
9
Extraction cycle
Desulfurization of [BMI][DCA] (IL:oil,1:1; 298K; 20min)
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21
ILs Regeneration: A Typical Result
Gasoline
Diesel Fuel
S-content in oil (ppm)
300
250
200
150
100
50
0
0
1
2
3
Regeneration cycle
4
5
S-content vs regeneration cycle with [BMI][N(CN)2] (temperature:
25°C; mass ratio of IL:oil=1:1; extraction time: 20 min)
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22
Mutual-solubility of ILs and Oil: A Typical Result
Solubility, in mass percentage, of real FCC gasoline and diesel fuel in IL at 25°C
fuel solubility in IL, wt%
[BMI][N(CN)2]
[EMI][N(CN)2]
solubility of gasoline in IL
4.66
4.64
solubility of diesel fuel in IL
1.97
1.93
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23
Comparison with Other Results (Model Gasoline)
Nernst partition coefficient
mg(s)•Kg(IL)-1/mg(s)•Kg(oil)-1
ILs
Model oil
Temp. (K)
1:1
1:3
1:5
0.76
0.87
[BMI][N(CN)2]
n-hexane, toluene
298
0.91
[EMI][N(CN)2]
n-hexane, toluene
298
0.65
[EtMe2S][N(CN)2]
n-hexane, toluene
298
0.43
[S2][N(CN)2]
n-hexane, toluene
298
0.6
[EPy][NO3]
n-heptane, xylol
room temperature
0.37
0.48
[EPy][AC]
n-heptane, xylol
room temperature
0.30
0.32
[EPy][BF4]
n-heptane, xylol
room temperature
0.22
323
0.28
0.29
[BPy][BF4]
n-heptane, xylol
room temperature
0.83
0.61
[BPy] [NO3]
n-heptane, xylol
room temperature
0.43
0.31
[BPy] [AC]
n-heptane, xylol
room temperature
0.47
0.34
[(CH2)4SO3HMIm][Tos]
i-octane
room temperature
0.61
[HPy][BF4]
n-dodecane
room temperature
0.70
[OPy][BF4]
n-dodecane
room temperature
0.79
[C43MPy][BF4]
n-dodecane
room temperature
0.85
[C63MPy][BF4]
n-dodecane
room temperature
1.00
2014/5/29
Ref.
IL : model oil
this
work
32
84
31
83
24
Comparison with Other Results (Model Diesel Fuel)
KN mg(s)Kg(IL)-1/mg(s)Kg(oil)-1
ILs
Model oil
Temp. (K)
IL : model oil
Ref.
1:1
1:3
1:5
2.30
2.01
[BMI][N(CN)2]
n-hexane
298
2.28
[EMI][N(CN)2]
n-hexane
298
1.3
[EtMe2S][N(CN)2]
n-hexane
298
0.84
[S2][N(CN)2]
n-hexane
298
1.08
[(CH2)4SO3HMIm][Tos]
n-tetradcane
room temperature
1.08
[BMI][PF6]
n-dodecane
333k
-
-
0.68
[BMI][CF3SO3]
n-dodecane
333k
-
-
0.81
[BMI][BF4]
n-dodecane
333k
-
-
0.95
[EMI][BF4]
n-dodecane
323k
-
-
0.55
[HPy][BF4]
n-dodecane
room temperature
1.42
-
-
[OPy][BF4]
n-dodecane
room temperature
1.79
-
-
[BMI][BF4]
n-dodecane
room temperature
0.7
-
-
[BMI][OcSO4]
n-dodecane
room temperature
1.9
-
-
[EMI][EtSO4]
n-dodecane
room temperature
0.8
-
-
[MMI][Me2PO4]
n-dodecane
room temperature
0.7
-
-
[BMI][PF6]
n-dodecane
333k
0.9
-
-
[C43MPy][BF4]
n-dodecane
room temperature
2.08
-
-
2014/5/29
this work
-
84
29
14
83
25
Summary for Extractive Desulfurization
1.
2.
3.
4.
100% S-removal for model gasoline and diesel fuels
after a few cycles
<10ppm can be achieved for real FCC gasoline and
diesel fuels after >8 cycles
ILs can be regenerated, and reused with a negligible
loss of activity in tens of cycles
Extractive desulfurization is not a good method when it
is used alone.
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26
2. Oxidative Desulfurization
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27
Oxidative Desulfurization
Fuel oils
S
Oxidant
ILs
Cat.
S
O
O
•ILs as extractive reagents
•Oxidant, H2O2 solution
•Catalyst,
acetic
acid,
phosphotungstic
acid,
phosphomolybdic acid
Recycling and loss of catalyst
2014/5/29
28
Our ILs and Diesel Fuels
N
N
N
Zn2Cl5©
N
N
ZnCl3©
1
N
COOH
HSO4©
3
2
ILs as extractive reagent and catalyst
no additional
catalyst required
N
N
N
N
N
H
N
HSO4©
4
6
5
Cl/CuCl2
Cl/FeCl2
Cl/MgCl2
C4mim
Cl/ZnCl2
N
SO3H
HSO4©
HSO4©
Cl/SnCl2
Cl/CoCl2
NH
O
Cl/ZnCl2
N
FCC diesel fuel (S,380ppm)
Coker diesel fuel (S,225ppm)
2014/5/29
29
Investigated Factors
•Oil configuration
•ILs species
•Time
•Temperature
•IL:oil mass ratio
•O:S mass ratio
•Initial sulfur content
•Multiple-extraction
•Mutual-solubility
•IL regeneration
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30
ILs Species: A Typical Result
40
EDS
ODS
S-removal efficiency(%)
30
20
10
0
PO
] Tos
MIm] H2 4
Im] HSO4
m
I
H
M
M
H
O
H
S
O
3
)
) S 3
) SO3
[ ( CH2 4
[ ( CH2 4
[ ( CH2 4
IL/oil (w/w)1:2, 333.15K, 2 h for ODS and 30 min for EDS, O/S (mol/mol)8
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31
Temperature: A Typical Result
40
S-removal efficiency(%)
35
30
25
20
15
45oC
60oC
75oC
90oC
10
5
0
1
2
3
4
5
6
Time(h)
[(CH2)4SO3HMIm][Tos] , IL/oil (w/w)1:2, O/S (mol/mol)8
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32
IL/oil (w/w) Ratio: A Typical Result
S-removal efficiency(%)
40
35
30
25
20
15
10
[ HSO3-BMIm] Tos
[ HSO3-BMIm] Cl/ZnCl2
5
0
1:5
1:4
1:3
1:2
1:1
Mass ratio of IL/Oil
O/S (mol/mol)8, 75°C/3h for [(CH2)4SO3HMIm][Tos], 60°C/3h for
[(CH2)4SO3HMIm]Cl-ZnCl2)
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33
S-removal efficiency(%)
O/S (mol/mol) Ratio: A Typical Result
40
30
20
[ HSO3-BMIm] Tos
[ HSO3-BMIm] Cl/ZnCl2
0
10
20
30
40
50
Molar Ratio of O/S
IL/oil (w/w)1:2, 75°C/3h for [(CH2)4SO3HMIm][Tos], 60°C/3h for
[(CH2)4SO3HMIm]Cl-ZnCl2)
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34
ILs Regeneration: A Typical Result
[ HSO3-BMIm] Tos
S-removal efficiency(%)
50
[ HSO3-BMIm] Cl/ZnCl2
40
30
20
10
0
1
2
3
4
5
Recycling Time
IL/oil (w/w)1:2, O/S(mol/mol) 8, 75°C/3h for [(CH2)4SO3HMIm][Tos],
60°C/3h for [(CH2)4SO3HMIm]Cl-ZnCl2)
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35
Multi-oxidation: A Typical Result
[ HSO3-BMIm] Tos
[ HSO3-BMIm] Cl/ZnCl2
S-Content(ppm)
200
150
100
50
0
0
1
2
3
4
5
6
7
8
Times of ODS
IL/oil (w/w)1:2, O/S(mol/mol) 8, 75°C/3h for [(CH2)4SO3HMIm][Tos],
60°C/3h for [(CH2)4SO3HMIm]Cl-ZnCl2)
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36
Extractive-oxidative Couple Desulfurization (IL)
160
[Bmim]DBP
[Mmim]DMP
[Emim]DEP
140
S-content(ppmw)
120
100
80
60
40
20
0
1
2
3
4
5
6
Times
[(CH2)4SO3HMIm]Cl-ZnCl2), IL/oil (w/w)1:2, O/S(mol/mol) 8, 60°C/3h for
oxidation and 60°C/30 min for extraction
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37
Extractive-oxidative Couple Desulfurization (OS)
Entry
S-content (ppmw) S-removal efficiency
(%)
1
55.3
75.4
2
24.7
89.0
3
5
99.3
[(CH2)4SO3HMIm]Cl-ZnCl2), IL/oil (w/w)1:2, O/S(mol/mol) 8, 60°C/3h for
oxidation and 60°C/30 min for extraction
2014/5/29
38
GC Characterization (Before Desulfurization)
后部信号 (140327SCD 2014-03-27 11-21-47\原料-140325.D)
AIB1 B,
15 µV
800
alkyl-DBT
alkyl-BT
700
600
500
400
300
200
100
10
2014/5/29
20
30
40
50
60
39
S-compounds in Coker Diesel Fuel (Before Desulfurization)
Main sulfur species
C4/5-TS
BT
C1-BT
C2-BT
C3-BT
C4-BT
C5/6-BT
DBT
C1-DBT
C2-DBT
C3-DBT
Total sulfur
2014/5/29
Sulfur distribution(%)
1.05
0.636
3.63
9.43
15.5
10.5
7.38
7.06
15.6
22.7
6.47
99.956
40
GC Characterization (After Desulfurization)
后部信号 (140327SCD 2014-03-27 11-21-47\3-1-4.D)
AIB1 B,
15 µV
400
350
No sulfur was detected
300
250
200
150
100
50
10
2014/5/29
20
30
40
50
60
41
ILs Oxidative-Tech Embedded into Commercial HDS
2014/5/29
42
Summary for Oxidative Desulfurization
1.
2.
3.
4.
100% S-removal for model gasoline and diesel fuels
after only ONE cycle
<50ppm can be achieved for FCC and coker diesel
fuels after a limited cycles
<10ppm can be achieved for FCC and coker diesel
fuels after a few extractive-oxidative steps
Extractive-oxidative coupled desulfurization is a good
method to produce clean fuel oils, and its pilot test is
under way…
2014/5/29
43
Conclusions
1.
2.
To reduce the S-content in fuel oils to an acceptable
level (e.g., <10ppm), extractive desulfurization alone is
not a good way while extractive-oxidative coupled
desulfurization is;
An improved HDS process can be imagined, i.e.,
“crude fuel oils” with ~200ppm S is produced after
HDS at lower cost and less loss of oil quality; then
“clean” fuel oils is obtained through ILs extractiveoxidative desulfurization in next step.
2014/5/29
44
Published Results (Papers)
[1] J. Ibrahim, et al. Extractive desulfurization of fuel oils with dicyano(nitroso)methanidebased ionic liquids. Sep. Sci. Tech., 2014, under review (LSST-2014-7776).
[2] R. Abro, et al. A review for extractive desulfurization of fuel oils using ionic liquids. RSC
Advances, 2014, under review (RA-REV-04-2014-003478).
[3] X. Chen, et al. Extractive desulfurization and denitrogenation of fuels using functional
acidic ionic liquids. Sep. Pur. Tech., 2014, under review (SEPPUR-S-13-02348).
[4]A. Charlie, et al. Desulfurization of real fuel oils by extraction with ionic liquids. Sep. Sci.
Tech., 2013, 48:2582.
[5] G. Yu, et al. Deep oxidative desulfurization of diesel fuels by acidic ionic liquids. Ind. Eng.
Chem. Res., 2011, 50:11690.
[6] G. Yu, et al. Deep desulfurization of fuel oils by using low-viscosity 1-ethyl-3methylimidazolium dicyanamide. Ind. Eng. Chem. Res., 2011, 50:2236.
[7] X. Chen, et al. Deep oxidative desulfurization of diesel fuels by Lewis acidic ionic liquids
based on 1-n-butyl-3-methylimidazolium metal chloride. J. Mol. Cat. A-Chem., 2012, 359: 8.
[8] X. Chen, et al. Extractive desulfurization of fuel oils with thiazolium-based Ionic liquids.
Sep. Sci. Tech., 2012, 47: 819.
[9] C. Asumana, et al. Extractive denitrogenation of fuel oils with dicyanamide-based ionic
liquids. Green Chem., 2011, 13:3300.
[10] C. Asumana, et al. Extractive desulfurization of fuel oils with low-viscosity dicyanamidebased ionic liquids. Green Chemistry, 2010, 12: 2030.
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Published Results (Patents in Chinese)
[11] 陈晓春，浦承皓，于光认. 一种多孔交联季铵氟磷酸盐聚合物的合成及其吸附脱硫技术
[P]. 发明专利申请号：201110128754.1.
[12] 陈晓春，宋丹丹，于光认. 一种基于Lewis 酸性离子液体的氧化脱硫方法[P]. 发明专利
申请号：201110304679.x.
[13] 于光认，赵晶晶，陈晓春，董婷婷. 一种基于Brønsted 酸性离子液体的氧化脱硫方法
[P]. 发明专利申请号：201010554836.8.
[14] 于光认，陈晓春，刘辛兴，浦承皓. 一种季铵六氟磷酸盐离子液体聚合物及其合成方
法[P]. 发明专利申请号：201010191653.4.
[15] 陈晓春，刘辛兴，于光认，浦承皓.一种基于聚合季铵盐离子液体的吸附脱硫方法[P].
发明专利申请号：201010175019.1
[16] 陈晓春,李析,于光认.一种基于低粘度离子液体的油品深度脱硫方法[P].中国专利，发明
专利申请号：201010175047.3
[17] 陈晓春, Charles Asumana, 于光认. 一种基于锍离子液体的油品深度脱硫方法[P]. 发明
专利申请号: 201010175036.5.
2014/5/29
46
Acknowledgement
(20806002, 20976005, 21176021, 21276020)
(2103051)
2014/5/29
(2010D-5006-0403)
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2014/5/29
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第 51 回熱測定討論会 ポスターセッション

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