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Synthesis and thermal stability of
imidazolium salts and identification of other
possible salts NREL FY2000-present
Physical properties, materials compatibility,
and extended thermal stability testing The
University of Alabama FY2001-present
Imidazolium Salts
R4
R3
R4
R5
N
R5
N
R1
R2
X
N
N
R1
R3
R2
Methyl
Ethyl
Butyl
Hexyl
Octyl
Phenyl
Silyl
Cl
OS O 2CH3
B F4
P F6
Cost
($/lb)
Cost per lb of
EmimBF4
Glyoxal (50%)
1.00
.73
(ethylene glycol)
(0.38)
(0.12)
Formaldehyde
.21
.03
Ammonia
.10
.01
Methylamine
.73
.11
Ethylchloride
2.00
.64
(ethylene)
(0.23)
(0.03)
Tetrafluoroboric acid
(50%)
.65
.58
OH
Variation 2
OH
Me
NH2
Et
Cl
Me
Me
Cl
Et
3H2O
Et
Et
HBF4
N
Me
Cl
Me
HCl
Me
O
NH3
partial
oxidation
Cl
Variation 1
BF4
Et
HCl
Ethylene
Glycol
Storage
Tube Reactor 5
Glyoxal
Ethylene
Storage
Reactor 1
Formaldehyde
Storage
Ethyl Chloride
Reactor 2
HCl
Reactor 4
HCl/Solvent
Solvent
Ammonia
Storage
EmimCl
Tetrafluoroboric
Acid Storage
Distillation
Tower
Reactor 3
EmimBF4
Storage
Methylamine
Storage
EmimBF4
Value
15%
Tab. 4
11 years
21 years
1 year
15% of total capital
40% of net income
5% of net income
10% of fixed capital
0/100
10,000,000 kg/yr
8,322 (95%)
$50/hr (loaded including supervision)
7% of fixed capital
$0.06/kWhr
100% (except glyoxal synthesis: 75%)
Reactant costs
4.75
3.30
2.02
Other operating
0.24
0.25
0.25
Capital
0.37
0.37
0.39
TotalCost ($/kg)
5.36
3.92
2.66
Table 8. Product cost dependence on plant size and internal rate of return
Process
1
2
3
Process
1
2
3
Cost ($/kg)
5.24
5.36
5.62
3.80
3.92
4.19
2.53
2.66
2.92
100%
$2.66
95
2.86
90
3.11
80
3.85
300
Wt.%
T = 235.9oC
60
/ hr.
Weight (%)
T = 285.4oC
350
65
-5.3
80
T = 338.1oC
100
250
200
40
150
T = 134.2oC
20
100
0
0
U of Alabama, 2001
500
1000
1500
2000
2500
3000
Time (min)
3500
4000
4500
Temperature ( C)
Constant Wt.%
50
5000
Overall Observations
We may have pushed the upper temperature
limit of imidazolium salts as high as
possible with anions Further
improvements may require changes in the
imidazolium ring substituents
A 300 C salt appears to be within reach
We will begin some work on alternative
types of organic salts and mixtures
Experimental Methods
0.1
3.27 10 3 i corr W
r=
d
0.0
-0.1
Ecorr = -0.138 V
-7
where:
r = corrosion rate (mm/yr)
W = equivalent weight (g)
d = alloy density (g/cm3)
icorr = corrosion current
density (A/cm2)
-0.2
-0.3
10-10
10-9
10-8
10-7
10-6
2
10-5
10-4
Ionic liquid
SS 316
[C8mim]PF6
1.3
LC
1.2
1018 Carbon
Steel
3.2
LC
5.6
[C6mim]PF6
0.4
13.0
13.0
[C4mim][Tf2N]
1.1
11.0
20.0
[C4mim]Cl
LC = localized corrosion
8.9
LC
2.6
Conclusions
Heat Capacities
Melting
point, oC
Density
g/ml
Viscosity
cPs
Cp
Jg1K-1
Cp, v
Jcm-3K-1
Dowtherm HT
NA
1.01
953
1.42
1.41
Thermal oil
NA
0.89
1.9
1.69
1.90
[C4mim]Cl
57.1
NA
1.58
>1.58
[C2mim][BF4]
5.8
1.20
34
1.12
1.34
[C2mim][PF6]
60.5
1.10
NA
1.00
1.10
[C4mim][PF6]
6.5
1.37
389
1.14
1.56
[C6mim][PF6]
-80(Tg)
1.30
688
1.34
1.75
[C4mim][Tf2N]
-5.1
1.44
53
1.05
1.50
Dowtherm MX
Syltherm XLT
Dowtherm G
[C4mim][NTf2]
2.5
[C4mim][PF6]
[C6mim][PF6]
-3
cv / Jcm K
-1
3.0
2.0
1.5
1.0
-50
Temperature / C
2.4
BMIC
HMIC
2.2
Log 10 (Viscosity/cp)
Log 10 (Viscosity/cp)
2.0
1.8
1.6
1.4
1.2
0.35
2.0
1.8
1.6
0.40
0.45
0.50
0.55
0.60
0.65
X (AlCl3)
C4mimCl at 300K
0.70
1.4
0.40
0.45
0.50
0.55
0.60
X (AlCl3)
C6mimCl at 300K
0.65
Experimental Procedure :
Hold the ionic liquid samples at a fixed temperature for
20 hours,
Then raise the temperature to a higher level and holding
for another 20 hours until significant weight changes are
observed.
100
60
T = 133.7oC
40
200
r
/h
Weight (%)
.%
Wt
22
91
-3.
T = 235.3oC
100
20
0
0
500
1000
1500
2000
Time (min)
2500
3000
3500
Temperature (oC)
300
80
90
350
hr.
300
T = 284.4oC
Weight (%)
80
250
T = 235.3oC
70
200
60
150
T = 133.9oC
50
100
40
50
0
500
1000
1500
2000
Time (min)
2500
3000
3500
Temperature (oC)
100
65
-5.3
300
T = 285.4 C
Wt.%
T = 235.9 C
60
/ hr.
Weight (%)
80
T = 338.1 C
250
200
40
150
T = 134.2 C
20
100
0
0
500
1000
1500
2000
2500
3000
Time (min)
3500
4000
4500
Temperature ( C)
Constant Wt.%
100
50
5000
Influence of ANION
120
100
Weight (%)
80
N
60
R2
N
R1
40
20
100
200
300
Temperature (C)
400
500
600
Universal V2.3C TA Instruments
Influence of ANION
120
100
O
O S CF 3
O
Weight (%)
80
60
Et
O
O S CH3
O
N
Me
40
20
1-ethyl-3-methylimidazolium OMs
1-ethyl-3-methylimidazolium OTf
100
200
300
Temperature (C)
400
500
600
Universal V2.3C TA Instruments
100
Me
Me
Weight (%)
80
60
Me
N
Me
Me
Me
P F6
N
Me
40
Me
Me
20
P F6
Me
P F6
N
Me
1,2,3,4,5-pentamethylimid PF6
1,3-dimethylimidazolium PF6
1,3,4,5-tetramethylimid PF6
100
200
300
Temperature (C)
400
500
600
Universal V2.3C TA Instruments
199.97C
99.08%
100
Weight (%)
80
60
N
Me
40
299.63C
58.67%
Bu
N
S O2 CF 3
S O2 CF 3
20
375.46C
0.9011%
100
200
300
Temperature (C)
400
500
600
Universal V2.3C TA Instruments
Reactants
Q1
Reactor
with heat
or photons
or catalyst
Q2
Q3
Collisions
e{P+}
{D+}
EI
Source
Turbomolecular
Pump
Turbomolecular
Molecular
Pump
Drag
Pump
National Renewable Energy Laboratory
Triple Quadrupole
Mass Analyzer
Detector
Argon
Collision
Gas
Turbomolecular
Pump
MeX
N
+
N
Me
N
X
N
Me
HX
Et
82
100
80
BF 4
N
Me
60
MW = 198
40
96
28
20
110
42
55
68
0
0
20
40
60
80
100
120
140
160
180
200
m/z
Et
Et
N
Me
m/z = 82
m/z = 96
m/z = 110
1) HF liberation at high T
2) de-alkylation of quat. amine salt
glyoxal
CHO
Me NH2
PF6
Me
Me
alkylamines
BuNH2
one-pot
synthesis
PF6
N
Me
HCHO
formaldehyde
HPF6
(aq. acid)
(mp= 91C)
Bu
N
N
PF6
Bu
* avoids chloride salts as intermediates !
* 'adjustment' of melting point and thermal stability
100
Weight (%)
80
60
40
20
Mixture
1,3-dibutylimidazolium PF6
1,3-dimethylimidazolium PF6
1-butyl-3-methylimidazolium PF6
100
200
300
Temperature (C)
400
500
600
Universal V2.3C TA Instruments
Conclusions
Imidazolium salts offer flexibility in designing melting
point and thermal stability
PF6 salts are easy to prepare and purify, and are probably
least expensive
Onset T for thermal decomposition must be determined
carefully. Kinetic data are needed for evaluation of longterm T stability
Reactivity of ANION has strong influence on T stability
Structure of imidazolium CATION appears to have less
influence, but more work is needed
Influence of IMPURITIES on T stability of ionic liquids is
not completely understood and is case-dependent.
Intermediate chloride salts in synthetic route must be
avoided due to residues in final ionic fluid (corrosion)
One-Step Synthesis of ionic liquid mixtures:
a) no chloride residues
b) lower complexity of synthetic process for ionic
fluids
c) possibly lower production cost
d) synthetic methods must be optimized