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CO2 Absorption by Ionic Liquids
CO2 Absorption by Ionic Liquids
1
Background
2
Global average temperature
Ref:http://climate.nasa.gov/vital-signs/global-temperature/ 3
CO2 Separation Techniques
Ref: E.T.Calleja, J.Skinner,D.G.Tauste CO2 Capture in Ionic Liquids: A Review of Solubility and
Experimental Methods Hindawi Publishing Corporation Journal of Chemistry
4
Absorption
5
Solvents for CO2 Capture
Physical
Absorption Capacity
Chemical
Partial Pressure
6
Disadvantages of Solvents
Energy intensive
High capture cost
Corrosion problems
Degradation of the solvent
Volatile in nature
7
Ionic Liquids
8
Ionic liquids Properties
Wide temperature liquid range
Designer solvents
Tunable miscibility
Stability
Good solubility
Negligible vapor pressure
9
Material Selected for Current
Study
1-butyl-3methyl-imidiazolium
tetrafluoroborate (bmim) [BF4]
1-butyl-3-methyl-imidiazolium
hexafluorophosphate
(bmim)[PF6]
Carbon Dioxide
10
Continued..
Methyldiethanol Amine(MDEA)
Piperazine
11
Schematic Diagram of the
Experimental Setup
12
Experimental setup
13
Method
=
=
=
Where subscript i,f represent the initial and final condition
14
EXPERIMENTAL RESULTS
15
CO2 Solubility with Ionic Liquids
0.25
0.15
0.1
bmim[BF4]
0.05 bmim[PF6]
0
3 4 5 6 7 8 9 10 11 12
Pressure(bar)
16
FTIR Spectra of bmim[BF4]
17
CO2 Solubility with Amine Solvents
0.8
0.7
Mole of CO2 / Mole of
0.6
0.5
solvent
0.4
0.3
0
0 2 4 6 8 10 12 14
Pressure(bar)
18
CO2 Solubility in IL-MDEA Blends
0.4
0.2
bmim[BF4]
0.1 .1MDEA+.9bmim[BF4]
.2MDEA+.8bmim[BF4]
0
4 6 8 10 12 14
Pressure(bar)
19
CO2 Solubility in IL-MEA Blends
0.6
0.5
Mole of CO2 / Mole of IL
0.4
0.3
0.2
.1MEA+.9bmim[BF4]
0.1 .2MEA+.8bmim[BF4]
bmim[BF4]
0
4 6 8 10 12 14
Pressure(bar)
20
IL-MEA Blend
21
IL-Amine Blends
0.6
0.5
Mole of CO2 / Mole of IL
0.4
0.3
0.2
bmim[BF4]
0.1 .2MDEA+0.8bmim[BF4]
.2MEA+.8bmim[BF4]
0
4 7 10 13 16
Pressure(bar)
22
CO2 Solubility in IL-MEA Blends
Promoted by PZ
0.7
Mole of CO2 / Mole of IL
0.6
0.5
0.4
10% PZ
0.3 5% PZ
0% PZ
0.2
4 6 8 10 12 14
Pressure(bar)
23
IL-MEA Blend Promoted by PZ
24
FTIR Spectra OF IL-MEA Blend
Promoted By PZ
25
CO2 Solubility in IL-MDEA Blends
Promoted by PZ
Mole of CO2 / Mole of IL 0.6
0.5
0.4
0.3
0.2 0% PZ
5% PZ
0.1
10% PZ
0
4 6 8 10 12 14
Pressure(bar)
26
IL-MDEA Blend Promoted by PZ
27
FTIR Spectra of IL-MDEA Blend
Promoted by PZ
28
Rate kinetics of Physical Solvents
Time(minute)
0
0 0.5 1 1.5 2 2.5 3 3.5
-0.2
Ln((Nt-Ne)/(N0-Ne))
-0.4
-0.6
-0.8
-1
-1.2
-1.4
-1.6
-1.8
a b c d
-2
29
Rate Kinetics of Physical Solvents
Solvent Density H (bar) at Average k*(Sec-1)
(g/cm3) 303 K molecular (10 bar)
weight (g/mol)
-0.5
-0.6
-0.7
-0.8
-0.9
-1
31
Solvent Density Average molecular K**(Sec-1)
weight (g/mol)
(g/cm3)
75% [bmim][BF4]- 1.154 176.87 6.60E-4
20% MDEA- 5% PZ
70% [bmim] [BF4]- 1.161 171.10 1.37E-3
20% MDEA - 10%
PZ
75% [bmim] [BF4]- 1.143 139.37 2.04E-3
20% MEA-5% PZ
32
Modeling and Simulation
33
Thermodynamic Modelling of
bmim[BF4]
30
Experimental NRTL
25
Pressure(atm)
Peng-Rob Elec-NRTL
20
15
10
0
0 0.1 0.2 0.3
Mole fraction CO2
34
Thermodynamic Modelling of
bmim[PF6]
30
experimental
25
NRTL
Pressure (atm)
Peng-Rob
20
Elec-NRTL
15
10
0
0 0.1 0.2 0.3
Mole fraction CO2
35
Calculated Binary Interaction
Parameter
Component i [bmim][PF6] [bmim][BF4]
Component j CO2 CO2
aij -8.89 -1429.40
aji 0 0
bij 0 1.44E+05
bji -4182.22 1.98E+05
cij -2.83 -5.97
dij 0.02 2.87E-02
eij 1.37 185.54
eji 0 0
fij 0 0
fji 1.7E-03 0
36
Thermodynamic Modelling of
bmim[TF2N]
37
Thermodynamic Modelling of
emim[TF2N]
38
Calculated Binary Interaction
Parameter
Component i [emim][ Tf2N ] [bmim][Tf2N]
Component j CO2 CO2
aij -0.93 4.96
aji 0 0
bij 0 0
bji -1070.76 5.62E+04
cij -4.68 -2.13
dij 0.02 9.70E-03
eij 0.34 -0.90
eji 0 0
fij 0 0
fji 2.54E-03 0.99
39
Simulation Study
40
Feed Stream Composition (mass %)
Component of Natural Gas Composition
Methane 64.754
Ethane 3.349
Propane 0.250
Carbon dioxide 13.688
Nitrogen 16.999
Butane 0.960
Kidnay AJ, Parrish WR. Fundamentals of natural gas processing. Boca Raton: Taylor & Francis
Group; 2006. 41
Stream and Block Parameters For
The Process
Solvent Stream (IL)
Pressure 18 atm
Feed Stream (natural gas)
Temperature 298 K
Pressure 18 atm
Feed flow rate 100 kg/hr
Absorber
Pressure(atm) 18
Number of stages 10
Solvent inlet stage 1
Solvent outlet stage 10
Feed gas inlet stage 10
1
Gas outlet stage
42
Effect of Ionic Liquid Mass Flow
Rate on CO2 Absorption
43
Calculated Circulation Rate of Ionic
Liquids for 95% CO2 Recovery
Solvent Circulation rate % CH4 loss
(kg/hr)
Absorber
column
IL feed
4632 5824 8045 8604 5797
rate(kg/h)
IL feed
301 301 301 301 301
temperature(K)
Flash drum
Operating
1 1 1 1 1
pressure(atm)
Operating
350 350 350 350 350
temperature(K)
IL recycle flow
4632 5824 8045 8604 5797
rate (kg/h)
IL recycle purity
99.99+ 99.99+ 99.99+ 99.99+ 99.96+
(wt %)
45
Heat duty(kW) 1.48 1.51 1.52 1.59 1.52
Heat exchanger
Feed
350 350 350 350 350
temperature(K)
Feed
1 1 1 1 1
pressure(atm)
IL pump
Feed
305 305 305 305 305
temperature(K)
Feed
1 1 1 1 1
pressure(atm)
Discharge
18 18 18 18 18
pressure(atm)
Work (kw) 5 5 4 4 3
46
Conclusions
Potential use of ionic liquids for CO2 absorption
47
Research outcomes
Publications
Md. Belal Haider, Zakir Hussain, Rakesh Kumar, A comparison of ionic liquids and selexol
process for CO2 removal from natural gas, Computers and chemical engineering
(Submitted).
Md. Belal Haider, Zakir Hussain, Rakesh Kumar, Experimental study of ionic liquid blends
Conferences
Md. Belal Haider, Zakir Hussain, Rakesh Kumar, Experimental study of ionic liquid blends
Hyderabad.
48
Md Belal Haider, Zakir Hussain, Rakesh Kumar, CO2 capture by ionic liquids blends with
Md Belal Haider, Zakir Hussain, Rakesh Kumar CO2 capture by ionic liquid blends,
Outstanding young chemical engineers (OYCE-2015) held on 11th -12th, March 2015 at D. J.
Sumit Kumar Singh, Nipun Kumar, Md. Belal Haider, Rakesh Kumar Carbon capture and
storage advances, world petro-coal congress-2015 (WPCC), 2014, 12th -13th February, 2015
at Delhi.
49
Selected References
[1] Anthony J.L, Anderson J.L, Maginn E.J, Brennecke J.F. Anion effects on gas solubility in
[2] Cadena C, Anthony J.L, Shah J.K, Morrow T.I, Brennecke J.F, Maginn E.J,Why is CO2 so
[3] Chinn D, Vu D, Driver M, Boudreau L, CO2 removal from gas using ionic liquid
[5] Treybal R.E, Mass Transfer Operations (3rd ed.)McGraw Hill ,1980.
50
[6] Liu H.B, Zhang C.F, Xu G.W, A Study on Equilibrium Solubility for Carbon Dioxide in
[7] Taib M.M, Murugesan T, Solubilities of CO2 in aqueous solutions of ionic liquids (ILs) and
monoethanolamine (MEA) at pressures from 100 to 1600 kPa. Chemical Engineering Journal
Assessment of Ionic Liquid-Based CO2 Capture Processes, Ind. Eng. Chem. Res., 53(29):11805
11817, 2014.
[9]Yang J, Yu X, Yan J, and Tu S.T, CO2 Capture Using Amine Solution Mixed with Ionic
322,1985.
51
Thank You
52