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Experimental Study of Ionic

Liquid Blends for CO2


Capture

By: Md. Belal Haider


Supervisor: Dr. Rakesh Kumar

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

Highly cost effective

Lesser energy requirement

Flexible in the operation

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

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Ionic Liquids

8
Ionic liquids Properties
Wide temperature liquid range
Designer solvents
Tunable miscibility
Stability
Good solubility
Negligible vapor pressure

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Material Selected for Current
Study
1-butyl-3methyl-imidiazolium
tetrafluoroborate (bmim) [BF4]

1-butyl-3-methyl-imidiazolium
hexafluorophosphate
(bmim)[PF6]

Carbon Dioxide

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Continued..
Methyldiethanol Amine(MDEA)

Monoethanol Amine (MEA)

Piperazine

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Schematic Diagram of the
Experimental Setup

12
Experimental setup

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Method

=


=

=
Where subscript i,f represent the initial and final condition

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EXPERIMENTAL RESULTS

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CO2 Solubility with Ionic Liquids

0.25

Mole of CO2 /Mole of IL


0.2

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

0.2 aqueous MDEA

0.1 aquous MEA

0
0 2 4 6 8 10 12 14
Pressure(bar)

18
CO2 Solubility in IL-MDEA Blends

0.4

Mole of CO2 / Mole of IL


0.3

0.2

bmim[BF4]
0.1 .1MDEA+.9bmim[BF4]
.2MDEA+.8bmim[BF4]

0
4 6 8 10 12 14
Pressure(bar)

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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)
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IL-MEA Blend

A-Before CO2 absorption B-After CO2 absorption

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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)

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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)
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IL-MEA Blend Promoted by PZ

A-Before CO2 absorption B-After CO2 absorption

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FTIR Spectra OF IL-MEA Blend
Promoted By PZ

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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)
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IL-MDEA Blend Promoted by PZ

A-Before CO2 absorption B-After CO2 absorption

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FTIR Spectra of IL-MDEA Blend
Promoted by PZ

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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

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Rate Kinetics of Physical Solvents
Solvent Density H (bar) at Average k*(Sec-1)
(g/cm3) 303 K molecular (10 bar)
weight (g/mol)

a-[bmim] [PF6] 1.340 65.59 284.20 3.56E-3


b-[bmim][BF4] 1.206 71.21 226.03 4.90E-3
c-90%[bmim] 1.203 52.10 206.10 7.90E-3
[BF4]-10%
MDEA
d-80% 1.189 39.23 191.50 1.02E-2
[bmim][BF4]-
20% MDEA
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Rate Kinetics of Chemical Solvents
Time(minute)
0
0 0.5 1 1.5 2 2.5 3 3.5
-0.1
-0.2
0% PZ 5% PZ 10% PZ
-0.3
-0.4
Ln CA

-0.5
-0.6
-0.7
-0.8
-0.9
-1

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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

70% [bmim] [BF4]- 1.155 132.94 2.69E-3


20% MEA -10% PZ

80% [bmim] [BF4]- 1.181 146.71 1.74E-3


20% MEA

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Modeling and Simulation

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Thermodynamic Modelling of
bmim[BF4]
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Experimental NRTL
25
Pressure(atm)
Peng-Rob Elec-NRTL
20

15

10

0
0 0.1 0.2 0.3
Mole fraction CO2

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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
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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
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Thermodynamic Modelling of
bmim[TF2N]

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Thermodynamic Modelling of
emim[TF2N]

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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

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Simulation Study

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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
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Effect of Ionic Liquid Mass Flow
Rate on CO2 Absorption

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Calculated Circulation Rate of Ionic
Liquids for 95% CO2 Recovery
Solvent Circulation rate % CH4 loss
(kg/hr)

[bmim][Tf2N] 8604 19.5

[bmim][BF4] 4632 20.2

[bmim] [PF6] 5824 20.5

[emim][Tf2N] 8045 19.8

Selexol 5797 20.2


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Solvent [bmim][BF4] [bmim] [PF6] [emim] [Tf2N] [bmim][Tf2N] Selexol

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 %)
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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)

Heat duty(kW) 14.86 15.49 15.44 15.4 10.15

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

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Conclusions
Potential use of ionic liquids for CO2 absorption

[bmim][PF6] and [bmim][BF4], have lower CO2 solubility


compared to conventional aqueous amine solvents, however,
the regeneration energy for both ILs was much lower than
conventional amines
Piperazine addition has positive behavior for CO2 absorption

Kinetics studies reveals that absorption is faster in the blends

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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

for CO2 capture, Materials and Manufacturing Processes. (Under preparation).

Conferences

Md. Belal Haider, Zakir Hussain, Rakesh Kumar, Experimental study of ionic liquid blends

for CO2 capture, Chemference-2015, to be held on 5th-6th December, 2015 at IIT

Hyderabad.

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Md Belal Haider, Zakir Hussain, Rakesh Kumar, CO2 capture by ionic liquids blends with

alkanolamines International conference on new frontiers of chemical, energy, environmental

engineering (INCEEE-2015), at NIT-Warangal

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.

Sanghvi College of Engineering, Mumbai.

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.

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Selected References
[1] Anthony J.L, Anderson J.L, Maginn E.J, Brennecke J.F. Anion effects on gas solubility in

ionic liquids J Phys Chem B;109:6366. 2005.

[2] Cadena C, Anthony J.L, Shah J.K, Morrow T.I, Brennecke J.F, Maginn E.J,Why is CO2 so

soluble in imidazolium-based ionic liquids?. J Am Chem Soc;126:5300, 2004

[3] Chinn D, Vu D, Driver M, Boudreau L, CO2 removal from gas using ionic liquid

absorbents US20050129598 A1:2005

[4] Levenspiel O, Chemical reaction engineering, 3rd ed,2008

[5] Treybal R.E, Mass Transfer Operations (3rd ed.)McGraw Hill ,1980.

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[6] Liu H.B, Zhang C.F, Xu G.W, A Study on Equilibrium Solubility for Carbon Dioxide in

Methyldiethanolamine-Piperazine-Water Solution, Ind. Eng. Chem. Res. 38:4032-4036, 1999.

[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

181, 5662: 2012.


[8] Huang Y, Zhang X, Zhang X, Dong H, and Zhang S, Thermodynamic Modelling and

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

Liquid, Ind. Eng. Chem. Res., 53 (7), 27902799, 2014.


[10] Wilhelm E. Solubility of gases in liquids: a critical review pure and appl. chem, 57(2)303-

322,1985.
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Thank You

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