Presentation given by George Romanos of the National Center for Scientific Research “Demokritos” (NCSRD), Greece, on "Novel IOnic LIquid and supported ionic liquid solvents for reversible CAPture of CO2- IOLICAP" at the EC FP7 Projects: Leading the way in CCS implementation event, London, 14-15 April 2014

1. 1
CO2 capture using innovative Ionic Liquids
G. Romanos
Institute of Nanosciences and Nanotechnology,
National Center for Scientific Research “Demokritos”-Greece
EC FP7 Projects: Leading the way in CCS implementation
Novel IOnic LIquid and supported ionic liquid solvents
for reversible CAPture of CO2- IOLICAP

2. IONIC LIQUIDS 2
“Ionic Liquids is the generic term for a class of materials, consisting entirely of
ions and being liquid below 100°C.”
“If they are liquid at room temperature, we call them (RTILs).”
What are Ionic Liquids?
EC FP7 Projects: Leading the way in CCS implementation

3. Cations and Anions 3
Generations of Cations and Anions
EC FP7 Projects: Leading the way in CCS implementation

4. 4
Alkylation Reaction
Na C(CN)3
CH2Cl2
r.t.
[C(CN)3]-
NaCl
N N
+
N N
+
Cl
–
nn
+ +
Synthesis
EC FP7 Projects: Leading the way in CCS implementation

5. 55
They can be used as solvents for
CO2 capture?
•Disadvantages compared to amines
Viscosity @ RT – 15-500cP
CO2 absorption capacity < 0.05 mol/mol at 1 bar
Binary CO2/IL diffusivity – 10-11 to 10-9 m2/sec
Cost – 100-200€ at the 100kg level
Properties
EC FP7 Projects: Leading the way in CCS implementation

6. 66
Why so intense research
about ILs?
•Advantages compared to amines
Zero vapor pressure
Potentially Green Solvents
Less corrosive
Chemically stable
Can be used as pore or surface modifiers in nanostructured materials
There is an incredible number of cation/anion combinations
Properties
EC FP7 Projects: Leading the way in CCS implementation

7. 77
Some numbers concerning ILs
Properties
EC FP7 Projects: Leading the way in CCS implementation

8. 8Gas absorption data
CO2 - 120 ILs
N2 -10 ILs
SO2- 20 ILs
H2S - 16 ILs
N2O – 11 ILs
dx.doi.org/10.1021/cr300497a1 Chem. Rev. 2014, 114, 1289
EC FP7 Projects: Leading the way in CCS implementation

9. 9IOLICAP Project
From molecular design of Ionic Liquids to the proof of
concept for their pilot scale application for CO2 capture
EC FP7 Projects: Leading the way in CCS implementation

10. 10Introduction of the participating Organisations
EC FP7 Projects: Leading the way in CCS implementation

11. 11Introduction of the participating Organisations
EC FP7 Projects: Leading the way in CCS implementation

12. 12
Ways to overcome the major
disadvantages
•High Viscosity
• Low CO2 absorption capacity
• Slow CO2 capture kinetics
•High Cost
•Use them in mixtures with
water
•Develop applications at
elevated pressures
•Apply ILs as thin layers on
nanoporous materials and
membranes
IOLICAP targets
EC FP7 Projects: Leading the way in CCS implementation

13. 13Ionic Liquids examined within IOLICAP
N+
N C-
NN
N
1-ethyl-3-methylimidazolium tricyanomethanide
N+
N C-
NN
N
1-butyl-3-methylimidazolium tricyanomethanide
N+
N C-
NN
N
1-hexyl-3-methylimidazolium tricyanomethanide
N+
N C-
NN
N
1-octyl-3-methylimidazolium tricyanomethanide
TCM-based ILs
N+
N
NH2
H2N
O
O-
1-ethyl-3-methylimidazolium lysinate
N+
N
NH2
HO
O
O-
1-ethyl-3-methylimidazolium serinate
Amino acid-based ILs
Lactam-based ILs
N+
O
O
O-
F
F
F
pyrrolidium-2-one trifluoroacetate
H H
N-
S
O
O
F
F
FS
O
OF
F
F
pyrrolidium-2-one bis(trifluoromethylsulfonyl)imide
N+
O
H H
N+
N
P
O
O O
O-
1-ethyl-3-methylimidazolium diethylphosphate
N+
N
O
O-
1-ethyl-3-methylimidazolium acetate
Acetate and Phosphate anions
EC FP7 Projects: Leading the way in CCS implementation

14. 14
Effect of water on the CO2 solubility and
diffusivity of ILs with the gravimetric technique
IOLICAP-Measurement of gas solubility
EC FP7 Projects: Leading the way in CCS implementation

15. 15
Effect of water on the CO2 solubility of ILs
N+
N C-
NN
N
1-ethyl-3-methylimidazolium tricyanomethanide
N+
N C-
NN
N
1-butyl-3-methylimidazolium tricyanomethanide
N+
N C-
NN
N
1-hexyl-3-methylimidazolium tricyanomethanide
N+
N C-
NN
N
1-octyl-3-methylimidazolium tricyanomethanide
TCM-based ILs
IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation

16. 16IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation

17. 17
Effect of water on the CO2 diffusivity of ILs
IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation

18. 18
Is this enough?
Perform tests in a scrubbing/stripping device
IOLICAP-Evaluation of CO2 capture
EC FP7 Projects: Leading the way in CCS implementation

19. 19
ILs could not compete with amines
Slow capture kinetics the major problem
IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation

20. 20
Use them in mixture with amines.
Try to reduce amine content.
A mixture consisting of 7% DEA, 6.9% MDEA and 7% ILs had the
same efficiency with the 20% DEA solution
IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation

21. 21IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation
N N
C2H5
N N
C2H5

22. 22IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation
Less Corrosive for Mild Steel
7% DEA, 6.9% MDEA and 7% ILs7% DEA, 6.9% MDEA
attack severely the surface of mild
steel, leading to dissolution of
metal over the entire surface and
significant weight loss
corrosion inhibition effect of the ILs
through the adsorption on the metal
surface and blocking active sites
surrounding MnS inclusions

23. 23IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation
7% DEA, 6.9% MDEA and 7% ILs7% DEA, 6.9% MDEA
Raman analysis-Detection of corrosion products
a-FeOOH (goethite)

24. 24IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation
Less Toxic
MDC (g/L) MIC (g/L)
DEA 1.577 1.314
MDEA 2.234 1.787
MIXA 2.016 1.008
MIXB 5.704 4.278
MIXC 2.809 0.175
MIXE 9.470 4.371
7% DEA, 6.9% MDEA and
7% ILs
20% DEA

25. 25IOLICAP-Results
EC FP7 Projects: Leading the way in CCS implementation
E-1
E-2
E-3
V-1
I-1
P-2 P-3P-4
P-6
P-7
P-8
E-4
E-5
E-6
E-7
P-12
E-8
P-14
P-15
E-9
P-16
E-10
P-17
E-11
P-19
I-2
S-1
S-2
I-4
V-2
I-5
P-21P-22
P-23
P-24
S-4
S-5
I-6
P-27
I-8
V-4
E-12
P-31
P-32
P-33P-34P-35
I-9
S-9
S-10
P
I-10
I-11
V-5
P-36 P-37 P-38
I-12
S-11
S-12
S-13
V-6
P-39
P-40
I-13
S-14
S-15
I-14
P-41
P-42
P-43
V-7
I-15
S-16
S-17
P-44
P-45
E-14
V-8
P-46P-47
P-31
P-31
I-16
P-48
P-49
I-17
S-18
S-19
P-50
P-51
S-20
G=150 Kmol/h
yCO2=0.01
P=0.98 bar
T=40 C
G=157 Kmol/h
yCO2=0.05
P=1.01 bar
T=50 C
H=10m
D=0.85m
Metal Pall rings
50mm
L=10 M3/h =
490 kmol/h
a=0.15
T=35 C
MEA=18 %(w)
L=10.3 M3/h
= 497 kmol/h
a=0.37
T=50 C
G=40 Kmol/h
yCO2=0.17
P=1.2 bar
T=105 C
Sat. steam
1300 kg/h
T=120 C
20 Sieve trays
D=0.80 m
H=10 m
L=33 Kmol/h
T=90 C
G=68 Kmol/h
P=1.5 bar
T=110 C
T=90 C
T=70 C
C. Water
F=35 M3/h
Tin=25C
Tout=35C

26. 26IOLICAP-Invitation
Topics
• Nuclei and Elementary Particles for Scientific Discoveries and Innovation
• Patenting and Licensing
• Advances in targeted Drug Delivery systems & biomaterials.
• Generic Pharmaceuticals: from R&D to society.
• Sustainable CCS technologies (July 3, 2014)
• Safety & Security
• Opening new frontiers for advanced research and innovative business: the Oil & Gas industry in
Greece
• Introduction to Data Science for Agriculture & Food Safety
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