1
Synthesis and Selection of New Amine Absorbents for CO2 Capture
ByFiroz Alam Chowdhury
Research Institute of Innovative Technology for the Earth (RITE)
9-2 Kizugawadai, Kizugawa-shi, Kyoto, Japan(URL: http://www.rite.or.jp)
1st Post Combustion Capture Conference17-19 May 2011Abu Dhabi, UAE
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Contents of Today’s Presentation
1. Background information
2. Research Target
3. Absorbent selection methodology
4. Summary and future work
3
1. Background Information
CO2 conc.> 99%
CO2 conc.< 2%
Figure 1. Chemical absorption Process
Ab
sorb
er HX
Reboiler
NewAbsorbent
(Lean)
Reg
ener
ato
r
Flue Gas
Flue Gaspre-treatment
(Absorption)(Regeneration)
Chemical Reactions:
RR'NH2 + RR'N-COO higherUnhinderedPrimary/
Secondary Amine
Hindered/TertiaryAmine
Fast absorption rate and Higher regeneration energy
Slower absorption rate and Lower regeneration energy
+ H2O
Heat2RR'NH + CO2
Absorption
Regeneration(R = H or alkyl, R' = alkyl)
RR'R''NH + HCO3 + lowerHeat
RR'R''NH + CO2
Absorption
Regeneration(R = H or alkyl, R',R'' = alkyl)
+
4
2. Research Target
Experimentally measured results of conventional amines
0.0
1.0
2.0
3.0
4.0
Reg
ener
atio
n en
ergy
[GJ/
t-C
O2]
Vapor
Solvent
Reaction
Heat balance
MEA30% Research(cal.) target
4.0
2.5
Solvent regeneration energy must be reduced for practical application
How?
By developing new solvent
0
2
4
6
40 60 80 100
Reaction Heat (kJ/mol-CO2)
Abs
orpt
ion
Rat
e(g
-CO
2/L/
min
.)
Target
MEA
AMPDEA
MDEA
Conventional Amines
5
Research Objectives
1. Development of hindered amine based absorbent with lower reaction heat and higher absorption rate
2. Fundamental Experiments on New Absorbents
・ Design and Synthesis
・ Screening
・ Reaction Heat
・ Vapor-liquid equilibrium (VLE)
・ 13C NMR study
6
Investigated amine absorbents short name and their chemical structures
Selected amine absorbents
Synthetic Amine: 1-5, 21-22, 24 and 34
7
0
20
40
60
80
100
120
0 60 120Reaction time (min)
Abs
orpt
ion
amou
nt (
g-C
O2/
L-so
ln)
30wt%_AMP
4. Absorbents selection methodology
Absorbent concentration : 30wt%Test absorbent : 50 mlAbsorption/regeneration time : 60 minPhoto: Six-bottle parallel screening system
Traditional screening apparatus
Experimental Conditions
Typical examples of screening tests
Absorptionrate
Absorptionamount
Absorptioncapacity
Initial absorption/regeneration performance
-Relative rate of absorption/regenaration-Relative cyclic capacity
Regenerationat 70℃
Absorptionat 40℃
Screening Test
CO2 analyzerGas supply
CO2 20%N2 80%
Flow rate 700 ml/min
Water bathabsorption (at 40 0C)
After 60min
regeneration (at 70 0C)
Absorbent30wt%、50 ml
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Screening test results (secondary amines)
Absorbents30wt%
aqueoussolutions
Absorptionratea
g-CO2/L-soln./min
Absorption amountb Regeneration amountc
g-CO2/ L-soln.
Cyclic capacityd
g-CO2/L-soln.
g-CO2/L-soln.
mol-CO2/mol-amine
1. MAMP 1.53 86 0.67 77 92. EAMP 1.47 86 0.76 79 73. IPAE 5.21 100 0.78 69 314. SBAE 2.51 86 0.76 55 315. IBAE 4.66 69 0.61 52 176. 2-PPM 4.55 95 0.83 75 207. 3-PPM 5.47 84 0.73 77 78. 4-PPM 4.80 89 0.77 78 119. 2-PPE 3.82 88 0.86 76 12
10. 4-PPE 5.30 82 0.80 72 1035. MEA (ref.) 5.39 117 0.54 108 9
aAbsorption rate calculated at 50% of total CO2 loading.
bMaximum CO2 loading at 40℃,1h.
cMaximum
regeneration at 70℃,1h.dDifference of CO2 loading between (40℃~70℃),
Hindered amines with open chain (1 ~ 5) Hindered cyclic amines (6 ~ 10)
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Screening test results (tertiary amines)
Absorbents30wt%
aqueoussolutions
Absorptionratea
g-CO2/L-soln./min
Absorption amountb Regeneration amountc
g-CO2/ L-soln.
Cyclic capacityd
g-CO2/L-soln.
g-CO2/L-Soln.
mol-CO2/mol-amine
11. 2DMAE 2.40 96 0.65 55 41
12. 3DMA-1P 1.47 71 0.55 52 19
13. 4DMA-1B 3.58 97 0.86 58 39
14. 6DMA-1H 3.97 80 0.88 51 29
15. 8DMA-1O 0.53 34 0.45 23 11
16. 2DEAE 3.10 95 0.84 59 3617. 3DEA-1P 3.10 88 0.87 67 2118. DMA-2P 0.90 57 0.45 46 1119. DEA-2P 2.30 76 0.76 54 2220. 2DIPAE 1.00 57 0.63 32 2521. 4DEA-2B 1.19 63 0.69 50 1322. 4EMA-2B 2.97 52 0.52 42 1038. MDEA (ref.) 1.21 53 0.48 30 23
aAbsorption rate calculated at 50% of total CO2 loading.
bMaximum CO2 loading at 40℃,1h.
cMaximum
regeneration at 70℃,1h.dDifference of CO2 loading between (40℃~70℃),
Diff. chain length (11 ~ 15):
Diff. substituent groups (16 ~ 22):
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Screening test results (tertiary amines)
Absorbents30wt%
aqueoussolutions
Absorptionratea
g-CO2/L-soln./min
Absorption amountb
Regeneration amountc
g-CO2/ L-soln.
Cyclic capacityd
g-CO2/L-soln.
g-CO2/L-soln.
mol-CO2/mol-amine
23. EDEA 1.00 49 0.49 28 2124. IPDEA 2.43 60 0.67 33 2725. tBuDEA 1.90 52 0.64 26 2626. 3DMA-1,2-PD 1.20 63 0.57 41 2227. 3DEA-1,2-PD 2.80 90 1.00 55 3528. DMAE-EO 1.80 58 0.59 28 3029. DEAE-EO 2.20 72 0.88 40 3230. Bis(2DMAE)ER 1.20 64 0.78 26 3831. TMN’(2HE)bis(2AE)ER 1.00 41 0.59 26 1532. 2HEPP 2.71 73 0.72 39 3433. 3PP-1,2-PD 3.33 57 0.69 40 1734. 1M-2PPE 2.65 79 0.86 52 2738. MDEA (ref.) 1.21 53 0.48 30 23
aAbsorption rate calculated at 50% of total CO2 loading.
bMaximum CO2 loading at 40℃,1h.
cMaximum
regeneration at 70℃,1h.dDifference of CO2 loading between (40℃~70℃),
Diff. –OH groups (23 ~ 27)
Diff. ether link (28~31) Piperidine link (32 ~34)
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Schematic diagram of VLE Test
Photo: VLE apparatus
VLE Test
CO2 conc. in liquid phase
(Total Organic Carbon Analyzer)
30wt% Test absorbent : 700 ml
Temperature : 40~120 ℃Pressure : ~ 1MPa
Experimental condition
Typical examples of VLE Tests
CO2 cyclic capacity
4. Absorbents selection methodology
MEA = 37g/L
1M-2PPE = 60g/L
IPAE = 67g/LMDEA = 44g/L
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Vapor-liquid Equilibrium test results
AmineAbsorbents
Absorbents30wt%
aqueoussolutions
CO2 Loadingg-CO2/L-soln.
Cyclic capacity c
g-CO2/L-soln.
Absorberconditiona
Regenerationconditionb
1 IPAE 94 27 675 IBAE 71 23 486 2-PPM 97 37 609 2-PPE 94 46 4811 2DMAE 94 22 7213 4DMA-1B 89 23 6614 6DMA-1H 83 19 6416 2DEAE 90 20 7017 3DEA-1P 86 23 6327 3DEA-1,2-PD 73 17 5629 DEAE-EO 67 15 5230 Bis(2-DMAE)ER 96 16 8032 2-HEPP 79 16 6334 1M-2PPE 82 22 6035 MEA 117 80 3738 MDEA 55 11 44
a Temperature 40℃, CO2 partial pressure 20kPa, b Temperature 120℃, CO2 partial pressure 100kPa,c Difference of CO2 loading between 40℃ (20kPa) and 120℃ (100kPa) under equilibrium condition.
FourSecondary
Amines
TenTertiaryAmines
ReferenceAmines
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Reaction Heat
Measurements:
Differential reaction calorimeter (DRC, SETARAM)
Semi-batch process
250ml reactor
[Test sample: 150ml, temp. : 40 ℃
(DRC, SETARAM)
Thermo couple
Heater
Dummy pipe
Thermo coupleDummy
pipeCO2
inlet
ReferenceReactor
SampleReactor
4. Absorbents selection methodology
Apparatus for reaction heat (DRC, SETARAM)
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40
50
60
70
DMAE
3DM
A-1P
4DM
A-1B
6DM
A-1H
2DEAE
3DEA-1
P
DMA-2P
DEA-2P
EDEA
IPDEA
3DM
A-1,2-
PD
3DEA-1
,2-PD
TMEDA
DMAE-EO
DEAE-EO
Bis(2D
MAE)ER
TMN’(2HE)
bis(2
AE)ER
MDEA
Rea
ctio
n H
eat
(kJ/
mo
l)
40
50
60
70
80
90
IPAE
SBAEIB
AE
2-PPM
3-PPM
4-PPM
2PPE
4-PPE
MEA
Rea
ctio
n H
eat (
kJ/m
ol-C
O2)
Reaction heat results
Selective 17 tertiary amines heat of reaction
Selective 8 secondary amines heat of reaction
MEA referencecompound
MDEA referencecompound
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(IPAE)(AMP)
-HCO3-
-COO-
-HCO3-
-COO-
13C NMR Analysis
a ratios of ([-COO−] + [HCO3−] + [CO3
2−]) to ([B] + [BH+] + [-COO−]) measured by total organic carbon analyzer and 13C-NMR. b ratio of [-COO−] to ([HCO3
−]) + [CO32−]) at 22℃
AmineAbsorbents
Absorbents30wt%
aqueoussolutions
CO2 Loadinga
mol-CO2/mol-amineratiob
13C NMR
pKa pH TOC 13C NMR
2 AMP 9.72 9.0 0.68 0.63 0.0387 IPAE 9.93 9.0 0.77 0.74 0.089
4. Absorbents selection methodology
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Summary of Results
Absorbents 30wt%aqueous solutions
Absorption ratea
g-CO2/L-soln./min
VLECyclic capacityb
g-CO2/ L-soln.
Reaction heatc
kJ/mol-CO2
3. IPAE 5.21 67 63.55. IBAE 4.66 48 62.86. 2-PPM 4.55 60 64.49. 2-PPE 3.82 48 70.811. 2DMAE 2.40 72 63.513. 4DMA-1B 3.58 66 61.714. 6DMA-1H 3.97 64 60.116. 2DEAE 3.10 70 58.917. 3DEA-1P 3.10 63 60.427. 3DEA-1,2-PD 2.80 56 56.329. DEAE-EO 2.20 52 66.230. Bis(2-DMAE)ER 1.20 80 63.532. 2-HEPP 2.71 63 64.334. 1M-2PPE 2.65 60 56.435. MEA_ref. compd. 5.39 37 86.938. MDEA_ref. compd. 1.56 44 58.8
aAbsorption rate calculated at 50% of total CO2 loading.
cdifferences of CO2 loading between 40℃ (20kPa) and 120℃
(100kPa) under equilibrium condition. dreaction heat measured α = ~0.4 mol-CO2/mol-amine at 40℃
FourSecondary
Amines
TenTertiaryAmines
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absorbent with lower reaction heat and higher absorption rate
Summary of Results
0
1
2
3
4
5
6
40 50 60 70 80 90 100
Reaction Heat (kJ/mol-CO2)
Abs
orpt
ion
Rat
e (g
-CO
2/L
/min
.) MEA
AMP
DEA
MDEA
Target
= tertiary amine = secondary amine
18
38
35
36
37
233026
31
12
2829
1119
4243234
27 221716
33 1314 9
58 763 10
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1. We selected and evaluated 38 amine based absorbents and found five secondary aminesand eight tertiary amines with higher CO2 absorption rates and lower reaction heat comparedwith conventional amines MEA and MDEA.
Five Promising Secondary Amines
Eight Promising Tertiary Amines
2. Several absorbent shows excellent performance in terms of cyclic capacities.
3. Absorbents with higher absorption rate and lower reaction heat will reduce solvent regeneration energy during CO2 stripping.
5. Research Summary
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5. Future work
- Amines with lower heat of reaction with CO2 will be used for the development new solvents and formulated (optimization concentration, blending, etc.)
- Study on process research with bench and pilot plant.
- Reaction kinetics and computational chemistry study
- Analysis of volatility, degradation, corrosion etc.
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Acknowledgements
This research work was done through the fund of COURSE 50
Project which is supported by NEDO.
We also evaluated RITE developed solvents in cooperation with Nippon Steel Engineering Company, Limited.
COURSE 50: CO2 Ultimate Reduction in Steelmaking process by Innovative
technology for cool Earth 50
NEDO: New Energy and Industrial Technology Development Organization)
21Plant scale (ton-CO2/day)
0.1 1 10 100 1,000 10,000
Co
nsu
mp
tio
n h
eat
ener
gy
(GJ/t
-C
O2)
CAT‐1
Developed absorbent 1 (estimated value)
Developed absorbent 2 (estimated value)
2.7
Literature values
CAT‐30 CCS commercial plant
Developed absorbent 1Developed absorbent 2
Developed absorbent 2 (under evaluation)
5.0
4.0
3.0
2.0
1.0
Developed absorbent 1
MEA(conventional absorbent) Absorbent developed by competitors
Evaluation of the performance (consumption heat energy)
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CAT-30
Photo was taken June, 2010
CAT-1
CAT: Chemical Absorption Test plant
The chemical absorbent is developed by RITE and Nippon Steel using the “CAT-LAB” (simulated gas testing equipment).
CAT-LAB
30t-CO2/d
1t-CO2/d
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Thank you for your attention
Contact:
http://www.rite.or.jp
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