synthesis and selection of new amine absorbents for co2 … · 2013-07-25 · 7. 0 20 40 60 80 100...

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

2

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

8

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)

9

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



cMaximum


Diff. chain length (11 ~ 15):

Diff. substituent groups (16 ~ 22):

10

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



cMaximum


Diff. –OH groups (23 ~ 27)

Diff. ether link (28~31) Piperidine link (32 ~34)

11

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


MEA = 37g/L

1M-2PPE = 60g/L

IPAE = 67g/LMDEA = 44g/L

12

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

13

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


Apparatus for reaction heat (DRC, SETARAM)

14

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

15

(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


16

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


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

17

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

18

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

19

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.

20

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)

22

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

23

Thank you for your attention

Contact:

http://www.rite.or.jp

[email protected]

http://www.rite.or.jp/�

synthesis and selection of new amine absorbents for co2 … · 2013-07-25 · 7. 0 20 40 60 80 100...

Documents