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N2O solubility at high amine concentration and validation of

N2O Analogy

Ardi Hartono, Emmanuel, O. Mba and Hallvard F. SvendsenThe 6th Trondheim CO2 Capture, Transport and Storage Conference

Trondheim, Norway, June 14-16, 2011

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Introduction Drawbacks and Aims Experimental Section Chemicals Used Solubility Apparatus

Results and Discussion N2O Analogy with H2O N2O Analogy with Neutralized Amine system

Conclusion and Future works

Outline

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Introduction

Physical CO2 solubility is important for detailed thermodynamic modeling and design Expressed as the Henry’s law Constant Can not measure directly in Amine solution But can be inferred from the N2O solubility via N2O analogy

N2O Analogy (Versteeg & van Swaiij, 1988)2

2

2

2

2403.04 expH ON OH OCO

HH T

− = ⋅

2

2

2 2 2

2

H OCOAm Am

CO N O H ON O

HH H

H

= ⋅

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Drawbacks :N2O Analogy was challenged:

Not valid over large range of concentrations(Pawlak and Zarzycki, 2002)

Valid for amine concentration less than 30 wt% (Hutenhius, et al. ,2008)

Aims : to measure the N2O solubility at high amine concentrations and to test the N2O analogy

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Experimental Section

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Chemicals used

CO2 gas (purity ≥ 99.999 mol %, from YARA-PRAXAIR) N2O gas (purity ≥ 99.99 mol %, from YARA-PRAXAIR) N2 gas (purity ≥ 99.6 mol %, from YARA-PRAXAIR) H2SO4 (purity 95-97% from SIGMA-ALDRICH)MDEA (purity ≥ 99mass%, from SIGMA-ALDRICH) De-ionised water was used as solvent throughout the

experiment

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1. Low Pressure Apparatus Up to 2 bar (abs) Up to middle range of CO2 loading Up to 90C

Hartono, et al. (2008)

Apparatus used

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2. Moderate/High Pressure Apparatus

Up to 6 bar Up to 200 C

Up to 60 bar Up to 250 C

Higher CO2 loading

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N2O and CO2 solubility was measured:

1. Water2. Neutralized amine system

with equinormal amount of amine and H2SO4

MDEA 50wt% + 2.2 M H2SO4MDEA 70wt% + 3.1 M H2SO4

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Results and discussion

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2.6 2.8 3 3.2 3.4 3.60

5

10

15

20

25

30

35

1000/T (K-1)

HN2

O (k

Pa⋅m

3 ⋅m

ol-1

)

Versteeg & van Swaaij (1988)Yaghi & Houache (2002)Jamal (2002)Hartono et al (2008)This workVersteeg & van Swaaij modelJamal modelMamun & Svendsen, 2009This model+/-5%

Comparing N2O solubility in H2O with literature

Very good agreement up to 70C within +/- 5%

Discrepancy at higher temperature

New high pressure apparatus gave certainty at higher temperature

2

2

14905.5exp 700.65 126.4 log( ) 0.238

4%

H ON OH T T

TAARD

= − + + ⋅ − ⋅

=

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2.6 2.8 3 3.2 3.4 3.60

2

4

6

8

10

12

14

16

18

20

1000/T (K-1)

HC

O2 (k

Pa⋅m

3 ⋅m

ol-1

)

Versteeg & van Swaaij (1988)Jamal (2002)Hartono, et al., (2008)This workVersteeg & van Swaaij modelJamal modelMamun & Svendsen, 2009Edward, et al.,1978This model+/-5%

Very good agreement up to 70C within +/- 5%

New data for higher temperature

2

2

2078.2exp 212.73 40.9 log( ) 0.09

3%

H OCOH T T

TAARD

= − + + ⋅ − ⋅

=

Comparing CO2 solubility in H2O with literature

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0 20 40 60 80 100 120 1401

1.5

2

2.5

Temperature (°C)

C1 =

[HN2

O-H

2O/H

CO

2-H2

O]

Versteeg & van Swaaij (1988)Jamal (2002)Ma`mun & Svendsen (2009)This work+/-5%

Very good agreement up to 70C within +/- 5%

Discrepancy at higher temperature

We provide a new correlation for N2O Analogy for a wider range of temperature

Comparing the obtained N2O analogy for water with literature

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Very good agreement up to 70C within +/- 5%

The neutralized solution follows the the N2O analogy from water reasonably well

Still need to work more at higher temperature (High Pressure Apparatus!!)

Comparing the obtained N2O analogy from Neutralized Solution

0 20 40 60 80 100 120 1401

1.5

2

2.5

Temperature (°C)

C1 =

[HN2

O-H

2O/H

CO

2-H2

O]

Versteeg & van Swaaij (1988)Jamal (2002) Ma`mun & Svendsen (2009)MDEA 50%+2.2M H2SO4

MDEA 70%+3.1M H2SO4

MEA 30%+2.55M H2SO4 (Hartono, 2009)

This work+/-5%

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Conclusions

Future Work More work needed to measure the Henry’s law constant at higher concentrations of amine and higher temperatures

The experimental procedure and apparatus was validated and the results obtained are consistent with literature data up to 70C

N2O Analogy was found to be valid even at high amine concentrations (50 wt% and 70 wt%)

We provide a new correlation for the N2O analogy

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The financial support from the CCERT project isgreatly appreciated.

The CCERT project is supported by: the Research Council of Norway (NFR 182607) Shell Technology Norway AS Metso Automation Det Norske Veritas (DNV) AS Statoil AS

Acknowledgement

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