Post on 18-Jun-2020
Kinetics of Carbonic Anhydrase in Promoted ChemicalKinetics of Carbonic Anhydrase in Promoted Chemical Solvents for Carbon Dioxide Absorption
Arne Gladis, Maria T Gundersen, Philip Fosbøl, John M Woodley, Nicolas von Solms
Post Combustion Capture Conference, Regina,08.09.2015
OverviewOverview
Introduction
Theory and methods
Experimental setup and Experiments
Results and Discussion
Conclusion and Outlook
OverviewOverview
Introduction
Theory and methods
Experimental setup and Experiments
Results and Discussion
Conclusion and Outlook
Interact projectInteract projectINnovaTive Enzymes and polyionic-liquids based membRAnes as
CO Capture TechnologyCO2 Capture Technology
Cooperation project funded within the 7th Framework program of the European Commission, theme ENERGY2013 5 1 2theme ENERGY.2013.5.1.2
EnzymesEnzymes
1vmax Michaelis Menten Kinetics
0 5
1
n ra
te ½ vmax
0
0.5
reac
tio
0 0.2 0.4 0.6 0.8 1Substrate concentration
Km
OverviewOverview
Introduction
Theory and methods
Experimental setup and Experiments
Results and Discussion
Conclusion and Outlook
Carbonic AnhydraseCarbonic Anhydrase
Present in almost every living organismy g g
faciliates different processes like Respiration, CO2
t t t h t f Ph t th itransport, rate enhancement of Photosynthesis
Metalloenyzme
One of the fastest enzymes known with up to
106 i d106 reactions per second
Absorption rate Enhancement in CCS process
One-step mechanism:
Structure and reactions of chemical solventsStructure and reactions of chemical solvents
OverviewOverview
Introduction
Theory and methods
Experimental setup and Experiments
Results and Discussion
Conclusion and Outlook
Experimental setupExperimental setup
Experimental setupExperimental setup
Wetted wall columnWetted wall column
ExperimentsExperiments
Carbonic Anhydrase in absorber conditions
Solvent: 30 wt% MDEA
Temperature: 313 K
Enzyme conc.: 1.5 g/l; 3 g/l
Solvent loading: 0-0.5
(mol CO2/mol MDEA)
OverviewOverview
Introduction
Theory and methods
Experimental setup and Experiments
Results and Discussion
Conclusion and Outlook
Effect of loading on CO absorptionEffect of loading on CO2 absorption
0.0230 wt% MDEA 313 K
0.015
/s)
30 wt% MDEA, 313 K
0.02 ldg 3 g/l CA
0.01
lux
(mol
/m2 /
0.02 ldg 1.5 g/l CA
0 35 ldg 3 g/l CA
0
0.005
Abs
orbe
d fl 0.35 ldg 3 g/l CA
0.35 ldg 1.5 g/l CA
-0.005
00 5000 10000 15000 20000 25000 30000
A
-0.01Driving force mean log pCO2 (Pa)
Effect of loading on CO absorptionEffect of loading on CO2 absorption
8.E-07
6.E-07
7.E-07
m2 /s
/Pa)
4.E-07
5.E-07
cien
t (m
ol/m
2.E-07
3.E-07
nsfe
r co
effic
0.E+00
1.E-07
mas
s tra
n
liquid 3 g/l CA liquid 1.5 g/l CA
0 0.1 0.2 0.3 0.4 0.5Solvent loading (mol CO2 / mol MDEA)
Overall enzyme reaction constantOverall enzyme reaction constant12,000
8,000
10,0003 g/l CA
1.5 g/l CA
6,000
,
v_en
z (1
/s)
2,000
4,000k ov
00 0.1 0.2 0.3 0.4 0.5
Solvent loading (mol CO2 / mol MDEA)
Accounted for gas side mass transfer resistance with Sherwood Analogy
A t d f l t ti b f i b ti i t ith t CA Accounted for solvent reactions by performing absorption experiments without CA
Enzyme reaction rate constantEnzyme reaction rate constant
4
3
3.51.5 g/l CA
3 /l CA
2
2.5
(L/m
g/s)
3 g/l CA
1
1.5
k en
z
0
0.5
0 0.1 0.2 0.3 0.4 0.5S l l di ( l CO / l MDEA)Solvent loading (mol CO2 / mol MDEA)
Apparent decrease in Enzyme rate constant with loading of solvent
Inhibition by HCO3- ? Test with a inhibition term
Bicarbonate inhibitionBicarbonate inhibition
430 t% MDEA 313 K
3
3.530 wt% MDEA, 313 K 1.5 g/l CA
3 g/l CA
Calculated
2
2.5
(L/m
g/s)
Calculated
1
1.5
k en
z
0
0.5
0 0.1 0.2 0.3 0.4 0.5S l l di ( l CO / l MDEA)
Inhibition term describes the trend of decreasing reaction rate
Solvent loading (mol CO2 / mol MDEA)
Accuracy of kinetic modelAccuracy of kinetic model
10,000
12,000
8 E 07
1.E-06
m2 )
8,000
(1/s
)
3 g/l CA
1.5 g/l CA 6.E-07
8.E-07
(mol
/Pa/
s/m
4,000
6,000
k ov
_enz
(
4.E-07
ulat
ed k
liq
0
2,000
0.E+00
2.E-07
sim
u0 0.1 0.2 0.3 0.4 0.5
Solvent loading (mol CO2 / mol MDEA)0.E+00 5.E-07 1.E-06
measured kliq (mol/Pa/s/m2)
OverviewOverview
Introduction
Theory and methods
Experimental setup and Experiments
Results and Discussion
Conclusion and Outlook
ConclusionsConclusions
Decrease of overall enzyme reaction rate with increased loading observed
Decrease of reaction rate independent of enzyme concentration
Product inhibition by HCO3- possible explanation of decrease in reaction rate
Good agreement between experimental data and simple kinetic model
enzyme reaction rate at 0.35 loading is half as high as for unloaded solvent
Account for that in process simulations
Future work Investigate enzyme performance at different temperatures Investigate enzyme performance at different temperatures
Implement temperature dependency into kinetic model
Compare with different solvents Compare with different solvents
Thank you for your attention!Thank you for your attention!