HiPerCap High Performance Capture Source CO 2 capture Transport Storage Natural gas Oil Bio-fuel Coal Absorption Systems Earl Goetheer, Principal scientist at TNO
HiPerCap High Performance Capture
Source CO2 capture Transport Storage Natural gas
Oil
Bio-fuel
Coal
Absorption Systems
Earl Goetheer, Principal scientist at TNO
21/06/2012 2
Capture in 1930
21/06/2012 3
Challenges Post-combustion Capture
Ab
sorb
er
Reg
ener
ato
r
Makeup water
CO2-lean gas
CO2-rich gas
Rich solvent
Bottom Tray
Top Tray
Bottom Tray
Top Tray
Pump
Pump
Condenser
Reflux Reflux drum
Reboiler
Lean solvent
Liquid
Vapor
Steam
Condensate
Rich solvent
Lean
so
lven
t
CO2 gas
Scru
bb
er
advanced heat
integration
reduce heat consumption
avoid emission solvent traces
reduce absorber, scrubber investment
Emission
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Aerosol emission Volatile emission
Particle number conc./[1/cm3]
104 105 106 107 108
ME
A/[
mg/N
m3]
0
200
400
600
800
1000
1200
1400
Low Soot
High Soot
Low level H2SO4 aerosol
Middle level H2SO4 aerosol
High level H2SO4 aerosol
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FGD
FFSCR
~
infiltration air
infiltration air
CO2 to storage
DCC
1 2 3
water/steam
air
CO2
coal
coal millI air
II air
PZ process
flue gas
APH
Integration
Energy Consumption
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Spe
cifi
c e
ne
rgy
du
ty G
J th/t
CO
2
Technologies
• Enzymatic catalysed CO2 capture
• Biomimicking
• Strong bicarbonate formers
• Precipitating solvent systems
• Capture integrated with algae cultivation
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Precipitating solvent systems
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9
CO2 absorption with amino acid salts Resistant to oxidative
degradation
Less waste generated products
Zero emissions of active reactant
Potential energy savings
• Limited solubility in water
Ionic equilibria In water:
R-(NH2)COOH R-(NH3)+COO- zwitterion
- H+ - H+
R-(NH3)+ COOH ↔ R-(NH3)
+COO- ↔ R-(NH2)+COO-
R-(NH3)+COO- + KOH R-(NH2)COO-K+ reactive
Taurine
Glycine
10
Effect of solid precipitation
Experimental: Aqueous potassium taurate.
Dark points: precipitation
From: Kumar et al. Ind. Eng. Chem. Res. 42, 2003, 2841-2852
40 oC ; 6M AmA
10
100
1000
10000
100000
0 0,1 0,2 0,3 0,4 0,5
Loading [mole CO2/mole AmA)C
O2 P
ressure
[P
a]
Combined process
No precipitation
With precipitation
Schematic picture: effect of solvent precipitation
Enhanced absorption capacity: DECAB principle
11
Reactions with CO2 (similar to “normal” amine systems):
Carbamate formation (primary and secondary amines)
CO2 + 2 -OOC-R-NH2 ↔ -OOC-R-NH-COO- + -OOC-R-NH3+ (1)
amine carbamate protonated amine
Carbamate hydrolysis -OOC-R-NH-COO- + H2O ↔ -OOC-R-NH2 + HCO3
- (2) carbamate amine bicarbonate
Bicarbonate formation (tertiary amines, sterically hindered secondary amines)
CO2 + -OOC-R-NH2↔ -OOC-R-NH3+ + HCO3
- (3) amine protonated amine bicarbonate
Why do you get higher capacity?
Removed by precipitation
12
Working with solids in the process
• Controlled precipitation of the solvent
• Solids should appear where they can be handled
• Equipment selected for solids handling
• Process complexity increased
Working with solids IF there is an economic breakthrough
13
DECAB Process (Design & Modelling Results)
Absorption column
Spray column
Flash vessel
Stripper
HX-2
Loaded solvent
Flue Gas
Clean Gas
Pre-loaded solventHX-3
Carbon dioxide
HX-1
10MW
76 MW
16MW
36MW
190 Nm3/s
8vol%
90 C => 50 C 89MW
504 kg/s
Loading
0,13mol/mol
120 C
Loading 0,13 mol/mol
Loading
0,26mol/mol
Loading
0,43mol/mol
Loading
0,33mol/mol
14
From DECAB to DECAB+
Absorption column
Spray column
Stripper
HX-1
Loaded solvent,
slurry
Loaded solvent,
Particle free
Lean solvent
Flue Gas
Depleted
Flue gas
Clean Gas
Strip gas
Pre-loaded solvent,
particle freeHX-2
Make – up water
Lean solventCondenser
Reflux
CO2 to compresion
Conditions to enhance absorption and desorption
Absorption: High pH (basicity) Desorption: Low pH (acidity)
15
Effect of DECAB+. Enhanced desorption
VLE 100ºC
0,01
0,1
1
10
0 0,1 0,2 0,3 0,4 0,5 0,6
Loading [mol CO2 / mol Amino acid]
CO
2 P
art
ial p
ress
ure
[b
ar]
VLE 4M / 4M 100ºC
Fit 4M / 4M 100ºC
VLE 3.5M / 5M 100ºC
Fit 3.5M / 5M 100ºC
VLE 80ºC
0,001
0,01
0,1
1
10
0 0,1 0,2 0,3 0,4 0,5 0,6
Loading [mol CO2 / mol Amino acid]
CO
2 P
arti
al p
ress
ure
[b
ar]
VLE 4M /4M 80ºC
Fit 4M / 4M 80ºC
VLE 3.5M / 5M 80ºC
Fit 3.5M / 5M 80ºC
The pH shift increases the partial pressure of CO2 at a given
loading
16
Proof of principle
Liquid removed
Vol (%)
Conc.
M
T
C
Rich
Loading
mol/mol
Lean
Loading
mol/mol
0% 4 74.1 0.65 0.36
21% 4.3 77.1 0.65 0.3
42% 4.9 76 0.65 0.17
0% 4 89.7 0.65 0.24
21% 4.3 95.4 0.65 0.13
42% 4.9 93.7 0.65 0.09
Low lean loadings are
possible at relatively low
temperatures
CO2
N2
To analyzer
flask
17
Key advantages of DECAB+
• Low desorption temperature • Possibility to use low grade heat / waste heat (Ideal for the
refinery case) • Possibility to achieve lower lean loadings without increasing
reboiler temperature (Ideal for streams with low CO2 concentrations such as flue gas from gas turbines combustion)
• High pressure desorption
• Lower operating costs due to enhanced desorption
• All environmental advantages from amino acids
18
DECAB+ Process Concept
CO2 capture algae cultivation
19
20 21/06/2012
M. Tredici. Symposium “ I Biocarburanti di seconda e terza generazione” Roma 14 April 2011
Biomass community Location Yield
(t d.w. ha-1 y-1)
Photosynthetic efficiency (%)
Hybrid poplar (Populus spp.) (C3) Minnesota 8 -11 0.3- 0.4
Water hyacinth (Eichornia
crassipes) Mississippi 11 – 33 (>150) 0.3- 0.9
Switch grass (Panicum virgatum)
(C4) Texas 8-20 0.2- 0.6
Sweet sorghum (Sorghum
bicolor) (C4) Texas-California 22 - 47 0.6-1.0
Coniferous forest England 34 1.8
Maize (Zea mays) (C4) Israel 34 0.8
Tree plantation Congo 36 1.0
Tropical forest West Indies 60 1.6
Algae Different locations
70 2-2.5
Sugar cane (Saccharum
officinarum) Hawaii-Java 64-87 1.8-2.6
Napier grass (Pennisetum
purpureum) Hawaii, Puerto
Rico 85-106 2.2-2.8
21
EXAMPLES OF HIGH
PRODUCTIVITY BIOMASS
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22
Per kg dry biomass ~ 4,4 kg of CO2 is needed
21/06/2012
Ab
sorb
er
Reg
ener
ato
r
Makeup water
CO2-lean gas
CO2-rich gas
Rich solvent
Bottom Tray
Top Tray
Bottom Tray
Top Tray
Pump
Pump
Condenser
Reflux Reflux drum
Reboiler
Lean solvent
Liquid
Vapor
Steam
Condensate
Rich solvent
Lean
so
lven
t
CO2 gas
Scru
bb
er
~75% OPEX is
predominantly
CO2 desorption/
solvent regeneration
~20% efficiency loss of
power plant due to high
energy demand for
desorption
23 21/06/2012
Al
Ab
sorb
er
Algae based Regenerator
Makeup water
CO2-lean gas
Flue gas
Rich solvent
Bottom Tray
Top Tray
Pump
Lean solvent
Rich solvent
Lean
so
lve
nt
Scru
bb
er
Biomass/ products
Need for major cost reduction of
CO2 capture and limited efficiency
loss for power plants and
industrial emission sources.
Leads to new business models for
Algae to biofuels production.
24 21/06/2012
From algae to products – improvement options
Cultivation
Open systems
Closed systems
Algae-strain
Oils & hydrocarbons
Proteins
Carbohydrates
Biomass
Biofuels
Pharmaceutical Industry
Animal feed
Electricity generation
Aquaculture feed
Chemical Industry
Inoculation Harvesting & Processing Valorization Nutrients/ CO2
Growing System
Advanced Nutrient Delivery
Technology.
Advanced algal Strain Technology
Energy efficient
harvesting, extraction and
processing system.
25 21/06/2012
Advanced algal Strain Technology
26
21/06/2012
Solution: Light efficient strains
Improved Strain Wild strain
Same algal density 1,5 gr/ltr
Max. algal cell density of 8 gr/ltr for Light Efficient Strain
Non-GMO
Limitation: Mutual shading
Decreased light penetration
=
Slower growth
=
Lower biomass density
27 21/06/2012
Advanced Nutrient Delivery Technology.
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Efficient CO2-nutrient feeding
Pure CO2 bubbling Flue gas washing/bubbling (diluted CO2 stream)
Current state-of-the-art
29 21/06/2012
Enzyme promoted CO2 capture
Carbonic Anhydrase enhances the uptake rate of CO2 into an absorption liquid
Algae regenerate the carbonate-based absorption liquid
Two possible routes researched at TNO
Amine based CO2 capture
– Cultivation of algae directly on CO2 “captured” in amine-based solvents
– Algae regenerate solvent which can be reused for CO2 capture
(source: Premkumar et al. (2005) PNAS, 102 (21) p,7493-7498)
Carbonic Anhydrase II
(source http://www.energen.it/inglese/
olio_da_alghe.html)
Spirulina platensis
30 21/06/2012
Route 1: Enzyme promoted CO2 capture
Carbonic Anhydrase effects on CO2 loading
Kinetic experiments showing the rate of CO2 loading in the reference (▲, 2M sodium carbonate) and catalyzed (, 2M sodium carbonate plus 400mg/L carbonic anhydrase) tests
Carbonate solutions are cheap compared to other CO2 absorption liquids, but have a slow CO2 uptake rate
Addition of carbonic anhydrase to sodium carbonate solution increases the rate of CO2 uptake
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Route 1: Enzyme promoted CO2 capture
Concept process design of a carbonate based CO2 capture system using carbonic anhydrase as promoter and algae as
solvent regenerator
32 21/06/2012
Route 2: Combining CO2 capture with amine based solvents & algae cultivation
The uptake of CO2 by a amine-based solvent
CO2 stripping of solvent by consumption through algae in a solvent & medium solution
Recycle of the solvent for new cycle of CO2 uptake
The algae biomass can be used for product.
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Algae Bioreactor
Algae Biomass
Nutrients
Light
Down stream processing
Biomass
C o n c e p t
Products
Ab
sorb
er
Makeup water
CO2-lean gas
CO2-rich gas
Rich solvent
Bottom Tray
Top Tray
Lean solvent
Route 2: Algae-mediated CO2 desorption from amine-based solvents
Concept process design of a amine based CO2 capture system using algae as solvent regenerator
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Capture solvent selection criteria
• 1. Non-toxic to algae culture • 2. Slow biodegradable by algae culture • 3. Cheap/abundant • 4. Efficient capture of CO2
(partly absorbed CO2 should be bicarbonate species)
It is of importance to note that 90% CO2 capture is not the objective
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From problem to business
www.stichtingmilieunet.nl/.../sailing-algae.bmp
www.altdotenergy.com/wp-content/uploads/2009/...
36 21/06/2012
Some references
US2014295531 (A1) - ENZYME PROMOTED CO2 CAPTURE INTEGRATED WITH ALGAE PRODUCTION – Goetheer et al.
WO2013022349 (A1) - COMBINING ALGAE CULTIVATION AND CO2 CAPTURE – Goetheer et al.
37
Acknowledgement
21/06/2012