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Carbonation-Calcination Reaction(CCR) Process for High Temperature CO2 and Sulfur Removal
Shwetha Ramkumar, William Wang, Dr. Songgeng Li, Siddharth Gumuluru, Zhenchao Sun, Nihar Phalak, Danny Wong, Mahesh Iyer
Dr. Robert M. Statnick, Dr. L.-S. FanWilliam G. Lowrie Department of Chemical and Biomolecular Engineering
The Ohio State UniversityColumbus, Ohio, USA
Bartev SakadjianBabcock and Wilcox Power Generation Group
U.S. Patent Application No. 61/116,172
1st Meeting of the High Temperature Solid Looping Cycles NetworkSeptember 15th –September 17th
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Steam
GeneratorCO2
Capture
CO2 Compression, Transportation
and Sequestration
Gasifier Gas Cleanup WGSR CO2
capture
Reformer
Boiler Steam Generator
Gas Turbine
Steam Turbine
PSA FT Reactor
Coal OrNatural Gas
Coal OrNatural Gas
Coal
Natural Gas
Air
Boiler
Electricity
N2 and Steam
Hydrogen•Ammonia Synthesis•Hydrogenation•Other chemicals synthesis
Liquid Fuels
Electricity CO2 free Flue Gas
Electricity
or
ASU
Post Combustion
Oxy Combustion
Pre Combustion
Steam Generator
CO2Capture
CO2 Compression, Transportation
and Sequestration
Gasifier Gas Cleanup WGSR CO2
capture
Reformer
Boiler Steam Generator
Gas Turbine
Steam Turbine
PSA FT Reactor
Coal OrNatural Gas
Coal OrNatural Gas
Coal
Natural Gas
Air
Boiler
Electricity
N2 and Steam
Hydrogen•Ammonia Synthesis•Hydrogenation•Other chemicals synthesis
Liquid Fuels
Electricity CO2 free Flue Gas
Electricity
or
ASU
Post Combustion
Oxy Combustion
Pre Combustion
CO2 Capture from Fossil Fuel Based Plants
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General Overview
Coal-fired power plants generate 50% of electricity in United States and accounts for 33% of United States CO2 emissions
Generate 41% of world’s electricity and accounts for 42% of world’s CO2 emissions
Necessary to develop economic, post-combustion CO2 removal technology for existing power plants to sustain energy demand while protecting environment
Solvent based scrubbingoxyfueladsorbentsMembranesreactive sorbents
U.S. Patent Application No. 61/116,172
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Use of metal oxide (CaO) in a reaction-based cyclical capture cycleCarbonation: CaO + CO2 → CaCO3
Sulfation: CaO + SO2 + ½ O2 → CaSO4
Calcination: CaCO3 → CaO + CO2
Advantages of Carbonation/Calcination Reaction (CCR) Operation under flue gas conditionsHigh equilibrium capacities of sorbentCalcination produces pure CO2 streamLow sorbent costSimultaneous CO2/SO2 removalHigh-temperature operation allows for heat utilization
Concept of the CCR Process
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Demonstration Project Team
CONSOL Energy
Project ManagerClear Skies Consulting
First Energy
AEP
Duke Energy
Collaborator
Babcock & Wilcox
Project Lead, Testing, Data AnalysisOhio State UniversityRolesOrganization
Collaborator
CollaboratorCollaborator
Collaborator
Collaborator
Shell Global Solutions
Carmeuse
Collaborator
CollaboratorLittleford Day
U.S. Patent Application No. 61/116,172
© The Ohio State University. All rights reserved.
Basic ReactionsBased on high-temperature, reversible reaction of metaloxide (CaO)
CO2/SO2 Lean Flue Gas
CARBONATOR
DehydrationCa(OH)2 CaO + H2O
CarbonationCaO + CO2 CaCO3
SulfationCaO + SO2 + 1/2 O2 CaSO4
450 C – 650 C
Flue Gas
CaO/CaSO4
CALCINER
CalcinationCaCO3 CaO+CO2
900 C – 1200 C
CaO/CaCO3/CaSO4
CO2 to sequestration
Energy
Fresh CaCO3
Purge
Waste CaO/CaCO3/CaSO4
HYDRATOR
CaO + H2O Ca(OH)2
500 C, P ~ 1 atm
Ca(OH)2/CaSO4
H2O
Boiler
Energy
Particulate Capture Device
Energy
Fly Ash
Particulate Capture Device
Recycle CaO/ CaCO3/CaSO4
CO2/SO2 Lean Flue Gas
CARBONATOR
DehydrationCa(OH)2 CaO + H2O
CarbonationCaO + CO2 CaCO3
SulfationCaO + SO2 + 1/2 O2 CaSO4
450 C – 650 C
Flue Gas
CaO/CaSO4
CALCINER
CalcinationCaCO3 CaO+CO2
900 C – 1200 C
CaO/CaCO3/CaSO4
CO2 to sequestration
Energy
Fresh CaCO3
Purge
Waste CaO/CaCO3/CaSO4
HYDRATOR
CaO + H2O Ca(OH)2
500 C, P ~ 1 atm
Ca(OH)2/CaSO4
H2O
Boiler
Energy
Particulate Capture Device
Energy
Fly Ash
Particulate Capture Device
Recycle CaO/ CaCO3/CaSO4
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Process Flow Diagram of the CCR Process
BoilerHydrator
Carbonator
Calciner
Fresh Sorbent
Pure CO2
Co2 Free Flue Gas
Steam
Bag House
Spent Sorbent Purge
Flue Gas
Calcined sorbent
AirBoiler
Hydrator
Carbonator
Calciner
Fresh Sorbent
Pure CO2
Co2 Free Flue Gas
Steam
Bag House
Spent Sorbent Purge
Flue Gas
Calcined sorbent
Air
Coal
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Single cycle (once-through) testing
Multiple sorbentsSolids loading (Ca:C ratio)Residence timeReaction Temperature
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Sub-pilot Plant Set-up
SorbentInjection
Coal Stoker
Gas samplingsystem
Baghouse
Clean Flue GasTo Atmosphere
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CO2 Removal by Ca Based Sorbents
U.S. Patent Application No. 61/116,172
CO2 Removals for Calcium-Based Sorbents
0
10
20
30
40
50
60
70
80
90
100
0 0.5 1 1.5 2 2.5 3 3.5 4Ca:C Mol Ratio
% C
O2
Rem
oval
Calcium Hydroxide
Pulverized Ground Lime
Ground Lime
Log. (Calcium Hydroxide)
Linear (Pulverized GroundLime)Linear (Ground Lime)
CO2 Removals for Calcium-Based Sorbents
0
10
20
30
40
50
60
70
80
90
100
0 0.5 1 1.5 2 2.5 3 3.5 4Ca:C Mol Ratio
% C
O2
Rem
oval
Calcium Hydroxide
Pulverized Ground Lime
Ground Lime
Log. (Calcium Hydroxide)
Linear (Pulverized GroundLime)Linear (Ground Lime)
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SO2 Removal by Ca-based Sorbents
U.S. Patent Application No. 61/116,172
SO2 Removals for Calcium-based Sorbents
80
82
84
86
88
90
92
94
96
98
100
0 0.5 1 1.5 2 2.5 3 3.5 4Ca:C Mol Ratio
% S
O2 R
emov
al
Calcium HydroxidePulverized Ground LimeGround Lime
SO2 Removals for Calcium-based Sorbents
80
82
84
86
88
90
92
94
96
98
100
0 0.5 1 1.5 2 2.5 3 3.5 4Ca:C Mol Ratio
% S
O2 R
emov
al
Calcium HydroxidePulverized Ground LimeGround Lime
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Effect of Residence TimeCO2 Removal vs. Reaction Residence Time
0
10
20
30
40
50
60
70
80
90
100
Relative Residence Time
CO
2 Rem
oval
(%)
1/2 2/3 1
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Multicyclic Testing
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Calcination under Realistic Conditions
0
10
20
30
40
50
60
70
OriginalSorbent
0% 33% 50%
Steam Concentration in Carrier Gas
W
t% C
aptu
re
0
10
20
30
40
50
60
70
OriginalSorbent
1 2 3
Number of Cycles
Wt%
Cap
ture
Sorbent reactivity reduced to half during calcinationEffect of sintering reduced by steam calcinationIncrease in steam concentration improves reactivity
Calcination at 900C with 50% steam and 50% CO2
Reduced sintering over multiple cyclesReactivity reduced to half in 4 cycles
U.S. Patent Application No. 61/116,172
© The Ohio State University. All rights reserved.
CCR with hydration
0
10
20
30
40
50
60
OriginalSorbent
CalcinedSorbent
WaterHydration
SteamHydration
W
t % C
aptu
re
Sorbent reactivity reduced to a third
after calcination at 1000C
Calcined sorbent regenerated
completely by hydration
U.S. Patent Application No. 61/116,172
© The Ohio State University. All rights reserved.
Cyclic Studies Set-up
Coal StokerRotary Calciner
SorbentInjection
Baghouse
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Multicyclic CO2 and SO2 Removal
U.S. Patent Application No. 61/116,172
0
10
20
30
40
50
60
70
80
90
100
0 1 2 3 4 5Cycle Number
% C
O2 R
emov
al
© The Ohio State University. All rights reserved. U.S. Patent Application No. 61/116,172
500 MWe power plantCoal Composition: Pittsburgh #820% Excess Air41% Turbine Efficiency10% in-house electricity consumption119 kWh/tonne CO2 for compression to 14 MPa (~140 atm)1
( ) ( ) 100*Control CO2 w/oGenerationy ElectricitNet
Control w/CO2Generationy ElectricitNet Control CO2 w/oGenerationy ElectricitNet n ConsumptioEnergy Parasitic
−=
1. Wong, S. “CO2 Compression and Transportation to Storage Reservoir”. Asia-Pacific Economic Cooperation. Building Capacity for CO2 Capture and Storage
in the APEC Region. Module 4
Aspen Simulation Assumptions
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Aspen Simulation of CCR Process
U.S. Patent Application No. 61/116,172
B-BURNIN
PRI-IN
SEC-IN
BOI-FLU
B-AIR
PRI
SEC
CO2-OUT
Q-CAL
CAR-SORB
SEP-SORB
FLU-OUT
RECYCLE
SORBMIX
CAL-OUT
CAL-CO2
CAL-CAO
CAOH2
H-PURGE
COAL
CAO
APH-FLU
CACO3
B-DECOMP B-BURNER
B-ASEP
Q-BOI
CO2-S02 SORB-SEP
SORB-MIX
CALCINER CAO-SEP
REGEN
PURGE
Q-CO2
ECON
AIR1
Q-CAO
Temperature (C)
Pressure (atm)
Mass Flow Rate (tons/hr)
Duty (MW)
Q Duty (MW)246.9HEAT-1
Q
Q-CAL FLU-GASASH
FLUNOASH
ASH
QCAL
-0.0 HEAT-4
Q
QAIR
STACKFLU
Q-ASH
ASH-OUT
219.3 HEAT-5
Q
80.8HEAT-6
Q
394.1HEAT-3
Q
172.7 HEAT-7
Q
Pittsburgh #8 Coal, 1506.84 MWth input1.33:1 Ca:C mol ratio90% CO2/100% SO2 removal3% purge stream698.7 MWth from Boiler647.6 MWth from CCR90% Heat Extraction582.8 MWth41% Turbine efficiency525.4 MWe Gross10% in-house consumption472.8 MWe51.3 MWe compression (119 kWh/tonne CO2)421.5 MWe NETParasitic Energy Consumption = 15.8%
CO2 toSequestration
CO2/SO2 LeanFlue Gas to Stack
Ash
COAL205 tons/hour
AIR2465 tons/hour
ASHPCD
PURGE/RECYCLE
CALCINER
BOILER
S T E A M T U R B I N E
Q-GAS FLU-ASH
232.5 HEAT-2
Q
AIR1
AIR2
PURGE
AIR2 CAL-NEW
CaCO364 tons/hour
CO2/SO2REMOVAL
CO2CO2
Purge
15% - 20% Parasitic Energy Consumption (with compression)
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Overall Electricity Production Efficiency
05
101520253035404550
Air FiredSC/Air* Base
Air FiredUSC/Air*
EconoamineSC/Air*
Oxy FuelSC/ASU*
CCR SC/Air
Net
Eff
icie
ncy,
HH
V (%
)
*Ciferno et al. 2008 Sakadjian et al, 2009
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Conclusions
Greater than 90% CO2 and ~100% SO2 Removal at a C:C of 1.3
Ca(OH)2 has highest reactivity leading to low Ca:C and residence time
13 hours of continuous operation conducted and repeatable results obtained
Sorbent reactivity maintained constant over multiple cycles
Reduction in sorbent circulation and make up rate
Low parasitic energy requirement of 15% -20% for CCR depending on heat integration
Competitive with existing CO2 control technologies
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Thank You
Questions