carbonation-calcination reaction(ccr) process for high ... septiembre/c13.pdf ·...

© The Ohio State University. All rights reserved.

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


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


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



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


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



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


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


Energy

Fly Ash


Recycle CaO/ CaCO3/CaSO4


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


Single cycle (once-through) testing

Multiple sorbentsSolids loading (Ca:C ratio)Residence timeReaction Temperature


Sub-pilot Plant Set-up

SorbentInjection

Coal Stoker

Gas samplingsystem

Baghouse

Clean Flue GasTo Atmosphere


CO2 Removal by Ca Based Sorbents


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)


SO2 Removal by Ca-based Sorbents


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


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


Multicyclic Testing


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



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



Cyclic Studies Set-up

Coal StokerRotary Calciner

SorbentInjection

Baghouse


Multicyclic CO2 and SO2 Removal


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


Aspen Simulation of CCR Process


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)


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


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


Thank You

Questions

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