advanced solvent to capture co22 from flue gas

Mitsubishi Heavy Industries, Ltd.


March 7th, 2003Nobuo Imai, Project Manager

Environmental Project Department

Second International Forum onGeologic Sequestration of CO2

in Deep, Unmineable Coal Seams “Coal-Seq II”

Second International Forum onGeologic Sequestration of CO2

in Deep, Unmineable Coal Seams “Coal-Seq II”

Advanced Solvent to CaptureCO2 from Flue Gas

Advanced Solvent to CaptureCO2 from Flue Gas


Flue Gas CO2 Capture Technology

Commercially Available

StatusCapture Cost*3

(US$/T-CO2)Type

MEA

KS-1

Chemical

Absorption

PSA Method

PTSA MethodAdsorption

R&D Companies

Fluor DanielABB Lummus

KEPCO*1 / MHI*2

KEPCO / MHI

MHI (Nagasaki R&D)Others

Commercially Available

UnderResearch

35.0

Lower than MEA

84.0

Kvaerner Process SystemsOthers

UnderResearch

Amine &

Membrane

Amine Solvent

+ Membrane42.3

*1) KEPCO = Kansai Electric Power Company, *2)MHI = Mitsubishi Heavy Industries, Ltd.*3) Based on cost evaluation study conducted by IEA


Comparison Flue Gas CO2 Capture Technology

Solvent

CO2 Prod. Capacity

Steam for Reboiler

Electric Power

Cooling Water

Chemical

Licensor

KS-1

160(max. 210)

1.52(800)

18{70} *4

159(∆T=10℃)

2.1

MHI*1

MEA(30wt%)

200

1.94(988)

80

165(∆T=10℃)

4～5

Fluor Daniel*2

MEA(15～20wt%)

200

2.7(1365)

100

79.5(∆T unknown)

2.25

ABB Lummus*3

T/D

T/ton-CO2(kcal/kg-CO2)

Kwh/ton-CO2

m3/ton-CO2

US$/ton-CO2

*1) Commercial Experience in Malaysia*2) Energy Convers. Mgmt Vol.33, “First International Conference on Carbon Dioxide Removal”, M.T. Sanders, et al. 1992.*3) Hydrocarbon Processing, “CO2 recovery”, May 2002*4) Expected value of electric power consumption when S/T is replaced with motor (for comparative purpose).


Process Flow for Amine AbsorptionTreated Flue Gas

C.W.

STRIPPERSTRIPPER

Captured CO2(Purity 99.9%)

C.W.

ABSORBERABSORBERC.W.

FLUE GASCOOLERFLUE GASCOOLER C.W.

SteamREBOILERREBOILER


Coal Fired Flue Gas CO2 Recovery Pilot Test Unit

W aterO x. AirCaCO 3

NaO H Absorbent

G ypsum Recovery W aste W ater

NH

3

C .W .

C.W .

Water

Steam

De-NOx

De-SOx

De-CO 2

Treated Flue GasCO 2

OBJECTIVEOBJECTIVE

•• Applicable to various fossil fuel evaluation testsApplicable to various fossil fuel evaluation tests

•• Evaluation of total material balance, including Evaluation of total material balance, including ｔｔrace materialrace material

•• Optimization of COOptimization of CO22 recovery processrecovery process

SPECIFICATIONCapacity: 200 m3N/h Flue GasCO2 Recovery: 1 Ton/Day

Coal

De-Dust


Research and Development Activities

MHI and Kansai Electric initiated R&D since 1990.• Laboratory tests• Bench scale tests• Pilot plant tests• Data collection and analysis from commercial plants

COAL-FIRED PILOT PLANT

LABORATORY BENCH-SCALE PILOT PLANT


Amine Reaction Mechanism

MonoMono--ethanol Amine (MEA)ethanol Amine (MEA)

2 R2 R--NHNH22 + CO+ CO22 RR--NHNH33+ + + R+ R--NHNH--COOCOO--

RR--NHNH22 + CO+ CO22 + H+ H22O RO R--NHNH33++ + HCO+ HCO33

--

Sterically Hindered Amine (KSSterically Hindered Amine (KS--1)1)

2 R2 R--NHNH22 + CO+ CO22 RR--NHNH33+ + + R+ R--NHNH--COOCOO--

RR--NHNH22 + CO+ CO22 + H+ H22O RO R--NHNH33++ + HCO+ HCO33

--


Solubility of CO2 in KS-1 and MEA SolutionC

O2

Part

ial P

ress

ure

Regeneration RegionRegeneration Region

Absorption RegionAbsorption Region

MEAMEAKSKS--11

0 0.1 0.2 0.3 0.5 0.6 0.7 0.8 0.9 10.4Loading (mol.CO /mol.Amine)CO 2 2 CONFIDENTIAL


Heat of Dissociation (Heat of Absorption)

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

MEA

KS-1

14

16

18

20

22

Hea

t of D

isso

ciat

ion

(kca

l/mol

)

CO2 Loading (mol.CO2/mol.Amine) CONFIDENTIAL


Deteriorated Product of MEA and KS-1

KS-1 CommercialKS-1 PilotMEA Pilot

HE

AT

ST

AB

LE

SA

LT

S (w

t%)

+4+4

+3+3

+2+2

+1+1

BaseBase0 100 200 300 400 500 600

RUNNING TIME (hours) CONFIDENTIAL


Corrosion Test Result

MEA

MEA + inhibitor

KS-1

93.0

9.5

3.1

76.4

8.3

3.6

Test 1 Test 2(Unit : mils per year)(Unit : mils per year)

Test condition : 130Test condition : 130°°C, in the presence of OC, in the presence of O22


KS-1 Process Excellency

Lower Dissociation Heat Low Regeneration Energy

Low Regeneration Low Regeneration EnergyEnergy

Higher CO2 Loading

Lower Corrosion

Lower Degradation

Corrosion InhibitorNot Required

Corrosion InhibitorCorrosion InhibitorNot RequiredNot Required

Low SolventCirculation Flow Rate

Low SolventLow SolventCirculation Flow RateCirculation Flow Rate

Minimal Reclaiming Requirement

Minimal Reclaiming Minimal Reclaiming RequirementRequirement


Process Comparison

KSKS--11MEAMEA

Solution Circulation RateSolution Circulation Rate

Regeneration EnergyRegeneration Energy

Degradation of the SolventDegradation of the Solvent

Solvent LossSolvent Loss

Corrosion Inhibitor

11

11

11

11

YES

0.60.6

0.80.8

0.10.1

0.10.1

NOCorrosion Inhibitor YES NO


Performance of Amine CO2 Capture Process

Comparison Basis of KS-1 and MEA

1. Flue Gas Sources: Coal Fired (CO2 Conc. = 12%[d])Gas/Oil Fired (CO2 Conc. = 9%[d])Gas Turbine (CO2 Conc. = 3%[d])

2. Utility Unit Rate: LP Steam 3.0 US＄/MMBTUElectricity 5 US￠/KwhC.W. 1 US￠/T

3. Solvent Price: KS-1 6.5 US＄/ kgMEA 1.8 US＄/ kg

4. Plant Depreciation: 15-Years


Comparison of OPEX (CO2 Capture)

Coal Fired, CO2 Concentration = 12%(d)

(US$/T-CO2)Operation &25 MaintenanceSolvent

20

Cooling Water15

Electricity10

LP Steam5

0KS-1 Process MEA Process

Operation

MEA process needs frequent reclaiming, reclaimer sludge disposal and tube cleaning.



Gas/Oil Fired, CO2 Concentration = 9%(d)

(US$/T-CO2) Operation &25 Maintenance

Solvent20

Cooling Water15

Electricity10

LP Steam5


Operation




Gas Turbine, CO2 Concentration = 3%(d)

35(US$/T-CO2) Operation &

Maintenance30 Solvent

25Cooling Water

20Electricity15

10 LP Steam

5


Operation



CO2 Capture Cost of KS-1 Process

(CO(CO22 = 12%)= 12%)Coal

(CO(CO22 = 9%)= 9%)Boiler

(CO(CO22 = 3%)= 3%)G/T

30(US$/T-CO2)

Operation &MaintenanceSolvent25

20 Cooling Water

15 Electricity

10LP Steam

5

0


Cost Comparison between KS-1 & MEA

(US$/T-CO2) Operation &40 Maintenance35 Solvent30

Cooling Water25

20 Electricity15

LP Steam10

5 CAPEX0

KS-1 Process MEA Process


MHI’s Experience

PILOT PLANTPILOT PLANT

LocationLocation :: Nanko Power Plant, Osaka, JapanNanko Power Plant, Osaka, Japan

CapacityCapacity :: Flue Gas 600 NmFlue Gas 600 Nm33/H/HCOCO22 Capture Rate 2 Ton/DCapture Rate 2 Ton/D

Start UpStart Up :: April, 1991April, 1991

Research ItemsResearch Items: New Solvent Development : New Solvent Development : System Improvement: System Improvement


MHI’s Experience (MEA)

150 T/D CO150 T/D CO22 Capture PlantCapture Plant

ClientClient :: Kokusai TansanKokusai Tansan

LocationLocation :: Chiba, JapanChiba, Japan

Feed GasFeed Gas :: Naphtha CrackedNaphtha CrackedHeavy Oil Firing Boiler Flue GasHeavy Oil Firing Boiler Flue Gas

CapacityCapacity :: Flue Gas 36,500 NmFlue Gas 36,500 Nm33/H/H

Use of COUse of CO22 :: Dry Ice, Etc.Dry Ice, Etc.

Start UpStart Up :: April, 1994April, 1994


MHI’s Experience (KS-1)

160 T/D CO160 T/D CO22 Capture PlantCapture Plant

ClientClient :: Petronas Fertilizer Petronas Fertilizer (Keda)(Keda) Sdn. Bhd.Sdn. Bhd.

LocationLocation :: Kedah Darul Aman, MalaysiaKedah Darul Aman, Malaysia

Feed GasFeed Gas :: Steam Reformer Flue GasSteam Reformer Flue Gas

CapacityCapacity :: Flue Gas 47,000 Nm3/HFlue Gas 47,000 Nm3/H(Max. Capacity = 210 T/D)(Max. Capacity = 210 T/D)

Use of COUse of CO22 :: Urea ProductionUrea Production

Start UpStart Up :: October 1999October 1999


Large Scale CO2 Capture Plant (Conceptual)

ABSORBERABSORBER

STRIPPERSTRIPPERCOOLERCOOLER


Large Scale CO2 Capture Plant

Solvent

CO2 Prod. Capacity

Steam for Reboiler

Electric Power

Cooling Water

Chemical

Licensor

KS-1

160(max. 210)

1.52(800)

18{70} *3

159(∆T=10℃)

2.1

MHI*1

KS-1

3,000

1.53(790)12.2

{40}*3

174(∆T=10℃)

1.8

MHI*2

T/D

T/ton-CO2(kcal/kg-CO2)

Kwh/ton-CO2

m3/ton-CO2

US$/ton-CO2

*1) Commercial Experience in Malaysia*2) Conceptual Value of 3,000 T/D Large Scale CO2 Capture Plant*3) Expected value of electric power consumption when S/T is replaced with motor (for comparative purpose).

advanced solvent to capture co22 from flue gas

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