co2 capture and latest developments standard solvents ... steam use reduces plant efficiency ......

CO2 maîtrisé | Carburants diversifiés | Véhicules économes | Raffinage propre | Réserves prolongées

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CO2 Capture and Latest developments

“Promoting CO2 capture and storage in Romania" Workshop John ROESLER - Bucharest, 11-12 September 2008

“Promoting CO2 capture and storage in Romania" Workshop - John ROESLER - Bucharest, 11-12 September 20082

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CO2 emissions

Fixes sources

Main industries of concern : Coal Power plants, Steel production, Cement production, Refining

Emissions from fossil fuels :

26,5 Gt CO2 / y (7 Gt of carbon / y) (37 Gt CO2 / y in 2030 – AIE)


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Estimated costs of the CCS chain

Capture

Cost of capture (CO2 avoided) : 37-44 €/tCO2(with compression at 110 bar)

Transport

Cost of transport :1-3 €/tCO2 for 100 km

Cost of storage :• 15 € / tCO2 for 1 M t / an,• 5 €/t for 10 M t / an

Total cost between 43 et 52 € / tCO2 avoided for 10 M t/y

Storage


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What is CO2 capture?

CO2 capture: getting a purified CO2 stream after collecting the energy from carbon oxidation .


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FuelCombustion

CO2

ExtractionCO2Flue gas

Air

N2/H2O

1. Post-combustion capture

2. Oxy-combustion capture

3. Pre-combustion capture

AirH2 N2/H2O

CO2

Steam reformingATRPOx

Shiftreactor Extraction

CO2 CombustionFuel

02/H20 ATR : autothermal reformingPOx : partial oxidation

CombustionFuel

Air separation unit

Air O2

H2O

CondensationH2O

CO2CO2 /H2O

N2

CO2 capture approaches


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1. « Post-combustion » Capture

• Technology suited for existing units

• Large volumes of flue gas at atmospheric pressure with low CO2 partial pressure large units

FuelCombustion

CO2

ExtractionCO2Flue gas

Air

N2/H2O


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Post-combustionFlue gas constituents

CO2 diluted in N2 and O2

Presence of SOx and NOxPresence of solid particles Low pressure (~1 bar)

Typical composition of flue gas (% vol)

H20 5

N2 75

O2 6

Ar 1

CO2 13

SOx 10 vpm

NOx 20 vpm


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Post-combustion CO2 capture technologies

Solvants

membranesnot mature

solid adsorbentsnot mature

cryogenic (hydrates + antisublimation)

not mature

chemicalstandard solventsdemixing Solventsammonia

physicalnot suited


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Chemical solvent capture processCO2

Fumes

SolventTreated fumes

Absorption Desorption

40 °C1 bar 120°C

1-3 bar


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Solvent CaptureGeneral process considerations

Diluted gas : 10 to 15 %vol CO2 with low pressureLow PCO2 : need reactive solvent large size absorbers

Presence of oxygen, NOx, SOxDegradation reactions : Solvent consumption, corrosive degradation products

Pressure drop constraint Use of packing (structured or random)Blower at absorber inlet

Regeneration energysteam use reduces plant efficiency

Target : 90 % CO2 capture


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Vision du futur procédé intégré de Captage du CO2


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Capture with solventsOne example: MEA

+ Highly reactive molecule, even at low pressure+ Base chemical product (low cost, 1500€/t)+ Well known technology- Regeneration is highly energy consuming (4GJ/t CO2)- Use of steam to perform the solvent regeneration- sensitive to NOx, SOx, O2 additives- volatile40-45€/tCO2 capture only

30% in waterΔH = -1919 kJ/kgCO2


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Capacity: 1 t CO2 / h

5000 Nm3/h flue gas(Coal combustion)

Start up : March 2006 First solvent MEATwo other solvents tested (CASTOR1 and CASTOR2)3 others to be tested within CESAR

The greatest post-combustion pilot worldwide (at the time)

CASTOR pilot plant


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oc. i

nfo

14

Comparison of MEA, CASTOR 1 and CASTOR 2

Flue gas flow ≈5000 Nm3/h, Stripper pressure 0.85 -1.0 bar(a), 90 % CO2 recovery

50

60

70

80

90

100

3,5

3,7

3,9

4,1

4,3

4,5

10 12 14 16 18 20 22 24

CO

2re

cove

ry (%

)

Ste

am c

onsu

mpt

ion

(GJ/

ton)

Solvent flow (m3/h)

Steam consumption (MEA)

Steam consumption (CASTOR 1)

Steam consumption (CASTOR 2)

CO2 recovery (MEA)

CO2 recovery (CASTOR 1)

CO2 recovery (CASTOR 2)


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Post-Combustion with solvents

R&D issuesLower size of equipments

hydrodynamic studies: gas-liquid contactors, pressure losses

Finding high performance solvents+additivesresistance to impurities contained in flue gas O2, NOx, SOx, ...low regeneration energylow vapor pressure (losses)reduced corrosion ...

Process integration


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Some innovative solutions

Post-combustion capture


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Demixing Solvents – Principle

CO2

amine + H2O + amine salt

amine + H2O

absorption

CO2

If CO2 loading > critical valuePhase separation

amine + H2Oamine salts +

H2O

CO2


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NN

Demixing Solvents – Principle30€/t CO2


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NN

Demixing Solvents – gains

reduced solvent flow (40%)reduced energy for regeneration (40%)reduced power plant efficiency loss (30%)reduced solvent make up (50%)

30€/t CO2


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Post-combustionChilled Ammonia Process (Alstom, EPRI)

(NH4)CO2+H2O+CO2 2(NH4)CO3

carbonate bi-carbonate

ΔH=-607 kJ/kgCO2

Slurry regenerated at 20 bars


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Chilled Ammonia Process

Cooling and Cleaning

CO2 Absorption CO2 Regeneration

CO2 Regenerator

Booster Fan

From FGD

PressurizedCO2

CleanCombustion

Gas

G4

G5

G6

G7

Bleed

G1

G2 G3

GasWaterRich SolutionLean SolutionCO2

RefrigerationSystemREF

REFREF

StripperREF

Water Wash

DCC2

DCC1

CO2 Absorber

Cooling

Steam

Cooling

Steam

ALSTOM


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Post-combustionChilled Ammonia Process (Alstom, EPRI)

++regeneration energy = 15% that of MEA50% less CO2 compression cost energy for regeneration low solvent cost (130-170 €/t)resistant to O2, SOx, NOx

--flue gas chilling (2°C) to reduce solvent loss (risk for low kinetics large equipt size & capex)increased process complexity

20€/t CO2

5MW pilot under startup, hope for results at GHGT9


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2. « Oxy-combustion » Capture

• New units or revamping of existing units

• Lower gas volumes and higher CO2 concentration

Combustion

FuelASU

(Cryogenic Distillation or

other)

Air O2

H2O

CondensationH2O

CO2CO2/H2O

CO2 recycle


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Oxy-combustion CO2 capture technologies

Air separation unitscryogenicmembranesadsorbents

Combustion adaptation strategiesflue gas recirculationflameless combustion

Chemical looping combustion (CLC)


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Flue gas recirculation

fuel combustion with pure oxygen generates high temperatures

2250 Ksynthetic air (27%O2, 73%CO2)

CH4

1750 K21% O2, 79%CO2CH4

3050 KO2CH4

2250 Kair(21%O2, 79%N2)

CH4

Tflamme at STP

oxidantfuel

Flue gas recirculation mixing with O2

same flame temperaturesviscous considerationsradiation heat transfer considerations +20-30% (lots of CO2)corrosion issues


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Oxy-combustion capturePlant scheme with flue gas recirculationUse of pure oxygen – instead of Air -


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Oxy-combustionEnergy balance for pulverised coal unit


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Oxy-combustion

R&D issuesLowering cost of O2 production

membranes, sorbents (PSA, TSA, stripping), cryogenic, integration

Combustion control, furnace, burner designflue gas recirculation use of synthetic airflameless combustion CFD model developments & validationheat flux


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Oxy-combustion:Schwartze Pumpe Pilot plant (Wattenfall)

Output: 30 MW – Costs: 50 M€ - Start up : end 2008


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TOTALLACQ pilot plant

Output: 30 MW – Costs: 60 M€ - Start up : 2009


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Some innovative solutions

Oxy-combustion capture


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Oxy-combustionFlameless combustion with internal recirculation


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Metal(Ni,Cu,Fe)

MetalOxide

NiO, CuO2, Fe2O3

Air

Hot Air

Fuel

CO2H2O

MetalOxidationReactor

MetalReductionReactor

Oxy-CombustionChemical Looping Combustion

Process characteristics full CO2 capture (100%) no Air Separation Unit

One of the best candidate for 20 €/tCO2 target

No energy penalty for:oxygen production,for CO2 separation


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CLC Application to Solid Fuels Boilers

air

depleted air

fuel

CO2H2O

metaloxidation

metalreduction

air

flue gas

fuel

ConventionalCFB boiler

CFB boilerwith CLC


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Chemical LoopingDevelopments

Status: 100 kW lab pilot unitsFluidization technologies well understoodNeed: stable low cost innocuous materials

Number of new material investigated Natural ores Industrial wasteSpecific formulated and prepared materials

Evaluation of materialsOxygen transfer (O2 capacity & reactivity)Chemical and mechanical stabilityScale up and selection of manufacture processCost estimate


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« Pre-combustion » Capture

• New units

• The route to hydrogen

ATR : autothermal reformingPOx : partial oxidation

Air

H2 N2/H2O

CO2

Steam reformingATRPOx

Shiftreactor Extraction

CO2 CombustionFuel

02/H20


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Pre-combustion

AdvantagesHigh industrial experience

H2 production

Technological breakthroughTurbine for burning hydrogenLow cost O2 production

Other problemshigh capture cost (~100 €/tCO2)Chemical process

Unknown for electrical producers…


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Pre-combustion

PrinciplesPartial combustion (Coal…)

coal+O2 CO + H2O +...CH4+ O2 CO + 2H2

Or Steam reforming (Gas)CH4+ H2O CO + 3H2

“Water Gas Shift“ reactionCO + H2O CO2 + H2

CO2 / H2 separationAmines units

endothermic

exothermic

exothermic


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HyGenSys (CACHET)

HyGenSys is a promising process for converting gas to hydrogen and power with reduced carbon emissionIt reduces the cost of CO2 capture processes thanks to a high level of heat integrationMostly well proven technologies


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HyGenSys process 1/3

BFW

AirCO2 freeFlue gas

Hot Gas Generator

H/E SMR Reactor

HRSGSteam turbine

SH Steam

Hydrogen rich gas fuel only

Steam

Expander Generator


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BFW

Natural Gas

AirCO2 freeFlue gasShift

Converter

Hot Gas Generator

H/E SMR Reactor

HRSGSteam turbine

SH Steam

H2 / CO2Separation


waterCO2 for

sequestration

Expander Generator


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BFW

Natural Gas

AirCO2 freeFlue gasShift

Converter

Hot Gas Generator

H/E SMR Reactor

HRSGSteam turbine

SH Steam

H2 / CO2Separation


waterCO2 for

sequestration

Expander Generator

Air

Main H2 GT


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HyGenSys process and performance Summary

= 375 MWe(75.%)

SGT5-4000F

HRSG

3 x SGT-700

Total Power = 503 MWeNet Power = 469 MWe

Net efficiency = 44.5%CO2 capture rate = 78.2%

HRSG = 43 MWe(9%)

9 MWe (2%)

34 MWe (7%)

HRSG = 43 MWe(9%)

84 MWe (17.%)

291 MWe (58.%)

3 x E-248

HRSG = 43 MWe(9%)


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Capture development status

Post combustion•adaptable to current units•well known with solvents•best short term solution

Pre combustion• new plants• technologies exist

(except for H2 combust)• complex integration

Oxy-combustion• existing and new plants• technologies exist (at low powers)• demo units today

•pilot testing level today•demo plants: 2011•40-45€/tCO2 for coal •worse $ for NG

20 €/t CO2with new developments

• 40-45€/tCO2 • O2 separation cost• new technologies coming (CLC)

20-30€/t CO2

• plants possible by 2011• ~100 €/tCO2 with NG • ~100 €/tCO2 with coal • new technologies coming (CLR)


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Conclusions

CO2 can be readily capturedExisting technologies are still considered costlyMany demo plants in progressR&D to reduce costs to 20-30 €/tCO2 captured


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co2 capture and latest developments standard solvents ... steam use reduces plant efficiency ......

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