co2 purification unitco2 purification unit for oxy-coal ... 3_b/1st iea ghg oxyfuel... · co2...

CO2 Purification UnitCO2 Purification Unitfor Oxy-Coal Combustion

SystemsSystems

Jean-Pierre TranierJean Pierre TranierPhilippe Court

Arthur DardeNicolas Perrin

Air Liquide

1st International Oxyfuel Combustion Conference, CottbusSeptember 9, 2009

Air Liquide roadmap for CPU development

Industrial Demonstration

Pilot Plants

Black Hills Energy (Wyoming, USA)

Callide (Australia)Total Lacq (France)

Lab tests

Total Lacq (France)

Th ll

21st International Oxyfuel Combustion Conference, Cottbus 09/09/09

Thermo cell

Objectives of Callide CO2 CPU Pilot PlantDemonstrate the whole oxy coal flue gas compression and purificationDemonstrate the whole oxy-coal flue gas compression and purification chain based on the downscale of a large unit

Performance• CO2 purity (99.99%+)

CO f ibilit ( ti l t t i l i t)• CO2 recovery feasibility (operation close to triple point)Near Zero Emission PlantImpurities management (Particle Matter (PM), SOx, NOx, Hg)

Enable cost reduction and performance improvement for large scale unitsReduce contingencies for risk mitigationOptimize impurities removal (including upstream flue gas purification)

Provide feed back from operation (corrosion and ageing phenomena)


Downscale of a large unitUse of structured

NH3 cascade for CO2

Use of centrifugal integrally geared compressor

packing

CO2liquefaction

Ar, N2, O2

SO2, NO2

Flue Gas Use of brazed


SO2, NO2Gasaluminium heat exchanger

PerformanceCO purity (99 99%+) : Callide Pilot Plant is designed to demonstrateCO2 purity (99.99%+) : Callide Pilot Plant is designed to demonstrate the feasibility of achieving ppm level for all impurities contained in the flue gas (at a reasonable cost)

H2O N2SO2/SO3NO/NO2PM

Process studies have demonstrated feasibility and best conditions for

ArO2CO

Process studies have demonstrated feasibility and best conditions for high CO2 recovery and low power consumption


Near Zero Emission Plant

Callide Pilot Plant is designed to demonstrate near zeroCallide Pilot Plant is designed to demonstrate near zero emission feasibility for most of the impurities contained in the flue gas

P ti l M tt d t t blParticle Matter non detectableSO2/SO3 non detectableNO at least 95% abatement, probably 99%+NO d t t blNO2 non detectableHg non detectableCO2 at least 70% capture due to air

i filt ti b t ti l t t i linfiltration but operation close to triple point will demonstrate feasibility to achieve 90%+ recovery based on higher CO2 flue gas concentrationg g


Impurities management : H2O

Removed by adsorption at high pressureRemoved by adsorption at high pressure

Total Lacq Pilot Plant will allow to check the qperformance of an acid-resistant adsorbents and to assess the ageing phenomenon


Impurities management : PM

Two strategies :Two strategies :No specific dust abatement for CPU, fouling management to be considered with following options :

• 2 x 100 % (or 3 x 50 %) compressors• 2 x 100 % (or 3 x 50 %) compressors• 2 x 100 % (or 2 x 70 %) coolers• Periodically stop CPU for compressors cleaning

Specific dust abatement for CPU in order to reach same levelSpecific dust abatement for CPU in order to reach same level of dust load than centrifugal compressors used in air separation units

Air Liquide is working on both pathways to cover customers specific requests


Impurities management : NOx

The most interesting subject for a chemical engineer !

Several strategies can be considered :Low pressure scrubbingCompressor coolers condensates (with water)Compressor coolers condensates (with water)High pressure scrubbingAdsorptionDistillationDistillation

Distillation is the preferred solution in order to produce a mixture of CO and NO for :produce a mixture of CO2 and NO2 for :

Reduction in the boiler (NO2 is sent to the burners)Use as reagent for SO2 elimination


Impurities management : SO2 (1/5)For the 1st generation of CPUs, Air Liquide will use a sodiumFor the 1st generation of CPUs, Air Liquide will use a sodium scrubber for SO2 polishing

CO2

Ar, N2, O2

NaOH

Flue SO


Flue Gas

Na2SO4

SO2

NO2

Impurities management : SO2 (2/5)First strategy for 2nd generation of CPUs : low pressure drier (belowFirst strategy for 2 generation of CPUs : low pressure drier (below 10 bar abs) to avoid/limit H2SO4 formation, production of liquid SO2 and possibly NO2 (either mixed or separated by distillation) e.g. for co-sequestration with CO2

CO2

Ar, N2, O2

Flue SO


Flue Gas

SO2

SO2, NO2

Second strategy for the 2nd generation of CPUs : use NO2 directly (or

Impurities management : SO2 (2/4)Second strategy for the 2 generation of CPUs : use NO2 directly (or indirectly as HNO2/HNO3/NO2-/NO3-/N2O4/…) as reagent for SO2removal at low pressureNO2 (pure or diluted) can be recovered from compressor

Membrane

recovered from compressor coolers condensates, HP scrubbing, adsorber regeneration gas and/or distillation

CO2

Ar, N2, O2

NO

Flue Overall chemical reaction :NO2,HNO2, HNO3,…

NO2,HNO2, HNO3,…

121st International Oxyfuel Combustion Conference, Cottbus 09/09/09 H2SO4

Flue Gas NO2 + SO2 + H2O <> H2SO4 +NO

NO2

CO2

Impurities management : SO2 (3/5)For medium sulfur content in the coal, NO2 (directly or i di tl ) b d t l th i d

Raw coal CO2

CPU

CO2

NO

indirectly) can be used as reagent only on the primary and CPU flows

BoilerID Fan

CPUNO2

NO

Coal

er

ESP FGDC

H2SO4NO

SO2

Preh

eate

Primary Fan

ASU

FD Fan

Waste nitrogen


AIR

nitrogen

CO2

Impurities management : SO2 (5/5)For high sulfur content in the coal, NO2 can also be used as reagent on the o erall fl e gas

Raw coal CO2

CPU

CO2

NO

reagent on the overall flue gasCO2 CPU is used as an oxidizer of NO in NO2

NEED HIGH NOx BURNERS !!!

BoilerID Fan

CPUNO2

NO

SO

Coal

er

ESP FGDC

H2SO4NO

SO2

Preh

eate

Primary FanNO

ASU

FD Fan

Waste nitrogen


AIR

nitrogen

Impurities management : Hg

Two strategies :Do nothing special : scrubbers, flue gas condenser, coolers may remove enough mercury to have a level compatible withmay remove enough mercury to have a level compatible with the use of brazed aluminum heat exchangers, especially in the presence of strong acids like H2SO4 and HNO3Guard bed with an adsorbentGuard bed with an adsorbent

Callide Pilot Plant will confirm the best design for mercury removal including ageing of adsorbentsmercury removal including ageing of adsorbents


Impurities management : CO

Two strategies :Do nothing special : CO will go to atmosphere with vent gasC t l ti d ti ith O2 b id dCatalytic reduction with O2 can be considered


Conclusions

CPU can bring a lot of value to the power plants :Selective Catalytic Reduction of NOx is no more necessaryT diti l Fl G D l h i ti ith li t liTraditional Flue Gas Desulphurization with limestone or lime may not be required anymore in the future

O ll b ti i th t ffi i t l tiOverall, oxycombustion is the most efficient solution for CCS with the lowest emissions

Thanks to Callide and Total Lacq Pilot Plants together with lab tests and studies, Air Liquide will be able to extrapolate the design to any size of CPU and toextrapolate the design to any size of CPU and to validate new concepts for future generations of CPU


Acknowledgements

Contactsjean-pierre tranier@airliquide comjean [email protected]

[email protected]@airliquide.com

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