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CSIRO ENERGY TECHNOLOGY / ADVANCED COAL TECHNOLOGY

Post-combustion capture technology development for Australian coal fired power plants Paul Feron – Research Program Leader/PCC Stream Leader 04 June 2012

International Advanced Coal Technologies 04 June 2012

Content Presentation

Introduction Overview of PCC programme at CSIRO Pilot plants

• Loy Yang A Power Station • Delta Electricity Munmorah Power Station • Stanwell’s Tarong Power Station Summary

CO2-Capture and Storage: Decarbonisation of fossil fuel chain

CCS = Capture+Transport+Storage

CO2-storage least understood, hence main R&D topic

CO2-transport: Available technologies, but requires infrastructure

CO2-capture technologies available, but relatively expensive



Decarbonisation routes for power plants

air separation

energy conversion

air

fuel

N2 CO2

powerO2

fuel conversion

CO2

separation

air

fuel

power

flue gasenergy

conversionH2

air

CO2

energy conversion

CO2

separation

air

fuel

power CO2

flue gas

Post-combustion

CO2-N2 separation

Pre-combustion

CO2-H2 separation H2-CO, O2/N2 separation

Denitrogenation

O2/N2 separation

Leading PCC technology is liquid absorbent based


Why liquid absorbent based PCC process?


PRO CON

Low technology risk High cost

Flexible operation, in tune with market requirements

Loss of generation efficiency

Ability to adopt technology improvements

Not demonstrated in integrated power plants scale

New and retrofit applications Sensitive to O2, SOx and other flue gas constituents


Key projects in CSIRO’s PCC program

PCC

Pilot plants Research & Development

Delta Electricity

Loy Yang Power

China Huaneng

Tarong Energy

Novel solvents CET Ionic liquids

CET

Novel processes CET

Economics & Integration CET

Solvent synthesis CMSE

Adsorbents CESRE

Environmental impacts CET

Enzymes

CES

Learning by doing Learning by searching


Established Pilot Plants in Australia

2008

2009

2010


Loy Yang A Power Station PCC Pilot Plant Victoria

ETIS support Lignite Amine based No FGD/DeNox Operational May 08

Presenter

Presentation Notes

Will start off with the Loy Yang pilot plant. This is part of the La Trobe Valley Post Combustion Capture Project which is in collaboration with Loy Yang Power, International Power, the CO2 CRC and CSIRO and is funded by the Victorian Government Energy Technology Innovation Strategy It was the first pilot plant designed and built by CSIRO. It was designed to be transportable Loy Yang power station is a brown coal fired, and has no FGD or deNOx technologies. The pilot plant is an amine based plant, with a design capacity of 1000 tpa It was designed for solvent testing. The pilot plant was established on site in Jan 2008, with the pilot plant operational and the first CO2 captured in May 2008. They are currently well into their research program, which is set to continue through until mid-2010?


CSIRO PCC Pilot Plant @ Loy Yang A Simplified Process Flow Diagram

P-9

Steam

Condensate

Reboiler (plate type)

Stripper

Absorber 1Absorber 2

Solvent make-up

Tank

Make-up

Flue gas

Treated flue gas

CO2 product

Make-up NaOH

Spent NaOH recycled

Knock-out drum

Blower

Condensates and Particulates

Flue Gas pre-treatment

Gas sampling Solvent sampling

Presenter

Presentation Notes

Stripper temperatue = 116 deg C/ pressure = 1.5 bar Gas flow rate 125 – 140 m3/h

7 campaigns with different solvents completed

• 30% MEA (Design basis) • MEA/AMP • PZ/AMP • Proprietary developmental solvent

Outcomes

• > 85% CO2 recovery with purity > 99.5 % • Solvent performances ranked • MEA performances validated • Pilot plant has undergone several

modifications to enable efficient 24/7 operation

Research overview Loy Yang pilot plant


50

60

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90

100

1.5 2.0 2.5 3.0 3.5 4.0 4.5

L/G (L/Nm³)

CO2 r

ecov

ery

(%)

Liquid analysis CO2 product based treated flue gas based

4.0

4.5

5.0

5.5

6.0

1.5 2.0 2.5 3.0 3.5 4.0 4.5

L/G (L/Nm³)

Reb

oile

r hea

t dut

y (M

J/kg

CO

2)

(75%)

(72%)(60%)

(69%)

(81%)

(83%)

(83%)

(84%)

(90%)

(89%)

Artanto, et al., 2009

http://www.rite.or.jp/top_e.html

Collaboration with EU consortium in the iCap

project. • CSIRO is part of an Australian consortium (coCAPco)

working with iCap • Aim to develop and test a combined CO2 and SO2 control

process

PCC process emissions assessment • Experimental campaign dedicated towards sampling and

analysis of emissions from an MEA based PCC process

Future activities with CSIRO pilot plant at Loy Yang



Munmorah Power Station PCC Pilot Plant New South Wales

APP support Black coal Aqueous ammonia based No FGD/DeNox Operational Feb 09

Presenter

Presentation Notes

The Munmorah power station is black coal fired and has no FGD or de-NOx technologies The pilot plant is an ammonia based plant, with a design capacity of 3000 tpa Funding through Australian Government (APP Cleaner Fossil Fuel Taskforce) Plant was established on site in Jul 2008. First CO2 captured in Feb 2009. Current experimental program set to run through till mid-2010 Advantages - Low cost solvent; Does not degrade in the presence of oxygen; High CO2 loading capacity; Less corrosive and so less damaging to equipment; Potential to remove multiple components (SOx, NOx and CO2) simultaneously and produce value added products Challenges - Loss of ammonia; Accommodate low temperature flue gas, precipitate formation Currently going through a series of campaigns to improve our understanding of the process and determine whether it is a suitable technology for Australia

How aqueous ammonia based PCC works


NH3/(NH4)2CO3 Lean solvent

NH4HCO3 Rich Solvent

CO2

Flue gas in

Flue gas out

Absorber Stripper

2HOC2H4NH2 + CO2 HOC2H4NHCOO- + HOC2H4NH3

+ (MEA) (Carbamate)

NH3 + H2O + CO2 { NH4

+ + HCO3

- (bicarbonate)

NH4++NH2COO- (carbamate)

NH4+

+ CO32- (carbonate) }

NH4HCO3

(NH4)2CO3

NH2COONH4

Solid precipitation

Presenter

Presentation Notes

The process is a cyclic process, firstly in a gas liquid contactor, so called absorber, in which flue gas from power stations make a contact with ammonia solvent (lean in co2, lean solvent), at low temperature below 30oc, at this low temperature, co2 with react with nh3 solution, which drive co2 from gas to liquid. Gas is purified, the solvent is rich in CO2. it is then heated up, moved to another gas liquid contactor, stripper, desorber, regenerator. At high temperatures, co2 is released from solution, the solvent has less co2 and become lean solvent, starting another cycle. Nh3 is the simplest amine if you like. Normally amines, such as MEA, monoethananol amine, its reaction with co2 leads to formation of carbamate, while Nh3 with CO2 is not straight forward. Depending on the absorption conditons, it could lead to formation of bi, carbo, carba, with increase in nh3 and Co2 content in solution and decrease in solvent T, solid could precipitate. The process is complex but it gives an option to adjust conditions to achieve desirable results.

Aqueous ammonia, an emerging, challenging, promising solvent for PCC


Why ammonia Low cost Robust, more benign than other amines High CO2 loading capacity Low regeneration energy Potential to remove multi-components (SOx, NOx and CO2)

simultaneously and produce value added products Why not ammonia

Loss of ammonia Accommodate low temperature flue gas Slow absorption rate

Presenter

Presentation Notes

NH3 is an emerging solvent for PCC it has its potential but also challenges as well. Ammonia probably most cheapest chemical solvent, aqueous ammonia solvent 10 times less than reference solvent, monoethanaoamine (MEA), it is stable, does not decompose, degrade in the presence of o2 and other components present in flue gas at high temperatures. There is a concern that the amines can degrade and produce some other chemicals even carcinogenic chemicals, nitrosamine. Environmental and health impact of ammonia is well studied. Nh3 also has high loading capacity, potentially double than MEA, half the regeneration energies. In Aus, there is deno and desox facility installed, use of nh3 possibly could combine deNOX Desox and co2 in one process and produce . Otherwise, you might have to install deso deno and then doso2. But nh3 has its inherent issue. On the other hand, nh3 is volatile.

Technical feasibility of aqueous ammonia for PCC demonstrated CO2-capture efficiency in excess of 90% was achieved CO2 product quality ~ 99.8%; Regeneration at elevated pressure achieved SO2 was completed removed, little NOx removal Low absorption rates and ammonia losses are concern Precipitation was observed in the stripper condenser

Research overview Delta Electricity pilot plant


Average CO2 loading of solvent

0.0 0.2 0.4 0.6 0.8

Ove

rall

gas

mas

s tra

nsfe

r coe

ffici

etm

mol

/(s m

2 kPa

)

0.0

0.2

0.4

0.6

0.8

1.0

2-3 wt% NH3

4-5 wt% NH3

5 wt% NH Wetted Wall Column at 10oC

Hai Yu et al., 2010

P-3

Water Tank

Pretreatment column Absorber

Wash column

Flue gas

Lean solvent

Rich solvent

Time 08:00 10:00 12:00 02:00

SO

2, pp

m

0

50

100

150

200

250

300

Prereatment inletPretreatment outlet

SO2-removal CO2 mass transfer

Further trials after the plant is relocated to Vales Point Power Station as part of a Coal Innovation NSW Project

• Informing selection/design of demonstration scale PCC plant in NSW

Planned trials will include: • Solar thermal energy for solvent regeneration • Impact of flue gas impurities • Evaluation of solid sorbents in real flue gases

Further trials might include: • Improved aqueous ammonia process • Evaluation of liquid absorbents for the NSW PCC demonstration

project

Future activities with Delta Electricity pilot plant


Tarong Power Station PCC Pilot Plant Queensland, Australia

APP support Black coal Amine based No FGD/DeNox Commissioned November 2010


Presenter

Presentation Notes

Our third Australian pilot plant is located at Tarong power station in Queenslands It is also funded by the Australian government through the Asia Pacific Partnership Cleaner Fossil Fuel Taskforce The Tarong power station is a black coal fired power station and has no de-SOx or de-NOx technologies installed, although they have recently installed low NOx burners The pilot plant is amine based with a design capacity of 1000 tpa This pilot plant design was maintained as flexible as possible to allow testing of process modifications The pilot plant is currently in its commissioning phase, and they should begin running MEA through the plant sometime this week. The current experimental program is set to continue through to June next year.

http://www.stanwell.com/Default.aspx

Research overview Tarong pilot plant Alternative process configurations tested:

rich split, inter-stage cooling and split flow


Cousins et al., 2012

http://en.wikipedia.org/wiki/File:Ethanolamine-3D-balls.png

http://en.wikipedia.org/wiki/File:Ethanolamine-2D-skeletal-B.png


Process modification testing – rich split


Process modification testing – rich split

75

80

85

90

95

100

105

110

115

0 5 10 15 20 25 30 35 40 45 50

Split fraction (mass%)

Sol

vent

rege

nera

tion

ener

gy (k

W)

Split data 0% Split

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25 30 35 40

Split fraction (mass %)

% o

f coo

ling

wat

er re

quire

men

t com

pare

d to

sta

ndar

d op

erat

ion

Split data 0% Split

Collaboration with University of Texas to enable trials with

concentrated piperazine High pressure and temperature regeneration Potentially lower regeneration energy solvent cf. MEA More stable (thermal/chemical) Low vapour pressure (reduced environmental emissions)

More modifications will be tested to provide experimental evidence on process modifications to reduce the energy consumption

Future activities with Tarong pilot plant


http://en.wikipedia.org/wiki/File:Piperazine-3D-balls-B.png

http://en.wikipedia.org/wiki/File:Piperazine_structure.svg

Pilot plant summary

Plant Loy Yang Munmorah -> Vales Point

Tarong Newcastle PDF

Solvent Amine Ammonia/Amine Amine Both

Flue gas source brown coal black coal black coal Synthetic

Scale 50 kg/hr 300 kg/hr 100 kg/hr 20 kg/hr

Focus solvent benchmarking

ammonia operation

process optimisation

process development

Other activities emission study solar thermal integration

Novel solvent cutting edge processes

Matrix approach helps cover many aspects of PCC as well as providing quicker delivery of information


Presenter

Presentation Notes

This slide covers some of the key points we have learnt to date through our PCC research programe firstly, PCC using liquid absorbent based technology is a viable option to capturing CO2 from flue gases from both brown and black coal fired power plants in Australia. With current technologies, the costs for PCC are between $60 and $110 per tonne CO2 avoided for the standard liquid absorbent. There is a sizeable scope for reduction of these costs. Cost reductions can be achieved by a further focus on reduction of the capital costs in addition to the reduction of the energy penalty. The flue gas quality of Australian power plants is such that FGD and possibly De-NOX need to be installed to enable the current commercially available PCC processes. This emphasises the need for more robust liquid absorbent technologies, which avoid the use of a separate FGD step. The nature, extent and environmental impacts resulting from PCC processes are not well understood and is an area that needs further investigation.


PCC Pilot Plant Research Summary CSIRO PCC Pilot plant programme is unique in depth and breadth Considerable PCC infrastructure now available Post-combustion CO2 capture demonstrated on:

• 3 different power plants in Australia • 6 different amine based absorbents, including ammonia

Process performances validated through modelling where possible

• Lends credibility to scale-up and costing studies • Process modifications illustrate performance improvements

Aqueous ammonia requires considerable performance improvements Establishment of international links with leading groups in the APP region and Europe

Thank you CSIRO Energy Technology Paul Feron OCE Science Leader t +61 2 4960 6022 e [email protected] w www.csiro.au/science/Post-combustion-capture.html

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