CSIRO PCC Pilot Plant Activities in Australia

Aaron Cottrell 19th May 2011 – Abu Dhabi, United Arab Emirates

1st Post Combustion Capture Conference The role of coal in Australia

Australia is heavily dependant on coal for electricity production Large reserves of coal will likely mean future power stations will be coal based

Electricity production ~ 261TWh CO2 emissions from electricity production ~ 235 Mt CO2

Other Other NG

Brown Coal Black Coal Black Coal

Brown Coal

Abare data : 2008-2009 PCC application in Australian coal fired power stations Generation capacity ~ 28 GW Electricity production 201 TWh Average generation efficiency

• Black coal: 35.6% - 0.9 tonne CO2/MWh • Brown coal: 25.7% - 1.3 tonne CO2/MWh CO2-emissions ~ 202 Mtonne CO2/a from ~ 60 flue gas streams SO2 levels: • Black coal: 200 - 600 ppm No FGD • Brown coal: 100 - 300 ppm

NOx levels: • Black coal: 300-700 ppm No DeNOx • Brown coal: 100-200 ppm +90% NO Flue gas temperature • Black coal: 120 oC High flue gas temps • Brown coal: 180 oC Cooling water: 1.5-3.0 m3/MWh

Data used from CCSD – technology assessment report 62 Opportunities for PCC in Australia

Only practical option for existing plants to substantially reduce CO2 intensity Potential for “all in one” multi pollutant control technology Compared to competing technologies, has high flexibility & adaptability • staged implementation, zero to full capture operation to match market conditions

• applicable to most stationary sources of CO2 emissions Special synergies with renewable energy • direct solar integration (provision of low temperature heat for solvent regeneration avoids reducing output of power station) • grid integration (provides a discretionary load to balance intermittency) Potential water production source Potential waste heat recovery options Integrated PCC R&D Programme

Pilot plant programme (Learning by doing)  Hands-on experience for future operators  Identification of operational issues and requirements  Testing of existing and new technologies under real conditions

Lab research programme (Learning by searching)  Support to pilot plant operation and interpretation of results  Develop novel solvents and solvent systems which result in lower costs for capture  Addressing Australian specifics (flue gases, water) PCC Programme Overview

PCC Learning by doing Learning by searching

Pilot plants Research & Development

Novel solvents Loy Yang Power CET Ionic liquids CET Adsorbents E&M Delta Electricity Enzymes Solvent synthesis ENT CMHT China Huaneng Novel processes Environmental impacts CET CET Tarong Energy Economics & Integration CET Pilot plant summary

Plant Loy Yang Munmorah Tarong Newcastle mini

Solvent Amine Ammonia Amine Both

Flue gas brown coal black coal Black coal Artificial source Scale 50 kg/hr 300kg/hr 100kg/hr 20 kg/hr

Focus solvent ammonia process process benchmarking operation optimisation development Other emission pressurised Solar thermal Cutting edge activities study absorption integration processes • Pilot work by nature is slow to deliver results • Matrix approach helps cover many aspects of PCC as well as providing quicker delivery of information • Multiple plants provide extra exposure for power generators Key gas analysis equipment

 Each pilot plant has sophisticated FTIR gas analysis equipment (Gasmet).  Enables online sampling of up to 8 different location on the plant  Currently includes spectra for calculating online concentration of CO2, H2O, CO, NO2, NO, N2O, SO2, HCl, HF, NH3, MEA, PZ and a number of breakdown products  Overall spectra are saved and can be analysed for other “unknown” constituents at a later date.  Highly valuable for measuring plant performance, safety and water balancing Loy Yang Power Station PCC Pilot Plant Victoria, Australia

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

• Develop experience operating PCC on brown coal flue gas • Strong focus on solvent testing and benchmarking • Identification of cost-effective options for reduction of

CO2-emissions in Victorian brown coal fired power stations

• Determine effects of CO2-concentration, moisture content, SOx, NOx and fly-ash on sorbent systems and novel separation technologies • Technical and economical assessment based on results from pilots and laboratory research Loy Yang Pilot Plant design

Basis of Design:

Two absorbers with CO2 capacity up to 50 kg/hr Each has 2 beds of 1.35 m packed with 5/8” Pall rings – 338 m2/m3, ID 211 mm Stripper: 3.9 m bed with Pall rings, ID 161 mm

Flue gas composition (11% CO2, 30% H2O) MEA concentration (30%)

Operation Conditions: Reboiler temperatures: 100 – 120 °C Stripper pressures: 1 - 2 bar Flue gas temperatures: < 180 °C

Objectives: determine Mass & Heat balances for the plant

determine CO2 recovery and CO2-product quality determine thermal and electrical energy requirements of the pilot plant Some results from the Loy Yang pilot plant

Liquid analysis CO2 product based treated flue gas based

100

• First CO2 capture in May 2008 90

• Able to successfully close 80 recovery (%) mass balances over the plant. 2 70 CO

Agreement between different 60 methods for determining plant 50 CO2 recovery 1.5 2.0 2.5 3.0 3.5 4.0 4.5 L/G (L/Nm³) Effect of L/G ratio of CO2 recovery • Effect of various operating 6.0 (69%) ) conditions of plant 2 (60%) (72%) 5.5 performance observed (e.g. (90%) (75%) (83%) effect of L/G ratio on CO (89%) 2 5.0 (81%) recovery and reboiler duty (84%) (83%)

4.5 Reboiler heat duty (MJ/kg CO (MJ/kg duty heat Reboiler Artanto et. al. 2009

4.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 Effect of L/G ratio of Reboiler duty L/G (L/Nm³) Conclusions/Remarks on Solvent bench-marking

• MEA has been used as a base case - minimum in pilot: 4.3 MJ/kgCO2

• MEA + AMP and AMP + PZ were used as amine blends and showed decreased heat duty of 10-30%. Kinetics dropped considerably though;

• The RITE solvent, a proprietary amine blend, shows a 20-34% decrease of the heat duty and combines that with seemingly good kinetics;

• Design choices such as packing height, based on MEA properties, has affected the optimal performance of slower reacting, low energy consuming solvents. The brown-coal case demands low investment costs, hence high reactive solvents;

• Operational issues such as viscosity limits and potential corrosion have limited the impact of results. Key learnings from LVPCC project

1. Due to the relatively cheap brown coal supply, cost reductions can be achieved by a focus on reduction of the capital costs and to a lesser extent on the reduction of the energy penalty. • Solvents with better kinetics • Solvents with lower vapour pressures • Thermally stable solvents • Cheaper materials for plant construction • Simple process design

2. Requirement of FGD and DeNOx may mean PCC for brown coal not feasible. “All in one” technology may have merit. • Once again capital driven • Less efficient solvent capable of multi pollutant control may be key • Maybe by-products give value Ongoing Research • Original ETIS project has been completed • Ongoing solvent testing and benchmarking • Detailed investigation of PCC emissions - quantify environmental impact of PCC - determine any associated control technologies are required • Collaboration with an EU consortium in the iCap project. - CSIRO will form part of an Australian consortium called coCAPco working with iCap - aim to develop and test a combined CO2 and SO2 capture process with stepwise regeneration. Munmorah Power Station PCC Pilot Plant New South Wales, Australia

APP support Black coal Aqueous ammonia based No FGD/DeNox Operational Feb 09 Why ammonia for PCC?

•Ammonia is a relatively cheap liquid absorbent.

•Ammonia is robust and not subject to degradation unlike other amines.

•Multi pollutant control – lower capital costs

•Potential for reduced energy consumption in solvent regeneration

•Potential for more efficient compression via high pressure regeneration pressure

•Potential income stream from ammonium sulfate and ammonium nitrate by-products Munmorah Pilot Plant design

Basis of Design:

Two absorbers with CO2 capacity up to 150 kg/hr Each has 2 beds of 1-2 m packed with 1” Pall rings – 207 m2/m3, ID 600 mm Stripper: 3.5 m bed with Pall rings, ID 400 mm

Flue gas composition (11% CO2, 30% H2O) MEA concentration (30%)

Operation Conditions: Reboiler temperatures: 100 – 180 °C Stripper pressures: 1 - 10 bar Flue gas temperatures: < 120 °C

Objectives: determine Mass & Heat balances for the plant

determine CO2 recovery and CO2-product quality determine thermal and electrical energy requirements of the pilot plant Finding the right balance

Smaller absorber (low capital cost), high Large absorber (high capital cost), lower operating cost and high solvent loss operating cost and lower solvent loss Some results

Ammonia losses in absorber Precipitation of solids in condenser

Measured and equilibrium ammonia concentrations in the flue gas at the outlet of absorber as a function of CO2 loading of lean solvent. Expt: 15-20oC; Model: 15oC. Key Outcomes of the Munmorah Pilot Plant

Benefits of aqueous ammonia process are confirmed ……. but further challenges also revealed: • The ammonia losses, as a result of its high volatility, can be substantial (depending on the operating conditions) necessitates the installation of a comprehensive gas washing and ammonia recovery/neutralisation system. operation at low temperature – refrigeration is expensive to buy and run • The CO2 absorption rates are low larger absorbers compared to the standard amine processes. effect on investment costs? • Matching operation to regular amine processes formation of ammonium-bicarbonate solids. blockage of the condenser – significant operational issue • May still be cost effective multi pollutant process for Australia if we can overcome these challenges with minimal cost Ongoing Research • Original project has been completed • Further trials are set to continue next year after the plant is relocated to Vales Point Power Station as part of a NSW Clean Coal Proposal • Plant to be reconfigured to overcome some existing operating issues • Information gathered to be used in selection/design of demonstration scale PCC plant in NSW • Trials will include: - pressurised absorption in an attempt to increase reaction rates, decrease ammonia slip and decrease the effective absorption column size. - Investigation of other ammonia slip reduction techniques - Potential of other solvents to be trialled also Tarong Power Station PCC Pilot Plant Queensland, Australia

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

• To obtain practical experience with real flue gases from a Tarong Energy’s black coal fired power plant

• To test the performance of pilot plant under nominal conditions

• Focus on process reconfigurations with an aim for optimising the CO2 capture process for minimisation of operating and capital costs

• To compare the results with simulation calculations Tarong pilot plant design

Demister • Pre-Treatment column (flue gas <120°C, 10-12% CO2) packing Condensate bed • 450mm diameter Wash section Structured • 2.7m packed height packing • 1 inch Pall rings

Bed 1 Structured Bed 1 • Absorber column packing Structured packing • 350mm diameter • Total packed height 7.2m (4 sections @ 1.8m each, spare

Bed 2 Structured 3.6m packed section) packing • Wash section packed height 1.6m • Sulzer Mellapak M250X structured packing Bed 2 Structured packing

Bed 3 Structured • Stripping column (up to 10 bar/180°C operation) packing • 250mm diameter

• Total packed height 7.2m (2 sections @ 3.6m each) Bed 4 Structured packing • Condensate packed height ~1m • Sulzer Mellapak M350X structured packing ABS-TNK1 Plant campaigns

• Base case determination • Validate pilot plant design with 30 wt% MEA solution. • Determine CO2 recovery performance • Validate liquid sampling system and gas analysis • Achieve stable operation of pilot plant with 30 wt% MEA solution • Close heat and mass balances • Rich split modification • Absorber intercooling Campaign 2 – Rich split case

• The plant was modified to enable an extra stream coming from the bottom of the absorber to be diverted from before the cross heat exchanger to the top of the absorber column. • The trials measured the change in plant performance by diverting 0-50% of the rich solvent to the top of the stripper column. • The trial showed that some saving could be made for both energy (up to 8%) and water consumption (up to 85% from the stripper condenser) and this aspect should be investigated further. • Stripper operation became unstable at higher diversion rates due to increased steam condensation in the column. • The increased condensation created a flooded region in the column and resulted in surging which caused the instability. Campaign 3 – Absorber intercooling case

• The absorber was modified to allow liquid to be withdrawn from the column, cooled and then reintroduced to the column at the top of the next section of packing. • The plant was run with different cooling water flowrates to try and show a trend in plant performance with absorber intercooling. • Analysis is shows that a small increase in performance can be achieved (2-3%) • Intercooling performance to be studied further with a modified intercooling circuit. • From an operating perspective the plant appeared to reach higher rich solvent loadings and in turn reduce energy requirements as a result of these higher loadings. Heat stable salt measurements

• The plant has run around 800 hours to date on an average flue gas (after treatment) of 5ppm SO2, 180-200ppm NO, ~1ppm NO2 • Solvent not showing any noticeable decrease in performance

0.4

0.35

0.3 Solvent discolouration also observed 0.25 – still to be investigated

0.2

0.15

Heat stable salt concentration (wt%) 0.1

0.05

0 0 100 200 300 400 500 600 Hours of operation Online Gas Analysis Corrosion testing

• Determine the corrosiveness of solvents for the different operating conditions within the plant • Corrosion testing is be conducted at various locations around the plant. • Access points have been included on both the absorber and stripping columns to allow placement of corrosion coupon test racks. • Different metals will be tested from mild steel to 316 stainless steel • Also examine the effects of corrosion of welds • All information collected assists in design and material selection of up coming plants and requirements for different • Corrosion studies are yet to be completed. Current Status and future work

• Unmanned 24hr operation tests complete. More solvent operation hours with no additional staff. • Preparing for tests on concentrated Piperazine in collaboration with University of Texas, DOE, URS and Trimeric • Upgraded cross heat exchanger to minimise approach temperatures • Upgraded intercooling circuit for more efficient cooling • In a couple of months tests on concentrated Piperazine in collaboration with University of Texas, DOE, URS and Trimeric utilising 2 stage flash skid. • Solar thermal integration for regeneration • Other process configurations Novel process development unit

• Located at Newcastle Energy Technology Labs

• Scale between Lab bench scale and Pilot scale

• Modular design

• Flexible operation

• Ventilated & bunded space

• “Controlled” environment PCC Novel Processes Test Facility - contactors

• Detailed profiles in multi- stage systems

• Separate operation of Absorber and Desorber

• Process and contactor options

• Currently being commissioned Learnings to Date from Ongoing Programme

• Liquid absorbent based PCC is a viable option for Australia. • Significant operating and capital costs reductions can be achieved in solvent selection, process configuration • Ammonia has potential to provide a multi pollutant control solution but operating difficulties and solvent losses need to be further addressed. • The flue gas quality of Australian power plants is such that FGD and possibly De-NOX may need to be installed to enable the current commercially available PCC processes to be successful in Australia • The Environmental impacts resulting from PCC processes are not well understood and need further investigation. What’s Next?

• Work closely with power industry and address their concerns • Scaled up demonstration projects are needed to show that CCS technologies work. • Further study into the environmental impacts of large scale CCS • Development of novel solvent processes to reduce capital costs and loss in efficiency • Further understanding of the PCC and renewable energy relationship for Australian conditions – opportunities for load balancing and energy reduction View of Tarong pilot plant CSIRO Energy Technology Aaron Cottrell PCC Pilot Plant Project Manager

Post-combustion CO2 Capture Phone: +61 (0)2 4960 6053 Email: [email protected] Web: www.csiro.au

Thank you