1. CO 2 Capture from Gasification Syngas via Cyclic Carbonation / Calcination Robert Symonds, University of Ottawa Supervisors Dr. A. Macchi Dr. E. J. Anthony Robin Hughes CANMET NRCan

2. Overview Introduction Hydrogen production in Canadian context Objectives Experimental Method Results Kinetic parameters Sorbent decay Morphology Observations Operational CANMET pilot facilities for CO 2 looping studies Summer 2008 Testing

3. Introduction - Gasification In Canada, very large quantities of H 2 will be produced via gasification for heavy and ultra heavy oil upgrading, power production, and possibly transportation The production of syngas (mainly CO and H 2 ) from a number of carbonaceous fuel sources including coal, petroleum coke, oil, asphaltenes, and biomass occurs via: 3C + O 2 + H 2 O -> 3CO + H 2 The syngas can be shifted to hydrogen via the water-gas shift reaction in the presence of steam CO + H 2 O -> CO 2 + H 2 The production of hydrogen via gasification results in high CO 2 emissions unless the CO 2 can be sequestered

4. Oil Sands – Need low cost hydrogen Production and upgrading facilities are expected to grow by a factor of 5 over the next 25 years. Aggregate Production Forecast: 2003 – 1.1 million b/d 2012 – 2.0 million b/d 2030 – 5.0 million b/d Natural gas price is volatile and supply will diminish; Will need alternative fuels (coal, petroleum coke and refinery residues) to meet the demand; however, Higher carbon fuels will increase CO 2 emissions H 2 Production for Oil Sands using Gasification

5. H 2 Production Comparison CO 2 emissions are increased when producing H 2 from asphaltenes and pet coke when compared to natural gas If 90% CO 2 capture with gasification assumed then emissions are less than SMR with natural gas Gasification for hydrogen with CO 2 capture and compression (ex. 150 bar) is less energy intensive and more cost effective W/O CO 2 CaptureW/ 90% CO 2 Capture Source: White 2007, Air Products CO 2 emission, tonne/kNm 3 H 2 SMR, NG0.9 Asphaltene gasification1.3 Pet coke gasification1.8 CO 2 emission, tonne/kNm 3 H 2 SMR, NG0.37 Asphaltene gasification0.17 Pet coke gasification0.19

6. Canadian Gasification with CCS EPCOR - 90% CO 2 capture Genesee 4 – 500 MW coal IGCC for electrical power production Front end engineering design underway FEED funding industrial/provincial/federal 8000 TPD coal Sherritt – ~4.5 Mt/yr CO 2 Dodds-Roundhill – 270 MSCFD hydrogen production via coal gasification Hydrogen to be used for oil sands upgrading Opti-Nexen – Long Lake project Oil sands operator producing very high quality synthetic crude oil Gasifying asphaltenes for H 2, steam, and power Phase I includes 4 Shell gasifiers

7. Introduction - CO 2 Sorbents Investigating methods for syngas CO 2 separation that can be performed at high temperature and pressure Metal oxides have high equilibrium capacities. Can generate a nearly pure stream of CO 2 (>85 %) needed for sequestration

8. Objectives Determine the effect of ‘slagging gasifier’ syngas on carbonation reaction kinetics for naturally occurring calcium oxide based sorbents. Determine reaction kinetics for the development of a single phase, plug flow, moving bed carbonator reactor model. Perform sensitivity / parametric analysis of carbonator reactor model.

9. Experimental Equipment – TGA

10. Measurement Techniques – Limestone

11. Experimental Conditions Naturally occurring calcium oxide based sorbents Havelock Limestone Newfoundland Dolomite Particle size range 250 – 425 micron

12. Experimental Conditions Feed Gas – Carbonation GE gasifier with Illinois bituminous coal as a feed (Simbeck et al., 1993) CH 4, H 2 S, NH 3, and HCN have been omitted from the syngas feed stream

13. Experimental Conditions Temperature – Carbonation 580, 620, 660, 700 o C Feed Gas – Calcination N 2 CO 2 and N 2 (similar to Abanades et al., 2003) Temperature - Calcination 850 and 915 o C Atmospheric pressure, 10 cycles

14. Rate of Reaction Reaction rate given by maximum slope for grain model

15. Effect of Carbonation Feed Gas Presence of CO/H 2 have increased the initial rate of carbonation by 70% Increased local CO 2 concentration at CaO surface? Believe CaO or an impurity may be catalyzing the water-gas shift reaction Calculated activation energies are 60.3 and 29.7 kJ/mol with and without the presence of CO and H 2 during carbonation Sun et al. (2008) determined activation energy was 29 ± 4 kJ/mol without CO/H 2

16. Sorbent Decay Presence of CO and H 2 during the carbonation of Havelock particles have little impact on the CaO conversion over 10 cycles Expected since particle sintering should be similar based on identical calcination conditions, but sorbent morphology indicates physical differences

17. Sorbent Decay - Gas Composition

18. Presence of Steam The presence of steam increases the carbonation conversion by approximately 30% at the end of the 10 th cycle Several authors (Lin et al., 2005 and Gupta et al., 2002) observed a significant increase in CaO conversion via the intermediate formation of Ca(OH) 2 but neither these processes lie within the carbonation conditions explored in this work In a recent study on sulphation under oxy-fired conditions evidence was advanced for the transient formation of Ca(OH) 2, with an effect on carbonation (Wang et al., 2008) The addition of steam seems to result in the creation of larger pores

19. Sorbent Decay - Temperature 250-425 micron Havelock calcined at 850 C with N 2, carbonated with 8% CO 2, 21% H 2, 42% CO, 17% H 2 O, and 12% N 2

20. Sorbent Morphology Calcined at 850 C with N 2 and carbonated at 580 C with 8% CO 2, 17% H 2 O, and 75% N 2 Calcined at 850 C with N 2 and carbonated at 580 C with 8% CO 2, 21% H 2, 42% CO, 17% H 2 O, and 12% N 2 After 10 cycles of calcination/carbonation

21. Sorbent Morphology Calcined at 850 C with N 2 and carbonated at 580 C with 8% CO 2, 17% H 2 O, and 75% N 2 Calcined at 850 C with N 2 and carbonated at 580 C with 8% CO 2, 21% H 2, 42% CO, 17% H 2 O, and 12% N 2 After 10 cycles of calcination/carbonation

22. Calcination Under a 90% percent atmosphere of CO 2, the initial rate of carbonation is 1/5 that of calcination with pure N 2. It is known that during sintering, necks develop between adjacent micrograins and continue to grow. The material for this is supplied from the rest of the micrograin, so that the distance between grain centers is diminished. This causes both the voidage and the surface area to decrease (Stanmore and Gilot, 2005).

23. Sorbent Morphology Images after first calcination/carbonation cycle Calcined at 915 C and carbonated at 620 C with 8% CO 2, 21% H 2, 42% CO, 17% H 2 O, and 12% N 2 Calcined under N 2; kept under CO 2 until temperature ready for calcine Calcined under 90% CO 2 ; balance N 2

24. CO 2 Looping Cycle Pilot Plant Sorbent Flue Gas Fuel Fresh Loaded Regenerated Coal Coke Air Oxygen Low CO 2 (< 5%) High CO 2 (~92%) Oxidant Oxy-Fuel CFB Calciner Air Blown Combustor Carbonator

25. Our small oxy-fuel CFBC Current Configuration 5 m in height, 0.1 m ID 18 kW of electric heaters surrounding dense bed region Primary and secondary oxidant ports with flue gas dilution Independent fuel and sorbent injection Recycle system includes condenser, condensate KO, and blower Utilities include steam, water & air Fluidizing gas 65+ mol% O 2 BFB or CFB

26. Oxy-Fired Circulating Fluidized Bed (CFB) 10 m; 0.6 m ID Maximum oxygen flow 250 kg/hr Currently set up for a maximum oxygen concentration of 27 mol% 1 m BFB adjacent with solids transport lines BFB opeated as a gasifier or combustor Previously operated as an Exxon style fluid bed coker (5 years) Proposal submitted for CO 2 looping in this facility

27. Effect of Hydration Hydrated Cadomin limestone derived sorbent conversion to CaCO 3 at various conditions Conversion as high as 0.57 after 20 cycles Sorbent was likely too friable for commercialization No SO 2 in sample gases Calcined in N 2

28. Sorbent Pelletization Conversion Cycle Number

29. Pilot Scale Work Summer 2008 Objective Investigate CO 2 capture processes at pilot scale under atmospheric pressure; flue gas & syngas Experimental equipment Batch or continuous operations in 0.1 m ID fluidized beds Calcine with oxy-fired wood pellets with recycled flue gas (dry recycle, O 2 up to 65 mol%) Carbonate with mildly fluidized or moving bed gas velocities Rotary tube furnace Pretreatment or periodic treatment Max 1400 C; 21 kW 1 m heated length; 1 - 5 rpm Can add steam etc. to heated zone Early results Tests to date with air/CO 2 /H 2 O Steam allowing CO 2 capture at equilibrium levels even below 580 C

30. Contact Robin Hughes, CANMET rhughes@nrcan.gc.ca Dr. E. J. Anthony, CANMET banthony@nrcan.gc.ca

31. Results and Discussion – Comparison of Calcium Oxide based Sorbents

32. Results and Discussion – Naturally Occurring Dolomite

33. Results and Discussion – Comparison of Calcium Oxide based Sorbents

34. Carbonation Temp Havelock Limestone