Steam Reactivation of Spent CaO-based Sorbent for Multiple CO2 Capture Cycles - SUPPORTING INFORMATION - by VASILIJE MANOVIC AND EDWARD J. ANTHONY* CANMET Energy Technology Centre-Ottawa, Natural Resources Canada 1 Haanel Drive, Ottawa, Ontario, Canada K1A 1M1 8 Pages, 3 Tables and 6 Figures * Corresponding author e-mail: banthony@nrcan.gc.ca; tel.: (613)996-2868; fax: (613)992-9335. S1 TABLE S1. Results of TGA analyses of sorbent hydrated after CO2 cyclesa Sample KR37 (75-150 μm) KR38 (300-425 μm) KR39 (600-750 μm) KR40 (75-150 μm) KR41 (300-425 μm) KR42 (600-750 μm) CaO sulphated (%) 29.77 28.09 26.59 0.00 0.00 0.00 CaO carbonated (%) CaO hydrated CaO unreacted (%) (%) Before After 4.69 10.44 50.66 9.13 4.08 8.72 53.98 9.21 4.86 9.60 55.76 8.05 19.31 24.80 68.74 6.46 14.60 18.98 70.74 10.28 16.46 20.76 70.55 8.68 a The values of CaO sulphated were calculated on the basis of mass increment at end of sulphation step and represent the CaSO4/totalCaO molar ratio. The values of CaO hydrated and carbonated were calculated on the basis of mass loss in the TGA experiments, which correspond to the Ca(OH)2 and CaCO3 decomposition and represent the Ca(OH)2/totalCaO and CaCO3/totalCaO molar ratio, respectively. The values of CaO unreacted are calculated by difference. TABLE S2. Behavior of Kelly Rock limestone in cyclic carbonation – short cycles Sample KR01 (75-150 μm) KR02 (300-425 μm) KR03 (600-750 μm) X1-2 (%) 64.75 64.89 66.50 X9-10 (%) 31.13 38.72 35.82 X29-30 (%) 24.95 29.32 27.02 X1-10 (%) 44.03 48.83 47.17 X1-30 (%) 32.10 37.17 36.98 TABLE S3. Results of TGA analysesb of sorbent calcined/sintered under different conditions and hydrated, where some fraction of CO2 in samples is probably result of reaction with CO2 in air during sample manipulation Sample KR43 (75-150 μm) KR44 (300-425 μm) KR45 (600-750 μm) KR46 (75-150 μm) KR47 (300-425 μm) KR48 (600-750 μm) KR49 (75-150 μm) KR50 (300-425 μm) KR51 (600-750 μm) b Conditions during CaO carbonated CaO hydrated CaO unreacted calcination/sintering (%) (%) (%) 1100°C, 24 h 5.88 82.50 11.62 1100°C, 24 h 2.42 83.02 14.56 1100°C, 24 h 2.85 81.59 15.56 850°C, 24 h 8.62 80.15 11.23 850°C, 24 h 3.67 88.62 7.71 850°C, 24 h 4.36 91.89 3.75 850°C, 2 h 5.75 87.86 6.39 850°C, 2 h 4.19 88.59 7.22 850°C, 2 h 5.18 87.89 6.93 The values of CaO hydrated and carbonated were calculated in the same way as in Table S1. S2 100 KR01 (0.075-0.150 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] a) 100 KR02 (0.300-0.425 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] b) 100 KR03 (0.600-0.750 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 c) 50 100 150 200 250 300 350 400 450 Time [min] FIGURE S1. TGA calcination/carbonation results for original limestone, particle size: 75150 μm (a), 300-425 μm (b), and 600-750 μm (c). S3 100 KR38 (0.300-0.425 mm), 28.09% sulfated Total CaO utilization [%] 90 80 70 60 50 40 30 20 Irreversibly used part of CaO in form of CaSO4 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] a) 100 KR39 (0.600-0.750 mm), 26.59% sulfated Total CaO utilization [%] 90 80 70 60 50 40 30 20 Irreversibly used part of CaO in form of CaSO4 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] b) FIGURE S2. TGA calcination/carbonation results for reactivated partially sulphated spent sorbent, particle size: 300-425 μm (a), and 600-750 μm (b). S4 100 KR40 (0.075-0.150 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] a) 100 KR41 (0.300-0.425 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] b) 100 KR42 (0.600-0.750 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] c) FIGURE S3. TGA calcination/carbonation results for reactivated unsulphated spent sorbent, particle size: 75-150 μm (a), 300-425 μm (b), and 600-750 μm (c). S5 100 KR01 (0.075-0.150 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 Time [min] a) 100 KR02 (0.300-0.425 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 Time [min] b) 100 KR03 (0.600-0.750 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 Time [min] c) FIGURE S4. TGA calcination/carbonation results for original limestone – 30 short-time cycles, particle size: 75-150 μm (a), 300-425 μm (b), and 600-750 μm (c). S6 100 KR43 (0.075-0.150 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] a) 100 KR44 (0.300-0.425 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] b) 100 KR45 (0.600-0.750 mm) Carbonation degree [%] 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 400 450 Time [min] c) FIGURE S5. TGA calcination/carbonation results for sorbent sintered at 1100°C, 24 h, and reactivated, particle size: 75-150 μm (a), 300-425 μm (b), and 600-750 μm (c). S7 a) b) c) d) FIGURE S6. SEM images of spent sorbent (a – sulphated, b – unsulphated) and reactivated sorbent after calcination (c – sulphated, d – unsulphated) S8