Krean Chem. Eng. Res., Vl. 43, N. 4, August, 2005, pp. 537-541 기포유동층반응기에서건식재생흡수제를이용한이산화탄소회수에미치는스팀및온도의영향 kkç i Ç Ç z * Çmy l v l ~rl vl 305-343 re q 71-2 *r l v 305-380 re v 103-16 (2005 3 25p r, 2005 6 15p }ˆ) Effects f Steam and Temperature n Capture Using A Dry Regenerable Srbent in a Bubbling Fluidized Bed Yngwn Se, Yung Sub Mn, Sung-H J, Chng Kul Ryu* and Chang-Keun Yi Clean Energy Research Center, Krea Institute f Energy Research, 71-2, Jang-dng, Yuseng-gu, Daejen 305-343, Krea *Glbal Envirnment Grup, Krea Electric Pwer Research Institute, 103-16, munji-dng, Yuseng-gu, Daejen 305-380, Krea (Received 25 March 2005; accepted 15 June 2005) k h l l r l p p e rp srba pn l p l p p k. srba ˆ r vv~ l p. 50-70 Cp m l, q p 120-300 Cp m l p lr. peq r srbal pr p p n, 50 Cl p 1-2 k 100Íp r pp m. ml q n e p p rp p r n p r ll. NMR d p p q p e p p Žk m. l l llv p p v l q p m nrl tn q p. Abstract A bubbling fluidized bed reactr was used t study capture frm flue gas using a sdium-based dry regenerable srbent, srba which was manufactured by Krea Electric Pwer Research Institute. A dry srbent, srba, cnsists f fr absrptin and supprters fr mechanical strength. capture was effective in the lwer temperature range f 50-70 C, while regeneratin ccurred in the range f 120-300 C. T increase initial remval, sme amunt f steam was absrbed in the srbents befre injecting simulated flue gas. It was pssible t remve mst fr 1-2 minutes at 50 C and residence time f 2 secnds with steam pretreatment. Little r n reductin in initial reactin rate and capture capacity was bserved in multicycle tests. The carbnated and regenerated srbent samples were analyzed by NMR t cnfirm the extent f reactin. The results btained in this study can be used as basic data fr the scale-up design and peratin f the capture prcess with tw fluidized bed reactrs. Key wrds: Bubbling Fluidized Bed, Carbn Dixide, Dry Srbent, Carbnatin, Regeneratin 1. p ˆ ( ) v m ~ p p d s p p pp t p. 2004 11 ek p Špr t p f r rp l vl k l r l ~ kl p r p t pp } l l l T whm crrespndence shuld be addressed. E-mail: ckyi@kier.re.kr ep p. l de,,, e p p p p p q rp v p. p t p r r~ m n p d } } n } l l v tlk p k. } p erp e p q n e r pn p l eq l [1-6]. e q ~ r pn p r ~m peˆ l d p d p, eˆ pp, q e sp de 537
538 në m Ës Ë ~ Ëp} l v rp ˆl p p lp p., q n r k m k Š p lv p r ml 200 C p p m l nr l p lp lp dp m p nrp. p qr l e q n ~ r pn p r (cst-effective)p r l v (energyefficient)p erp p p. e ~ r pn l p ˆ rp s l r, p,, p p. pp n l pp l rp mp l r ~rp lr p q p lrk, p p tp l p ƒk. p s p se t p p ˆ p m p p [7]. l l p l p m, r} e, q m p l e rp p p k. q e p p Žk l NMRp pn l m. 2. Fig. 1p e l n p e q p lt. q p tn p d tp, p, d } q m d l p. p 0.05 m, p 0.8 mp quartz rq lp r l vp l p. p ~ (Brks, Japan)l r l d l p l. p m r m m rl n l sr mp l lr l m r m. l pp p p m dp p tl p n l l l m v m. e r p l e r r p s v d t m sr m. p l ~ p p r l vp r l. v r d rn (ABB, USA) pn 10 p r m. e l n e ~ r r l (KEPRI)p Fig. 1. Experimental apparatus fr carbnatin and regeneratin. 43 4 2005 8k p srba m r m p p vv~ l p. srba 0.75 p bulk density, 104.6 µmp p 1.0p AI (Attritin Index) v. e l n p m N 2 ~ d d k. e l p l p er nr s p k l p p l p ~ e p 2 v l p l srba 90 gr r m p 0.03 m/s, p m 50 C r m. ~ e r d s p eˆ 10Í, N 2 77.83Í, H 2 O 12.17Í sr m. p kl n p ~(N 2 + ) prm (50 C) v l p ˆ(bubbler)p eˆp f v ˆ p l m. ˆp m l mr l r m er d r l ˆpp p m. ˆp p v p p rl p k m v m. nl p p p p eq r pre k N 2 ~ ˆp l dž p l p f rl pr p p r} m. q p N 2 ~ 3.0 L/minp p t p p m 120 C p p v l p lr. q e p p Žk v l (KBSI, Daegu)p Bruker 400 MHz ~ NMRp n l e m. 13 C NMR d p 10 khzp magic angle spinning(mas)p 100.6 MHzp Lamr frequencyl ll r 1.5 µsp pulse lengthm 100 sp pulse repetitin delay n m. 300 Kl 28.3 ppmp chemical shift v adamantane p n chemical shift tp n l. NMR l q p Se m Lee [8]p l l p. 3. y pn r~ pep k m. (s) + (g) + H 2 O(g) Ë 2NaH (s) H r = 135 kj/ml pp l pp pp n l pp., er rl pl e plp } t n l p np p }p p [7]. Fig. 2 p l srbap -q pp r ~ rp lt. p (dry basis)m p p m e l r m. r 60 kp p rp, 60 p q p rp. l pp p l p p m pe d m 50 C v p p. 0Íp 100Í p r p. m q p l rp p lv q k l l n r pp pv e p v l r v l r pp lv. 8 l perp v ˆl ˆ p d m p m e l
e q r pn p ˆ 539 Fig. 2. cncentratin and reactr temperature during carbnatin-regeneratin cycle (H 2 O pretreatment fr 30 min befre carbnatin, bubbler at 50G C). Fig. 3. Effect f H 2 O pretreatment time n remval (bubbler and reactr at 50G C). 50 C lr p. p r p 10 p l p vp p. p e r n l q p m p n p k p [2, 6]. p p srba l e q l e r n n n p p pp ke. q p 120 C p p m l N 2 3.0 L/minp p t p lr. l m p q l p p p. q l m p k 15Í r m. Fig. 2p -q l p e l r tlv e kp p q p lp p. Fig. 2l 135 Cl 1e kp q p p k 89Í q p l. p tl NMR p p l. Fig. 3p r} e p r pl m p lt p. r} lp ~m p el tp n, l rp 100Íp r pp ˆ p p lv, p r} n 1 p 100Íp r p p m. e tp m p ~p srba p m vr p r} p srbap pl sq p p p s p Ž. srbap p np r q sr l rs l. Fig. 4l p p ˆ m 50 Cl 3.0 L/minp p r} nl k 20 r p r} e p p r p l p p. qe p r} srbap p l p pp p slp p p l rr r} e p ˆ k. erp l e q l p l p ~ e p 2-3 l v k l p p p pl n p l rp tn r p. Fig. 4. remval as a functin f H 2 O pretreatment time (bubbler and reactr at 50G C). Fig. 5l p m r pl m p ˆ l. l l NaH pp l pp l pm p p. l k p p pm p n p p sk r~rp r pp n m. 80 C p l pp p p l v k p k r pp 70 C p l Wegscheiderite ( 3NaH ) p p pp pl p [6]. p m p pl v er r Krean Chem. Eng. Res., Vl. 43, N. 4, August, 2005
540 në m Ës Ë ~ Ëp} Fig. 5. Effect f reactin temperature n remval (H 2 O pretreatment fr 30 min befre carbnatin, bubbler at 50 C). l p p v k m p l nr k mp d n p p 50 C r p pm rr p Ž. srbap m vv~ l p. p vv~ p ˆ pv kp vp l 13 C NMR d p pp r k pl vp Žk pp p m. Fig. 6l 170.6 ppml p NaH 164.5 ppml p p., p vp p. pr 300 Cl srbap m p l ˆ l NaH np ˆ v kk. 50 Cl 1e pp eˆ srbap n pp NaH l m p v k k p l q m. p d p p rp p l srbap vv~ rn p p NaH 82Í, 18Íp p r r p p pl. Fig. 7l srba 50 Cl 1e k pp eˆ p 135 Cl N 2 t 1e k q eˆ e -q p p e p ˆ l. w p p ~ wl p p p lv p p. w p p w s r pp lr. NaH lt (Thermgravimetric Analysis, TGA) e p 120 Cl m q k r p [6]. l l n p l 135 Cl 1e r q m q p p lvv kkpp k p., 300 Cl 1e q eˆ ee w pp ~ p p p p 300 Cl q p m p lrpp ˆ. 43 4 2005 8k Fig. 6. 13 C NMR spectra f srbents (carbnatin). Carbnatin was carried ut after H 2 O pretreatment fr 30 min. Fig. 7. remval during fur carbnatin cycles (H 2 O pretreatment fr 30 min befre carbnatin, bubbler and reactr at 50 C).
p Fig. 8p NMR d p p p. 135 Cl q e q v NaH l m (164.5 ppm) sq, 300 Cl q n sq p k p. p l srba 3.0 L/min p N 2 1e k q n l re 120 C p m l q p p lrk m r p k p. TGA e l p e n m l q e l l pp m p r k pqp m pm v l q p j np pl p p Ž. p l q e p p t /q l l q l p p m pr ve t 120 Cl q p p p lv pp p. srbap q m q ƒ vl p p l v lk p Ž. l l p q l m p r r p l q ~ N 2 n mv er rl džp n l q p f rp q lp kl pn p. e q r pn p ˆ 541 4. l l t p e r pn l p l p p k. pp p m l peqr p p kp p nl p p p m. 30 r p r} n 50 Cl p 1-2 k 100Íp r pp m. 300 Cl 1e r q n e p p rp p r n p r ll. NMR d p p q p e p p Žk pl. e r rl q tn r rp, p m, plp rl, p p p tp p. l l llv p p v l q p m nrl tn q p. p l vp 21 Žl l (p ˆ r } )p p p ld. y 1. Hffman, J. S.Gand Pennline, H. W., Investigatin f Capture Using Regenerable Srbents, 17th Annual Int l Pittsburgh Cal Cnference, Pittsburgh, U.S.A(2000). 2. Green, D. A., Turk, B. S., Gupta, R. P., Lpez-Ortiz, A., Harrisn, D. P. and Liang, Y., Carbn Dixide Capture frm Flue Gas Using Dry Regenerable Srbents, Quarterly Technical Prgress Reprt, DOE Cperative Agreement N.: DE-FC26-00NT40923, US DOE(2001). 3. Granite, E. J. and Pennline, H. W., A Review f Nvel Methds fr Separatin f Carbn Dixide frm Flue and Fuel Gases, 20th Annual Int l Pittsburgh Cal Cnference, Pittsburgh, U.S.A (2003). 4. Ryu, C. K., Lee, J. B., Oh, J. M. and Yi, C. K., Dry Regenerable Srbents fr Capture frm Flue Gas, 20th Annual Int'l Pittsburgh Cal Cnference, Pittsburgh, U.S.A(2003). 5. Yi, C. K., J, S. H., Ryu, H. J., Y, Y. W., Lee, J. B. and Ryu, C. K., Reactin Characteristics f Dry Regenerable Srbents in Fluidized Reactrs, 7th Internatinal Cnference n Greenhuse Gas Cntrl Technlgies, Vancuver, Canada(2004). 6. Liang, Y., Harrisn, D. P., Gupta, R. P., Green, D. A. and McMichael, W. J., Carbn Dixide Capture Using Dry Sdium-Based Srbents, Energy&Fuels, 18(2), 569-575(2004). 7. Kunii, D. and Levenspiel, O., Fluidizatin Engineering, 2nd ed., Butterwrth-Heinemann, Bstn, U.S.A(1991). 8. Se, Y. and Lee, H., Phase Behavir and Structure Identificatin f the Mixed Chlrinated Hydrcarbn Clathrate Hydrates, J. Phys. Chem. B, 106(37), 9668-9673(2002). Fig. 8. 13 C NMR spectra f srbents (regeneratin). Regeneratin ccurred in N 2 flwing at 3.0 L/min after carbnatin was carried ut fr 1 hr at reactin temperature f 50G C with H 2 O pretreatment fr 30 min. Krean Chem. Eng. Res., Vl. 43, N. 4, August, 2005