A Study on Physical Properties and Catalytic Combustion of Methane of Sr Hexaaluminate Prepared using 1-butanol and Ethylene Glycol

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1 Krean Chem. Eng. Res., Vl. 45, N. 3, June, 2007, pp utanl ethylene glycll mk i Sr heaaluminatem n Š i mi i Çk m* r q l v r rte v v * re ( p r, p }ˆ) A Study n Physical Prperties and Catalytic Cmbustin f Methane f Sr Heaaluminate Prepared using 1utanl and Ethylene Glycl Jung Min Shn and Seng Ihl W* Department f Mineral Resurces & Energy Engineering, , Duckjin-dng, Duckjin-gu, Jenju, Jenbuk , Krea *Department f Chemical & Bimlecular Engineering and Center fr Ultramicrchemical Prcess Systems, Krea Advanced Institute f Science and Technlgy, Guseng-dng, Yuseng-gu, Daejen , Krea (Received 10 Octber 2006; accepted 26 December 2006) k Sr heaaluminate(sr 1- -α )m alkide r ~, 1utanl ethylene glyclp n n sl-gel p m. n l Sr heaaluminatep r p TG/DTA, XRD N 2 adsrptinp pn l m. s e l l p 1utanlp n n l heaaluminatem, ethylene glyclp n pn n n p p dehydrylatin pp l, r m d m. Dehydrylatin p r m p dp heaaluminatep p e p rp pp l. ˆl l pp r p l m p tlpp p m. h Abstract Sr heaaluminate(sr 1- -α ) were prepared by sl-gel methd f metal alkide with 1utanl r ethylene glycl as a slvent. The physical prperties f prepared heaaluminates were eamined by TG/DTA, XRD and N 2 adsrptin. When ethylene glycl was used as a slvent, the decmpsitin reactin and dehydrylatin reactin was bserved abve 400 C and the temperature f the frmatin f a crystal structure f heaaluminate was als increased resulting in small specific surface area and lw catalytic activity f methane cmpared t Sr-heaaluminate with 1utanl. Key wrds: Heaaluminate, Methane Cmbustin, Thermal Decmpsitin, 1utanl, Ethylene Glycl 1. l p l l vp l v qp prp pnp sp l e l edš p m l rk l. l p v p l l p p l pp p p l edšp [1]. l l m ˆ dp pp lp eˆ p p mr l l p ˆ T whm crrespndence shuld be addressed. jmshn@chnbuk.ac.kr m r rp. l sp l rl n rp ~w rml slp p, w p l mll kr l pp, w sp l r NO m ml k l s lp l NO p eˆ p p. l l p l p lp [1, 2], sl m 600~800 Cp rn m q d } l l p np p. d, p, afterburner p m, k l m l p p p pp en l l p. m l p er pnl pl lr kr p p 209

2 210 r Ën p vp p q tn r r p p 1,200 C p m mll sp l p pl p. m l l rrp pp pl p m mlp p r~ p mlp l p. np q n alumina vv~ tep m l p vveˆ p l v l m [3-12]. q vp l p v l v p, alumina vv~l ~ l aluminap ml p r qp p vle m l p p. Ba Srp ~ heaaluminate s 1,200 C p p ml q p l p v p p., heaaluminate sl Mn p rp p eˆp f ml n p m. pm, p ~ lp aluminap rs s r ~p s p m l p e v lm. Mizukami [13] p alkide pn alumina rse n n l alumina p pm kv ppp m. Vannice [14] p aluminap r ~p α-diaspre p rp α-alumina rs m m. l l, alkide pn heaaluminate rse n n rs l m l m l p m. Heaaluminate s r tp s kk TG/DTAm r p XRD r p N 2 adsrptin p p n m. rs p p ˆl p p m { Heaaluminate vv~(sr 1- -α ) metal alkidep hydrlysis p m [4]. Aluminum isprpide(p AIP, Aldrich 99.99%) 10 g s l Sr (Aldrich, 99%) p n 100 mll v v 5e l n m. n n l n r n l mlecular sieve l 3p k l p r m. n k m n 1utanl(Aldrich 99.8% HPLC grade) ethylene glycl(aldrich 99.8% anhydrus)p. p nkl Mn nitrate(wak)m nitrate (YAKURI PURE CHEMICALS 6-Hydrate) nkp }} ~ eˆ hydrlysis pp v e. nkp t l 80 C v p 12e (aging) e. eˆ p rtary vacuum evapratrl se. s k p l k 50~100 meshp e. p 500 Cl e ˆ l l 1,000 C, 1,200 C, 1,400 Cl 5e k e. e dm 2 C/minp. p p 20 ml/minp BROOKS mass flw cntrller rl m. n n l rs s e pl (1utanl)m -e(ethylene glycl) l m k 2-2. { Š TG/DTA(thermgravimetric analysis) TG/DTA92 thermanalyzer (SETARAM, France) pn m. s e 20 mgp Pt n l p, Ar(30 ml/min)p, 10 C/minp dm 1,000 C v m v m l v p m. Cu Kα X-ray tube q X-ray diffractmeter(riguku C.) n l r s m. p rk r 35 kv, 15 map p XRD spectra eml m. r rp ASAP 2000(micrmeritics)p n m. r r e 0.5~0.6 gp 300 Cl 2e r v l v p r m { m heaaluminatep ˆp l p e p k l m. l ˆ 1 vl%m 99 vl% l n m, p 50 ml/minp. p BROOKS mass flw cntrller sr m. n p kp 0.2 gp. n p n 10 mmp quartz rq m. l d p vr peˆ p r~ l r q m l re l l q l p K-type thermcuple m r m. pp d ice-ethanl trapp ~ p r, n-line gas chrmatgraphy(hp5840a, clumn: prapak Q; Detectr: TCD) pn m. pe p space velcity 20,000 h -1 r m. p p ˆp r pp 10% m (T 10% )m ˆ p r pp 90% m (T 90% ) ˆ l m, T 10% p l pp e m p }, T 90% l p p mr p lv m p } n p p. 3. s llv gelp rp heaaluminate rp v p. gel l rs e n n, r ~l p nitrate m ˆ p sq p. rl p p m l l ˆ r, l m l idep p eq v llv pqp mrphlgy,, r s l vr rp m p t., TG/DTA dm r tp v m l vp p p f llv heaaluminatep p l r m p. n e 1utanl ethylenep n l s heaaluminate r ~ n m. Heaalmintep s p e Sr 0.5 p. Fig. 1p Sr 0.5 (A)m Sr 0.5 -e(b)p TG/DTA prfilep. Sr 0.5 p n v p p l v pl. r 100 Cl 200 C v v p mll p l peak p p, p gel p k m n p v p p, p r~ v p k 40 wt% m. 200 C p l 2 p l peak p, 200 Cl ˆ peak sp

3 1utanl ethylene glyclp pn l Sr heaaluminatep r ˆ l pl l 211 Fig. 1. TG/DTA prfile f Sr 0.5 (A) and Sr 0.5 -e (B) precursr. peak p, p k 5 wt% p v p pl. p 250~350 C mll l peak ˆ p. p p v k 15 wt% r m. 2 p l peak gel r ~ l rp nitrate p l pp p r. p 1,000 C v v lp pr v p v p. p l Sr 0.5 r ~ 400 C p l r ~p p r l p. Sr 0.5 -ep n 200 C v v kp prfile p ˆ, p gel l sq p v p. p, k 25 wt%p v pl. 300 Cm 400~500 C l 2 p l peak, p k m, peak ˆ m 100 C d, peakp p n lv p p p. p gel p p p p pl m n krpp lt p. p m k 30 wt%p v pl p. p, 300~400 Cm 800 C l 2 p l peak ˆ p. 800 Cl p l p n pn k p rs tl [13], p behmite pl Al qm p hydryl grupp l p dehydrylatin p p. k 500 C v v p lp p 1utanl p n n n 100 CC r d p. Ethylene glyclp qlr m k 410 CC 500 C p l v q ethylene glyclp qlr p l p pp p. m l heaaluminate s l vv~ rs l l l m p p p p [11]. m p aging e, p e ~ p k[3], m, k m n p s p. Fig. 2(A) 1,200 Cl, Sr p s l Sr 1- p XRD diffractin(q )p. 1,000 C l p heaaluminate peak l. m l n heaaluminate p n heaaluminate r p p rp r r n p. Sr p n, XRD l 1,200 C 1,000 Cl heaaluminate r peak pnl peak sp peak k 1~2 p vrl, p p rp q p p. p peak 1,400 C l n ˆ p 2 p r p sq p. p Fig. 2. XRD spectra f Sr 1- G(A) and Sr 1- -e (B) calcined at 1,200 C. (a) =1 (b) =0.8 (c) =0.5 (d) =0.2 (e) =0. Krean Chem. Eng. Res., Vl. 45, N. 3, June, 2007

4 212 r Ën p p ~ Mnl p 2 v heaaluminate p p. Machida [12]p p heaaluminate r p Mnp s p p heaaluminate rp l p m. s p heaaluminate rp p rp p p ml p kr p k v p m p. Mnp s p p heaaluminate rp Sr p r. p s l lp p heaaluminate 1,000 C l rp lpp p l. p p ~ p p r p Srp l pl p p, mr np heaalminate r SrO 6Al 2 p v kpp lt p. 1,200 Cl heaalminatep Sr p s l XRD patternp, 2θ =32, 34, 36 p p t peakp q ˆ p p p. heaaluminate rl 2θ =32 (110), 2θ =34 (107), 2θ =36 (114) p rp ˆ p. s p 0.2m 0.5p n XRD pattern p p ˆ p p. Sr p sq Sr, 2θ =32p (110) p r qp p l. p p 0.5 p p n, 2θ =34p (107) p r qp p p ƒvl r rp lr ppp p., 2θ =36p (114) p r q lr l, Sr p nm, mr r q ˆ p p. p r q p p 1,400 C l r p heaaluminate p p p. Fig. 2(B) ethylene glyclp n l 1,200 Cl heaaluminatep XRD peak lt p. Ethylene glyclp n n n, 1utanlp n n nm 1,000 C XRDl heaaluminate r s peak v k. n n ethylene glyclp p -OH p v dil alkide l sq n, sl-gel p. p p p sl-gel p t heaaluminate pq t p p p lv p. p p heaaluminate rp m kv pp p. 1,200 Cl, llv e Sr p s l l p SrO 6Al 2 p r s p pl. 1utanlp n n l rs heaaluminatem Sr p s l lp XRDl peakp pattern p p dp m. XRD r n l lp 1,200 Cl m heaaluminate rp p p plp, 1utanlp n n ethylene glyclp n heaaluminate p r m kp, Sr rn m de p r s p p., alkide v hydrlysis p n sl-gel p p f p pn l heaaluminate Grppi [5]l p t p p v kk. Fig. 3p Sr 1- p m l r m 1,200 Cl Sr 1- -ep rp ˆ l. rp n m m l p m. Sr p n, 1,000 Cl 44 m /g 2 Sr 1- - bt q p rp mp, 1,200 Cl rp l 8.6 m /gp 2 l. p XRDl p p k Fig. 3. Surface areas f Sr 1- and Sr 1- -e. Sr 1- calcined at 1,000 C, GSr 1- calcined at 1,200 C, Sr 1- calcined at 1,400 C, Sr 1- -e calcined at 1,200 C. l } 2 p r p p p l 1,000 Cm 1,200 Cl n, = 0.5l p p ˆp p p. 1,400 Cl l =0.2 q p p pp, ~ k 5 m 2 /g r p d p p p. p ~ p f heaaluminate p rp lp Sr p p, q p r p m > 0.5p n rp m. Sr 1- -ep n, Srp s l lp p s p Sr 1- l n p p p p. r~rp 5 m 2 /gp p p rp p p. p 1,400 Cl Sr 1- p r d p. XRDl p r s p heaaluminate rp p p plp heaaluminate r p m m} k r lr lp ll. p s heaaluminate gel r ~ t heaaluminate rp r rl n p s vl l} t gelp m p p m p. TG/DTA m XRD r l n l rp p p. Jhnsn[15]p k pq qp pr pq pl l rp k hydryl grupp p l p r dehydrylatinl p v m. p p, pq p pq q rp plv m. p rp l l} t dehydrylatinp lr lk. TG/DTAp ethylene glyclp n n p n, 800 C l dehydrylatinl p p p l peak l, ml v v l. p p pq q p v l, p p ethylene glyclp n n heaaluminatep rp 1utanlp n l heaaluminatel p p pp p. Heaaluminatep l} tl dehydrylatinp p pp l Wang [16]l p p.

5 1utanl ethylene glyclp pn l Sr heaaluminatep r ˆ l pl l 213 Fig. 4. Pre size distributin f Sr (A) and Sr 0.5 (B) calcined at (a) 1,000 C, (b) 1,200 C, (c) 1,400 C. Fig. 4(a)m Fig. 4(b) Sr m Sr 0.5 p m l p l t p. 1,000 C l Sr m Sr 0.5 ˆ p lt p. Sr p n, 10 nm p l p mp, Sr nm p micrpre mll p p p., 10 nmp l p p sq ˆ p p. p rp vv~ 2 p p p v bimdal ˆ v k r p [17]. yp p pq pp l p ˆ p, qp yp p pq l r p. m kvl p p Ž, p m p v k k r p. p p p l q ˆ p. 1,200 Cl p m (Table 1). p 10 nm p p p p pp k p. Fig. 5. Catalytic cmbustin f methane ver Sr 1- calcined at 1,000 C(A) and Sr 1- and Sr 0.5 -e calcined at 1,200 C(B). 1,200 C p p 10 nm p p v p m pq q p l p p pl, p p rp lp p p., p m d l Sr p n, Sr 0.5 p n v m. Sr 1- p m l ˆl pl ˆ p r pp Fig. 5l ˆ l. 1,000 Cl p n, q p rm (T 10% )p p p Sr m. p p T 10% p 443 C pl. np p T 10% p k 460 C r d p m. 1,200 Cl, 1,000 Cl nm p p, p l Sr 0.5 q p T 10% p p p. Table 1. Pre vlume and avg. pre diameter f Sr (A) and Sr 0.5 (B) calcined at varius temperatures Sr Sr 0.5 Calcinatin temperature( C) 1,000 1,200 1,400 1,000 1,200 1,400 Ttal pre vlume(cm 3 /g) Avg. pre diameter(nm) Krean Chem. Eng. Res., Vl. 45, N. 3, June, 2007

6 214 r Ën p T 10% =0.5<1<0.8<0<0.2 kr. 1,000 C l q p rm p m Sr ,200 Cl q p p p p., Sr 0.5 p n 1,000 Cl e m 1,200 Cl e pp T 10% p 6 C l p v kk m p dp p r (33.8 m 2 /g -> 17.5 m 2 /g)l r pv k p. p np m d l 1,000 Cl e l T 10% p 16 C( )l 71 C(Sr ) kr. pp pp e rmmll p Sr p s l p p pp eq 650 C p l r p 2 p p ~ v } p. p p p Sr 0.5, m Sr p r p kv, Sr m Sr p r p kr. r p 90%l m p T 90% Sr m Sr Cp, Sr 0.5,, Sr C k 15 Cp p p. r T 10% p, q p rp p Sr 0.5 T 10% p q kp, pnp nl r p p pv k p. 1,200 Cl Sr 0.5 -ep n(fig. 5(B) Ì), 1,200 Cl Sr 1- p r p lt p. p Sr 1- l n p rp p p. 4. 1utanl ethylene glyclp n n l Sr-heaaluminate p r ˆ l p p p p ll. (1) Hydrlysis p pn sl-gel l n heaaluminate p r l m p tl. Ethylene glyclp n pn l heaaluminate 1utanlp n pn l heaaluminatel 400 C p p ml l dehydrylatin pp l, heaaluminate r 1,200 C l p pl. (2) 1utanl heaaluminatep rp Sr p l lp ethylene glycl p m l heaaluminatel p p m. p ethylene glyclp n heaaluminatep n, 1utanlp n heaalminatel l} t pq p dehydrylatin pl p heaaluminate r p vl p p. (3) 1utanl heaaluminate ethylene glycl p m l heaaluminatel ˆ p l p T 10% m T 90% mp, p heaalminate pp r pl p p. (4) rp l l 1utanlp n heaalminate ethylene glyclp n heaaluminatel m l} p lkr ˆ p m k y 1. Trimm, D. L., Catalytic Cmbustin, Applied Catalysis, 7, (1983). 2. Arai, H. and Machida, M., Recent Prgress in High-temperature Catalytic Cmbustin, Catalysis Tday, 10,G81-95(1991). 3. W, S. I., Kang, S. K. and Shn, J. M., Effect f Water Cntent in the Precursr Slutin n the Catalytic Prperty and Stability f Sr High-temperature Cmbustin Catalyst, Applied Catalysis B: Envirnmental, 18, (1998). 4. Shn, J. M., Kang, S. K. and W, S. I., Catalytic Prperties and Characterizatin f Pd Supprted n Heaaluminate in High Temperature Cmbustin, J.G Mlecular Catalysis A: Chemical, 186, (2002). 5. Grppi, G., Belltt, M., Cristiam, C., Frzatti, P. and Villa, P. L., Preparatin and Characterizatin f Heaaluminateased Materials fr Catalytic Cmbustin, Applied Catalysis A:General, 104(2), (1993). 6. Erssn, A. G., Jhanssn, E. M. and Jaras, S. G., Techniques fr Preparatin f Manganese-substituted nthanum Heaaluminates, Studies in Surface Science and Catalysis, 118, (1998). 7. Euzen, P., Le Gal, J. H., Reburs, B. and Martin G., Deactivatin f Palladium Catalyst in Catalytic Cmbustin f Methane, Catalysis Tday, 47(1-4), 19-27(1999). 8. Grppi, G., Belltt, M., Cristiani, C., Frzatti, P. and Villa, P. L., Thermal Evlutin Crystal Structure and Catin Valence f Mn in Substituted Baeta-Al 2 Prepared via Cprecipitatin in Aqueus Medium, J. Materials Science, 34(11), (1999). 9. Lee, S. G., Lee, H., Lee, C. H., Kwn, J. Y., Park, H. C., Hng, S. S. and Park, S. S., Synthesis and Catalytic Prperties f Barium Heaaluminates Incrprated with Chrmium and nthanum, Reac. Kin. & Catal. Lett., 86(2), (2005). 10. Yeh, T.-F., Lee, H. G., Chu, K. S. and Wang, C. B., Characterizatin and Catalytic Cmbustin f Methane ver Heaaluminates, Mat. Sci. & Eng. A, 384(1-2), (2004). 11. Machida, K., Eguchi, K. and Arai, H., Preparatin and Characterizatin f rge-surface-area BaO 6Al 2, Bull. Chem. Sc. Jpn., 61, (1988). 12. Machida, M., Eguchi, K. and Arai, H., Effect f Structural Mdificatin n the Catalytic Prperties f Mn-Substituted Heaaluminates, J. Catalysis, 123(2) (1990). 13. Maeda, K., Mizukami, F., Niwa, S., Tba, M., Watanabe, M. and Masuda, K., Thermal Behaviur f Alumina frm Aluminium Alkide Reacted with Cmpleing Agent, J. Chem. Sc., Faraday Trans., 88(1), (1992). 14. Ma, C.-F., Vannice, M. A., High Surface Area α-alumina. I.: Adsrptin Prperties and Heats f Adsrptin f Carbn Mnide, Carbn Diide, and Ethylene, App. Catal. A: General, 111(2), (1994). 15. Jhnsn, M. F. L., Surface-area Stability f Aluminas, J. Catalysis, 123, (1990). 16. Wang, J., Tian, Z., Xu, J., Xu, Y., Xy, Z. and Lin, L., Preparatin f Mn Substituted -heaaluminate Catalysts by Using Supercritical Drying, Catalysis Tday, 83, (2003). 17. Satterfield, C. N., Hetergeneus catalysts in industrial practices, 2 nd ed., McGraw-Hill, New Yrk, NY(1991).