Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005, pp. 691-695 종이나섬유를지지체로이용한제올라이트박막의제조 r pn 500-757 te n 300 (2005 10o 13p r, 2005 11o 24p }ˆ) Preparation of Zeolite Membranes on Papers or Fibers Kyeong-Keun Song and Kwang Ha Faculty of Applied Chemical Engineering, Chonnam National University, 300, Yongbong-dong, Buk-gu, Gwangju 500-757, Korea (Received 13 October 2005; accepted 24 November 2005) k sp, o, o o p vv~ ol p q l l p l rm p p rs m. r, rm p sq n o l rm p NaA( 0.5 µm)m silicalite-1( 0.2 µm) r p m, p r p vv~p l p pn l e. sq rp vv~ ol NaA silicalite-1 rm p p lp, rs p t rq p m, X-ray r m. h Abstract Zeolite membranes on various supports such as filter paper, cotton fiber, and glass fiber filter were prepared by secondary growth hydrothermal synthesis. First, zeolite NaA ( 0.5 µm) and silicalite-1 ( 0.2 µm) crystals were synthesized as zeolite seed crystals, and they were attached to the surfaces of the supports via chemical bonding. Zeolite NaA or silicalite-1 membranes could be synthesized on the supports coated with the seed crystals. The prepared zeolite membranes were observed by scanning electron microscope and analyzed by X-ray diffraction. Key words: Zeolite Membranes, Zeolite NaA, Silicalite-1 1. (zeo) (lite) p p p rm p p } p rp or s v r k mp psp pm r, r p n, ~ ˆ l l p pn p. rm p r, lr, r kr p l, p q p m d l vp q p p p q~(molecular sieve). l rm p l pq p ve pp, p d, ~ kqrp q p p ~, p q p p pp p pn p n [1-5]. lp r tl vp tn k v p. m l, v,, lž, p ˆ m p d p rl qt n ˆl lk To whom correspondence should be addressed. E-mail: hakwang@chonnam.ac.kr. l v tl p pn vp q, rp. n v p o v l l m r l kr l k kl rn p [1]. rm p p psp v p ~ k~p o q~ jp p. p rp rm p ˆ, p n l r r n l qp k p, v o k ˆ e l n. rm p p } srp p n l vp q pn o rm p p p ˆ p v. p p p pp, p p e p p. r p v v p lr p l, r p r s s v p p v l p [2]. r rm p p p rp l vv~p ol rm p p f. vv~ rvp e, e Ž, o, k Ž, ~ o, k k v p n p [5-19]. p p rs p l [8, 9, 11, 19], p q l [13, 14, 18], 691
692 [15] p p. vv~ rm p nkl vv~ ol rm p p eˆ l l rm p p r rp m vv~p v lk, p l vv~ p o p n v lk. vv~l rm p vv~p l l l p rs v, v kp nl vv~ p vp r r } e p [12]., vv~p l r m p jk r p r p pn l r p p nkl rm p p rs p q l p n. l vv~l kp, Ž p l p qeˆ. l e } α-k vv~ ol MFI rm p p r eˆ p l qp (xylene) p v~p e [16, 17]., α-k p FAU rm p p Si/Alp m pm kpml p ˆ, ˆ, v p Œ m ˆ r [18]. p l l r v, vv ~m rm p p lž} l q lp, p p l vp ˆ p lv. rm p p l l rl rn p p q rp v p. q n vv~, kr, ˆ, lr r n p kl l v pv, lp v k, r p rs p o kp p l n kp. p l l rs l d r p spm o o o p vv~ n l l p NaA m silicalite-1p rm p p rs mp, vv~p s l m pql l s m. 2. 2-1. ssz rm p p vv~ sp (Whatman), o o (Whatman), o p n m. vv~ 1cm 1cm r l lˆml 30 k eˆ ml s m, Š ll e 30 k e } m. } vv~ 100 Cl 3e s l p pl o n m. 2-2. oj mš pm om rm p NaAp p rsl p nk ˆ p Ludox HS-40(DuPont, 40 wtí SiO 2 ), sodium silicate(junsei, 98Í Na 2 Si ), sodium aluminate(kanto Chemical, 31-35Í Na 2 O, 34-39Í Al 2, NaAlO 2 ), sodium hydroxide(daejung, 98Í NaOH) p n mp, silicalite-1p p rsl tetraethyl orthosilicate(junsei, 95Í TEOS)m tetrapropylammonium hydroxide (Acros Organics, 10Í TPAOH) n m. k 0.5 µm p rm p NaA Na 2 O:Al 2 :SiO 2 :H 2 O =4:1:2:80p m. dž ƒ l v 20.0 gjp l l NaAlO 2 6.3 g p e 10.0 g p p p k 10 k l p nkp o43 o6 2005 12k m. nkp l l NaOH nkp l m l 12e eˆ (Nalgen, 250 ml) l k l m l k l. 100 Cl 6e peˆ m o p, NaA l l p k p v l } 100 Cl 2e k o s m. k 0.2 µmp silicalite-1p TEOS:TPAOH:H 2 O=3:1:330p m. dž ƒl v 58.7 g, TEOS 9.4 g, TPAOH 29.0 gp p nkp v ml k 6e e tl. p k pn l l 180 o C l 6e k p pe. silicalite-1p l l v l } 100 Cl 3e k o s. 2-3. oj mš m oo p rsl vv~l vv~ rm p l p eˆ (p q, primary growth), rm p sq rp vv~l p pn l r r p p sq r ol q (p q, secondary growth)p n m. vv~m rm p rp l (OH) pp, p v eˆ o l Š l n l 3-chloropropyltrimethoxysilane(CPMS) pe l r chloropropyl qn k. n l q polyethylenimine(pei)p n l vv~m sq rp e [20, 21]. NaAp p p p p rs m. v 60 gj l p p dž ƒl Na 2 Si 12.2 g NaAlO 2 14.0 gp p e p nkp m. nkp NaOH nkp lt l ml 4e k m. nkp l m, l vv~ v p n p l 100 o C m l k l vv~ ol p m. Silicalite-1 p rs p p. v 58.7 g TPAOH 29.0 gp l l l TEOS 9.4 gp ~ m. nkp ml 6e eˆ k pn l l. l vv~ vp n l 180 o C m l p m. vv~ ol rm p p p k l v l } 100 o C m l k 2e se. rm p NaA silicalite-1 p rs vv~l sq rp r r vp l, p, p m e s p Table 1 2l ˆ l. 2-4. rm p m rm p p r r r p Table 1. Synthesis conditions for preparation of zeolite NaA membranes Method Seeding SiO 2 :Al 2 :Na 2 O:H 2 O Temp. ( o C) Crystallization time (h) A-1 2 : 1 : 3.8 : 160 100 6 A-2 2 : 1 : 3.8 : 160 100 6 A-3 2 : 1 : 3.8 : 160 100 12
Table 2. Synthesis conditions for preparation of silicalite-1 membranes Method Seeding TEOS:TPAOH:H 2 O rl Rigaku(Model R-XAS, Japan) X- r (X-ray diffractometer, XRD) pn m. X- p Ni CuKα- p n mp, 40 kv 40 map s l r (2θ)p 5 ol 60 o v eˆ m. vv~, r m p sq r, rm p p k r ˆ t rq (scanning electron microscope, SEM; Jeol JSM-5400, Japan)p m. 3. y Temp. ( o C) 3-1. pm li oj mš m m rm p NaA p sp ol eˆ o l Table 1 l nk A-1, A-2, A-3 p n mp, vv~ n sp p SEM vp Fig. 1(a)l ˆ l. r lˆm Š lp } sp kl vv~ ol p A-1 pl p ol l v k, p n l rm p NaA r p rm p p rs 693 Crystallization time (h) S-1 3 : 1 : 330 180 12 S-2 3 : 1 : 330 180 6 S-3 7 : 1 : 330 180 12 S-4 7 : 1 : 330 180 6 lp, sp l rm p p l pv kk. CPMSm PEI n l NaA sq rp sp l e ˆ vv~(fig. 1(b)) n A-2m A-3 pl l l p NaA sq rm p NaA p q l sp p ˆl p q p SEMp pl (Fig. 1(c)). p e p p pl p p rm p p ˆ k p, p e p A-3 p l rm p p v dp n p l. A-3 pl rm p px- r Ž p Fig. 3(b)l ˆ p, o l sp vv~l p Ž p Fig. 3(a) l ˆ l. l m p r Ž sp ol NaA rm p lpp k p [22]. rm p NaA p rsem v silicalite-1 rsp nl vv~ kl p p(s-1 S-3)l sp ol p v k k. silicalite-1 sq rp l p vv~(fig. 2(a)) n S-2m S-4 pl silicalite-1 p l. S-2 pl p sp r~ mr v mv (Fig. 2(b)), TEOSp kp rp p S-4 p s l sp ol silicalite-1 p r~rp q lp p SEMp pl. S-4 pl p p SEM vp Fig. 2(c)l ˆ p, X- r Ž p Fig. 3(c)l ˆ l. vv~l rm p r pq eˆ o l n CPMSm PEI rm p p l m l Fig. 1. SEM images showing: (a) the morphology of filter paper, (b) zeolite NaA crystals attached to the surface of filter paper, (c) zeolite NaA membrane on filter paper after the reaction A-3. Fig. 2. SEM images showing: (a) silicalite-1 crystals attached to the surface of filter paper, (b) silicalite-1 membrane on filter paper after the reaction S-2, (c) silicalite-1 membrane on filter paper after the reaction S-4. Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005
694 Fig. 5. XRD patterns of (a) cotton, (b) zeolite NaA membrane after the reaction A-2 on cotton. Fig. 3. XRD patterns of (a) a bare filter paper, (b) zeolite NaA membrane on filter paper after the reaction A-3, and (c) silicalite-1 membrane on filter paper after the reaction S-4. s m. sp l v CPMS CPMS/PEI } sq rp pv kp vv~ ol NaA silicalite-1 p v kk. 3-2. li oj mš m o md 94~98Í t p p, k p, Ž, v p p lr p. Mintova p o r, rp } l op p r l rm p o ol m [11, 12]. p l l ol rm p NaA sq rp l p r r ol p e. rm p kl o n } o p A-1 pp o ol NaA p v kkp, rm p pq p ~ o o l l p p pl. l, NaA sq r p CPMS/PEI l q o(fig. 4(a)) n A-2 pl rm p NaA sq p q l p Fig. 4. SEM images showing: (a) zeolite NaA crystals attached to the surfaces of cotton fibers, (b) zeolite NaA membrane on cotton fibers after the reaction A-2. o43 o6 2005 12k op ˆ q lpp p (Fig. 4(b)). Fig. 5l vv~ n om o ol rm p NaA p XRD Ž p ˆ l. o ol silicalite-1 p v kk. rm p s q n v kp S-1 S-3 pl silicalite-1 r p o pl l rp l p p p l, sq n S-2m S-4 pl rm p sq rl p q mv ol lr m p dp pl. 3-3. l l i silicalite-1 m o op t p rm p m p e m k p, l l k p vp l pl rm p p vv ~ p l p [19]. o o m nkl l m nkl NaA p rs llp, o o ol silicalite-1 p rs e m. p nl TEOSm TPAOHp sq rp l p l llr. Silicalite-1 sq rp l pv kp o o n S-1 S-3p e l p v kk. TEOSm TPAOHp l silicalite-1 r p o o l l lpp pl. vv~ n o o m S-1 S-3 pl p o o ol silicalite-1 rp SEM vp Fig. 6(a), (b), (c)l ˆ l. o ol r silicalite-1 sq rp eˆ l vv~ n S-4 pl silicalite-1 r p o o p }n q p q l ppp p (Fig. 6(d)). 4. p l l sp, o, o o p vv~ n l rm p NaA silicalite-1p p rs m. p m p vv~ n nl rm p p vv~
rm p p rs 695 Fig. 6. SEM images showing: (a) the glass fibers, (b) silicalite-1 crystals synthesized on the surfaces of glass fibers after the reaction S-1, (c) after the reaction S-3, (d) silicalite-1 membrane on glass filter after the reaction S-4. ol eˆ l ov, p pn l vv~ l r rm p sq r p r t ol rm p p qeˆ nl rm p p q p k pl. p p 2003 r l vol p l l lp, vol. y 1. Bein, T., Synthesis and Applications of Molecular Sieve Layers and Membranes, Chem. Mater., 8(8), 1636-1653(1996). 2. Tavolaro, A. and Drioli, E., Zeolite Membranes, Adv. Mater., 11(12), 975-996(1999). 3. Caro, J., Noack, M., Kölsch., P. and Schäfer. R., Zeolite Membranes state of Their Development and Perspective, Microporous Mesoporous Mat., 38(1), 3-24(2000). 4. Noack, M., Kölsch, P., Toussaint, P. and Caro, J., Molecular Sieve Membranes for Industrial Application: Problems, Progress, Solutions, Chem. Eng. Technol., 25(3), 221-230(2002). 5. Valtchev, V., Mintova, S. and Konstantinov, L., Influence of Metal Substrate Properties on the Kinetics of Zeolite Film Formation, Zeolites, 15(8), 679-683(1995). 6. Valtchev, V., Schoeman, B. J., Hedlund, J., Mintova, S. and Sterte, J., Prepatation and Characterization of Hollow Fibers of Silicalite- 1, Zeolites, 17(5-6), 408-415(1996). 7. Valtchev, V., Hedlund, J., Schoeman, B. J., Sterte, J. and Mintova, S., Deposition of Continuous Silicalite-1 Films on Inorganic Fibers, Microporous Materials, 8(1-2), 93-101(1997). 8. Okada, K., Shinkawa, H., Takei, T., Hayashi, S. and Yasumori, A., In-situ Coating of Zeolite Na-A on Al 2 -SiO 2 Glass Fibers, J. Porous Mat., 5(2), 163-168(1998). 9. Zhang, F.-Z., Fuji, M. and Takahashi, M., In-situ Growth of Continuous b-oriented MFI Zeolite Membranes on Porous α- Alumina Substrates Precoated with a Mesoporous Silica Sublayer, Chem. Mater., 17(5), 1167-1173(2005). 10. Yamazaki, S. and Tsutsumi, K., Synthesis of an A-Type Zeolite Membrane on Silicon Oxide Film-Silicon, Quartz Plate and Quartz Fiber Filter, Microporous Materials, 4(2-3), 205-212(1995). 11. Valtchev, V., Mintova, S., Vulchev, I. and Lazarova, V., Influence of Reactive Radicals in Cellulose Fibers on the Formation of Zeolite Coating, J. Chem. Soc., Chem. Commun., 2087-2088(1994). 12. Mintova, S. and Valtchev, V., Deposition of Zeolite A on Vegetal Fibers, Zeolites, 16(1), 31-34(1996). 13. Bernal, M., Xomeritakis, G. and Tsapatsis, M., Tubular MFI Zeolite Membranes Made by Secondary (seeded) Growth, Catal. Today, 67(1-3), 101-107(2001). 14. Lai, R. and Gavalas, G. R., Surface Seeding in ZSM-5 Membrane Preparation, Ind. Eng. Chem. Res., 37(11), 4275-4283(1998). 15. Dong, J., Payzant, E. A., Hu, M. Z. C. and Depaoli, D. W., Synthesis of MFI-type Zeolite Membranes on Porous α-alumina Supports by Wet Gel Crystallization in the Vapor Phase, J. Mater. Sci., 38(5), 979-985(2003). 16. Lai, Z., Bonilla, G., Diaz, I., Nery, J. G., Sujaoti, K., Amat, M. A., Kokkoli, E., Terasaki, O., Thompson, R. W., Tsapatsis, M. and Vlachos, D. G., Microstructural Optimization of a Zeolite Membrane for Organic Vapor Separation, Science, 300(5618), 456-460(2003). 17. Lai, Z., Tsapatsis, M. and Nicolich, J. P., Siliceous ZSM-5 Membranes by Secondary Growth of b-oriented Seed Layers, Adv. Funct. Mater., 14(7), 716-729(2004). 18. Hasegawa, Y., Tanaka, T., Watanabe, K., Jeong, B.-H., Kusakabe, K. and Morooka, S., Separation of CO 2 -CH 4 and CO 2 -N 2 Systems Using Ion-exchanged FAU-type Zeolite Membranes with Different Si/Al Ratios, Korean J. Chem. Eng., 19(2), 309-313 (2002). 19. Larlus, O., Valtchev, V., Patarin, J., Faust, A.-C. and Maquin, B., Preparation of Silicalite-1/Glass Fiber Composites by one- and Two-Step Hydrothermal Synthesis, Microporous Mesoporous Mat., 56(2), 175-184(2002). 20. Lee, G. S., Lee, Y.-J., Ha, K. and Yoon, K. B., Preparation of Flexible Zeolite-Tethering Vegetable Fibers, Adv. Mater., 13(19), 1491-1495(2001). 21. Ha, K., Chun, Y. S., Kulak, A., Park, Y. S., Lee, Y.-J. and Yoon, K. B., Polyamines as Strong Covalent Linkers for the Assembly of Mono and Double Layers of Zeolite Crystals on Glass, Stud. Surf. Sci. Catal., 135, 3137-3144(2001). 22. Treacy, M. M. J. and Higgins, J. B., Collection of Simulated XRD Powder Patterns for Zeolites, 4 th Ed., International Zeolite Association, Elsevier(2001). Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005