Tp ch Ha hc, T. 47 (1), Tr.

47 - 53, 2009

NGHiN CU TNG HP V C TRNG ZEOLIT HZSM-5 DNG NGUN SILIC T V TRU

n Ta son 31-3-2008 L Th Hoi Nam1, Trn Quang Vinh1, Nguyn Th Thanh Loan1, Bao-Lian Su2 1 Vin Ha hc, Vin Khoa hc v Cng ngh Vit Nam
2

Trng i hc Namur, B Abstract

HZSM-5 zeolite was successfully synthesized by hydrothermal treament using silica derived from rice husk. The sample was characterized by XRD, IR, SEM, TEM, BET and 27Al-NMR methods. Characterization results revealed that HZSM-5 material synthesized from rice husk silica has crystallinity and acidity as high as standard sample. Apart from the conventional pores system in ZSM-5 zeolite structure, another one which has kinetic diameter in range of 10-50nm (mesoporous system) in synthesized material structure was discovered. This pore system is expected to increase significantly the catalytic activity of synthesized material.

I - M U Zeolit ZSM-5 c bit n t lu bi nhng ng dng rt rng ri trong lnh vc xc tc hp ph, x l mi trng. Khng nhng th, zeolit ny cn c bit n l mt xc tc rt hiu qu cho qu trnh to nhin liu sinh hc t cc loi du thc vt [1 - 3], cn du, cc polime ph thi hay cc phn on nng ca du m. Zeolit ZSM-5 c tng hp bng nhiu cc phng php khc nhau, c th dng hay khng dng cht to cu trc, c th s dng silic hay nhm t nhiu ngun khc nhau ty vo mc ch s dng v yu cu ca tng phng php tng hp. Tru l mt dng ph thi c to ra trong qu trnh sn xut la go. Hng nm Vit Nam, lng tru thi ra sau qu trnh xay xt go l hn 5 triu tn [4], lng tru ny c xem l rt t gi tr v hu nh khng c gi tr thng mi [5]. Bi vy, vic ti s dng tru theo hng c gi tr kinh t cao l rt cn thit v thu ht c rt nhiu cc nghin cu v vn ny. Tru c thnh phn ch yu l cc

oxit kim loi, trong SiO2 chim hn 20% v c chng minh l mt ngun cung cp silic c cht lng rt tt cho cc qu trnh tng hp ha hc [4, 6, 7]. Vi mc ch gii quyt vn ti s dng v tru theo hng to ra cc sn phm c gi tr kinh t cao, trong cng trnh ny chng ti trnh by cc kt qu nghin cu thnh cng v tng hp v c trng zeolit HZSM-5 t ngun v tru giu silic. Mu c c trng bng cc phng php ha l hin i nh IR, XRD, SEM, TEM, BET v 27Al-NMR. Kt qu thu c mt ln na khng nh ngun cung cp silic t v tru c cht lng tt, ph hp vi cc qu trnh tng hp xc tc. II - THC NGHIM 1. Tng hp vt liu Qu trnh tng hp vt liu c chia thnh hai giai on bao gm: giai on mt l qu trnh tch chit silic t tru v giai on hai l qu trnh tng hp xc tc. 47

a) To ngun silic t tru Ngun Silic cho tng hp vt liu ZSM-5 c chng ti chit t tru vi dung dch NaOH 1% trong 30 pht 80oC. Sau khi loi b b tru, dung dch lng thu c chnh l dung dch lng cha silic, c s dng lm ngun cung cp silic cho qu trnh tng hp HZSM-5 b) Tng hp vt liu HZSM-5 *Nguyn liu: - Ngun silic: dung dch chit t v tru (Vit Nam). Ngun nhm: sunfat nhm (Al2(SO4)3.18H2O) (Trung Quc). - Cht to cu trc vi mao qun: tetrapropylamonium bromua (TPABr) (c). - Nc ct 2 ln. *Phng php tng hp Vt liu ZSM-5 c tng hp bng phng php kt tinh thu nhit s dng cht to cu trc TBABr. Gel c kt tinh 170oC vi thi gian l 24 h. Sn phm rn sau khi kt tinh c ra bng nc ct n pH = 7, sy kh 100oC v nung 550oC trong khng kh 5 h loi b ht cht to cu trc. Sn phm sau c trao i H+ bng dung dch NH4NO3 2 M, ra, sy, nung li 500oC to sn phm cui cng l HZSM-5. 2. Cc phng php c trng vt liu - Ph hng ngoi (IR): Mu vt liu c ghi theo k thut p vin vi KBr theo t l 1 mg mu/100 mg KBr trn my Impact-410 (c), ti Vin Ho hc, Vin KH&CN Vit Nam, trong vng dao ng tinh th 400 1300 cm-1 nhit phng. - Phng php ph nhiu x tia X (XRD): Mu c ghi trn my Siemens D5005 (c) vi cc iu kin o nh sau: - ng pht tia X bng Cu, vi bc sng (l = 1,5406 ) - U = 30kV, I = 25 mA - Gc qut: 2 = 0,10-500 - Tc qut: 0,20/pht. 48

- Nhit phng: 25oC. - Phng php cng hng t ht nhn 27AlNMR: c o trn my quang ph Brucker MSL 400 i vi 27Al tn s 104,3 MHz. - Phng php hin vi in t qut (SEM): c o trn my Jeol JSM-7500F, mu c phn tn trong etanol, sy kh, a ln bn di dng lp mng sau c ph ln b mt mt lp vng mng trc khi chp. - Phng php hin vi in t truyn qua (TEM): c o trn my Philips Tecnai-10 microscope, phn gii kch thc nguyn t, in p 100 KV. Mu c trn vi epoxy v ct thnh tng mu mng c micro sau c a ln li ng c ph mng cacbon. - ng cong ng nhit hp ph-kh hp ph Nit c xc nh 77 K trn thit b Micromeritics ASAP 2010. Mu trc ht c loi b kh iu kin chn khng ti 593 K trong vi gi. Kch thc mao qun c xc nh bi phng php HorvathKawazoe [8]. B mt ring c xc nh s dng phng trnh BET vng p sut tng i P/Po thp (0,05 P/Po 0,25). III - KT QU V THO LUN 1. Ph hng ngoi xc nh nhanh cu trc, mu nghin cu c ghi ph IR trong vng dao ng 400 1300 cm-1, vng ny rt c trng cho cc dao ng mng ca zeolit. Hnh 1 trnh by ph hng ngoi ca vt liu HZSM-5 tng hp vi ngun silic t v tru c so snh vi mu zeolit ZSM-5 chun ca c trong vng dao ng t 400 - 1300 cm-1. T hnh 1 ta thy ph hng ngoi ca vt liu HZSM-5 tng hp t tru hon ton ph hp vi ph hng ngoi ca mu ZSM-5 chun, khng xut hin cc pic l, chng t vt liu tng hp c chnh l zeolit ZSM-5. Pic xut hin 550 cm-1 c trng cho dao ng ca cc vng 5-1 trong cu trc ZSM-5, n rt c trng cho trng thi tinh th ca vt liu. Theo [9], nu t l cng gia cc m ph 550 cm-1/450 cm-1 bng 0,8 th c th nh gi tinh th ca vt liu l 100%. Quan st trn ph, t l ny vt

liu tng hp c t tng ng vi cc mu chun bng 0,8. Kt qu ny cho php nh gi tinh th ca vt liu HZSM-5 tng hp c l 100%. Kt qu c trng XRD tip theo s khng nh thm mi tng quan ny. 2. Ph nhiu x Rnghen XRD tinh th ca mu nghin cu c xc nh bng phng php ghi ph XRD. Kt qu t phng php c trng XRD s lm r hn nhn nh c a ra trong phn c trng hng ngoi. Hnh 2 th hin ph XRD ca vt liu HZSM-5 tng hp t tru (hnh 2b) c ghi so snh vi ph ca mu ZSM-5 chun (hnh 2a). Quan st ph XRD ca HZSM-5 tng hp t tru, ta thy ph c ng nn rt bng phng, cc pic c trng cho cu trc zeolit ZSM-5 rt r nt v ph hp vi ph ca mu chun, khng xut hin pha l. Hn na, c th thy cng cc pic nhiu x c trng 2 = 5 - 100 v 2 = 20 - 250 cao tng ng mu zeolit ZSM-5 chun. T kt lun mu vt liu HZSM-5 tng hp t tru c tinh th rt cao (t xp x 100%), thnh phn ch tn ti hu nh duy nht mt pha tinh th. iu ny l hon ton ph hp vi cc kt lun a ra trong phn c trng hng ngoi. 3. nh SEM, TEM

xem xt r hn v cu trc tinh th, vt liu tng hp c phn tch bng cc phng php ghi nh SEM v TEM. nh SEM v TEM ca HZSM-5 ln lt c a ra trn cc hnh 3 v hnh 4. T nh SEM ca HZSM-5 (hnh 3) ta thy rng cc ht zeolit c hnh thnh trong qu trnh kt tinh c kch thc kh ng u, khong t 0,5 - 0,7 m. Khi nghin cu cu trc vt liu bng nh TEM (hnh 4), chng ti nhn thy trong cu trc vt liu HZSM-5 c tn ti h thng mao qun, l xp khng trt t, kch thc phn b kh rng. Cn c theo t l c th thy rng cc mao qun, l xp ny c kch thc khong t 10 50 nm. S tn ti ca cc mao qun, l xp ny c th c gii thch do s t chy vi oxi trong qu trnh nung mu ca cacbon cn li trong tru x l. Hin tng ny to nn h thng l xp, mao qun c kch thc trung bnh ca vt liu. 4. Phng php BET S tn ti ca h mao qun trung bnh trong cu trc ca vt liu HZSM-5 tng hp t tru c lm r hn bng phng php xc nh b mt ring BET. Quan st ng cong hp phkh hp ph N2 ca mu tng hp c th hin trn hnh 5 ta thy xut hin mt vng tr P/Po

630.25

(a)
ZS M-5 Chun

1225.16

795.23

545.69 1105.36 622.10 448.86

800.07

(b)
ZS M-5

548.42

1226.11 1096.68

451.32

1300

1200

1100

1000

S sng (cm-1 ) Wave number (cm-1)

900

800

700

600

500

400

Hnh 1: Ph IR ca zeolit ZSM-5 (a) Mu chun; (b) Mu tng hp t tru 49

(a)

(b) 5 10 20 30 2-Theta-scale 40 50

Hnh 2: Ph XRD ca zeolit ZSM-5 (a) Mu chun; (b) Mu tng hp t tru

200 nm
Hnh 3: nh SEM ca zeolit HZSM-5 gn 0,5 do c hin tng ngng t mao qun, mt dng c trng in hnh cho cu trc mao qun trung bnh ca vt liu [10]. iu ny cho thy vt liu HZSM-5 tng hp c c cu trc mao qun trung bnh. Kch thc mao qun c th hin chn lc trn ng phn b hnh 6 vi kch thc c a ra l 5,1 nm (mao qun trung bnh). Cc kt qu tnh ton t ng ng nhit hp ph-kh 50 Hnh 4: nh TEM ca zeolit HZSM-5 hp ph v ng phn b mao qun ca HZSM-5 cho thy vt liu tng hp c ngoi h thng vi mao qun cn tn ti h mao qun trung bnh vi th tch mao qun l 0,2635 cm2/g v din tch b mt ring vt liu l 483,51 m2/g. 5. Cng hng t ht nhn 27Al NMR S tn ti ca nhm trong khung mng zeolit c lin quan n tnh cht axit ca vt

liu. T kt qu thu c ta c th nh gi axit ca vt liu gin tip thng qua vic xc nh s phn b Al3+ trong mng li vt liu. y, chng ti s dng phng php cng

hng t ht nhn 27Al-NMR xc nh s phn b Al3+ trong, ngoi khung mng zeolit. Hnh 7 a ra ph 27Al-NMR ca mu zeolit HZSM-5 tng hp t tru.

180
Th tch hp ph, cm3

160 140 120 100 80 60 40 20 0 0,2 0,4 0,6 0,8 1,0

p sut tng i P/Po Hnh 5: ng ng nhit hp ph - kh hp ph N2 ca mu HZSM-5

2,0

1,5

dV/dD

1,0

5,1 +

0,5

10

15

20

Hnh 6: ng phn b kch thc mao qun ca HZSM-5 (nm) 51

(a) 180 140 100 60 20 -20 (ppm) -60 -100 -140 -180

Hnh 7: Ph 27Al-NMR ca HZSM-5 Quan st ph 27Al-NMR ca mu ta thy xut hin mt pic rt r nt vi cng ln gn 55 ppm, pic ny biu th lng nhm nm trong mng li zeolit [11, 12]. Ngoi pic ny ta cn thy khong 0 ppm xut hin thm mt pic. Pic ny c cng rt nh, khng ng k so vi pic 55 - 60 ppm. Theo [11, 12], pic ny c trng cho Al nm ngoi mng li zeolit. Kt qu ny chng t trong qu trnh tng hp vt liu HZSM-5, lng nhm a vo hu nh hon ton nm trong mng li zeolit. Cc kt qu thu c t phng php cng hng t ht nhn 27Al-NMR ca HZSM-5 cho thy vt liu tng hp t tru c axit cao. IV - KT LUN tng hp thnh cng vt liu HZSM-5 dng ngun silic t tru, mt vt liu c xem l ph thi trong qu trnh sn xut nng nghip. Cc kt qu c trng cho thy vt liu tng hp c c tinh th rt cao, tng ng vi vt liu chun. Mt c im mi v cu trc khi tng hp HZSM-5 t v tru c pht hin. Trong vt liu tng hp ngoi h thng mao qun ca zeolit cn pht hin thy tn ti mt h mao qun khng trt t, c kch thc phn b trong khong rng t 10 - 50 nm (h mao qun trung bnh). H mao qun ny c to ra do s t chy vi oxi trong qu trnh nung ca phn 52 cacbon cn li trong v tru x l. c im mi v cu trc HZSM-5 hi vng s lm tng ng k hot tnh xc tc ca vt liu. Cc kt qu thu c m ra thm mt hng nghin cu mi, c ngha trong vic tn dng ngun tru ph thi nng nghip tng hp cc cht xc tc trin vng khng ch trong lnh vc xc tc hp ph m cn trong qu trnh to nhin liu sinh hc t cn du thc vt, thay th ngun nhin liu t du m ang ngy cng cn kit. Cc nghin cu v vn trn s c cng b trong cc bi bo tip theo. TI LIU THAM KHO 1. S. P. R. Katikaneni, J. D. Adjaye, N. N. Bakhshi. Energy Fuels, 9 (4), 599 - 609 (1995a). 2. S. P. R. Katikaneni, J. D. Adjaye, N. N. Bakhshi. Can. J. Chem. Eng. 73 (4), 484 497 (1995b). 3. S. P. R. Katikaneni, J. D. Adjaye, R. O. Idem, N. N. Bakhshi. Ind. Eng. Chem. Res., 35 (10), 3332 - 3346 (1996). 4. L Vn Ct, Trn Th Kim Hoa. Ch to than hot tnh t v tru v tnh nng hp ph cht hu c trong nc. Vin Ho hc, Vin Khoa hc v Cng ngh Vit Nam (2005). 5. M. R. F. Gonc,alves, C. P. Bergmann.

Thermal insulators made with rice husk ashes: Production and correlation between properties and microstructure. Construction and Building Materials, In Press, Corrected Proof, Available online 17 October 2006. 6. Hiroaki Katsuki, Sachiko Furuta, Takanori Watari, Sridhar Komarneni. Microporous and Mesoporous Materials, Vol. 86 (1-3), 145 - 151 (2005). 7. Trn Th Kim Hoa. Lun vn thc s ho hc (2004). 8. G. Hortvath, K. J. Kawazoe, Journal of Chemical Engineering of Japan, 16, 470 (1983).

9. Kulkarni S. B., V. P. Shiralkar, A. N. Kosthane, R. B. Borade and P. Ratnasamy. J. Zeo. Vol. 2, 313 - 318 (1982). 10. HongVinh Thng, Qinglin Huang, Mladen Eic', Do Trong On and Serge Kaliaguine. Langmuir, 21, 5094 - 5101 (2005). 11. J. Jiao, S. S. Ray, W.Wang, J. Weitkamp, and M. Hunger. Z. Anogrg. Allg. Chem., 631, 484 - 490 (2005) 12. Michael Hunger, Eike Brunner. NMR Spectroscopy. Mol. Sieves, 4, 201 - 293 (2004).

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