V ol. 22 N o. 1 2 0 0 1 1 CHEM ICAL JOU RNAL O F CH IN ESE UN IV ERS IT IES 10 15 NaY (g ) (, 361005) (, 100083) N ay ( ), SiO 2gA l2o 3., N ay., n ( ) n ( ) 2 1,, N ay,. ; N ay; ; ; O 614. 35 A 025120790 (2001) 0120010206 Y. Y 1 000 nm [1 3 ]., Y,,, Y [4 14 ]., (< 100 nm ) Y., [15 19 ]., [15 ]. Bodart [16 ], Y 0. 8 Λm 0. 5 Λm. L inder [17 ],,,,,,. M aher [18 ],,, N, N 2, 0. 01 0. 1 Λm. Am bs [19 ], 0. 035 0. 069 Λm.,, SiO 2gA l2o 3, 2. 5. D utta [20 ],,. [20 ], (P recursors) [21 ],. N ay 0. 1 Λm, N ay, ED TA,. N ay,. : 1999206204. : ( : X598010). : (1967 ),,,,.
N o. 1 : N ay (g ) 11 1 1. 1 (26% SiO 2, 0. 8% N a2o, 73. 2% H 2O, ) [ (A l2 (SO 4) 3 18H 2O,, ]. (, ).. (, ). 1. 2 NaY 16N a2o A l2o 3 16SiO 2 210H 2O, 275 K 1 000 1 500 rgm in. ( 293 K) 48 h, :, 3. 2N a2o A l2o 3 10SiO 2 160H 2O,, A l2o 3 10%.,,.,, 373 K,. N ay, ( ),. A l2o 3 0. 5 8. 1. 3 R igaku D gm A X2g A X, R IPP N orm 146290 R IPP N orm 145290 [22 ],. JEM 2000 FX2g gq X22000, ; B ruker DRX24000M H z, TM S A l2 (SO 4) 3, 29 Si 27 A lm A S2NM R, [23 ]. 2 A SA P22400,. 1 N ay 1. 5, 363 K N ay. 1. T EM 2. XRD, Y. 1 1 2,,, N ay,. 29 Si 27 A lm A S2NM R, N ay,. 3 1 N ay 29 SiM A S2NM R. 3,, N ay F ig. 1 Crysta ll iza tion curve of zeol ite NaY syn thesized a t Si(A ln) (n= 0 3), 363 K w ith differen t complex ing agen ts[ n (com -, plex ing agen t) n (A l2o 3) = 1. 5 1 ]. NM R XRD N ay. 2 N ay 1. 5, 373 K N ay. 2 1. 1 363 K, 2 373 K N ay
12 V ol. 22 Table 1 Effect of complex ing agen t on max imum crysta ll in ity, time to max imum crysta ll in ity, and SiO 2gA l2o 3 ra tio and average crysta l size a t max imum crysta ll in ity of zeol ite NaY syn thesized a t 363 K and n (complex ing agen t) n (A l2o 3) = 1. 5 1 A dditive Crystallization tim eg n (SiO 2) gn (A l2o 3) BET A reag Crystal sizeg Crystallinity (% ) h XRD NM R (m 2 g - 1 ) nm None 48 90. 54 5. 18 5. 22 690 200 Editate 33 82. 63 5. 65 5. 74 734 70 Citrate 36 87. 54 5. 67 5. 75 770 70 A cetate 36 78. 25 5. 78 5. 85 732 60 F ig. 2 TEM p ictures of zeol ite NaY syn thesized a t 363 K in the absence of com lex ing agen t(a), in the presence of complex ing agen t of edita te (B), c itra te (C) and aceta te (D ) respectively n (comp lexing agent) n (A l2o 3) = 1. 5 1...,., [24 ].,, [25 ]. [17, 26, 27 ], SOD FAU,,., F ig. 3 29 SiM AS-NM R spectra of zeol ite NaY syn thesized, [28 ]. Kuh i [29 ] a t 363 K (a ) in the absence of complex ing agen t, ED TA in the presence of complex ing agen t of edita te (b),, OH -,, N ay. c itra te (c) and aceta te (d), respectively n (comp lexing agent) n (A l2o 3) = 1. 5 1. L inder [17 ],,, OH -,.,,.,,.,, OH -,.
N o. 1 : N ay (g ) 13 Table 2 Effect of complex ing agen t on max imum crysta ll in ity, time to max imum crysta ll in ity, and SiO 2gA l2o 3 ra tio and average crysta l size a t max imum crysta ll in ity of zeol ite NaY syn thesized a t 373 K and n (complex ing agen t) n (A l2o 3) = 1. 5 1 Crystallization tim eg n (SiO 2) gn (A l2o 3) BET A reag Crystal sizeg A dditive Crystallinity (% ) h XRD NM R (m 2 g - 1 ) nm None 36 94. 72 5. 20 5. 25 700 260 Editate 18 91. 77 5. 73 739 90 Citrate 21 94. 10 5. 81 5. 89 749 90 A cetate 24 85. 97 5. 79 5. 91 738 75. N ay, OH -,,,, N ay,., 1 2, ( ),, N ay, ; F ig. 4 Crysta ll iza tion curve of zeol ite NaY syn thesized a t, N ay, 373 K ;, n (citrate) n (A l2o 3) : a. ED TA. e. 4. 0; f. 6. 0; g. 8. 0. 0; b. 1. 0; c. 1. 5; d. 2. 0;, : > >.,, A l N ay,,.,. 3. 4 N ay 373 K. Table 3 Effect of c itra te addition w ith differen t n (c itra te) n (A l2o 3) ra tios on max imum crysta ll in ity, time to max imum crysta ll in ity and n (SiO 2 ) gn (A l2o 3 ) ra tio and crysta l size a t max imum crysta ll in ity of NaY syn thesized a t 373 K Crystallization n (SiO 2) gn (A l2o 3) BET A reag Crystal sizeg n (citrate) n (A l2o 3) Crystallinity (% ) tim egh XRD NM R (m 2 g - 1 ) nm 0 36 94. 72 5. 20 5. 25 700 260 1 24 95. 8 5. 84 5. 85 747 85 1. 5 21 94. 1 5. 81 5. 89 749 90 2 27 94. 37 5. 80 5. 83 765 100 4 39 94. 62 5. 63 5. 74 735 150 6 45 75. 05 5. 74 641 200 8 45 20. 54 5. 48 4 3,, N ay. [n ( ) n ( ) 2 1 ], N ay.,,, N ay ; [n ( ) n ( ) > 2 1 ],,,,,,, n ( ) n ( ) = 8 1, N ay, N ay.,,,
14 V ol. 22.,, A l2o 3 2. 3, 1. 5,,,, L inder [17 ]. N ay L inder [17 ],.,.,., ;,,., L inder [17 ], N ax 5. 4 Λm 3. 5 Λm, 35%, N ay., N ay, L inder. ( 275 K) [4 ] A l 3+,. 4 N ay,,,. ( A l2o 3 2 ),,,, N ay, ;,,. ED TA,,,.,,. 1 Ciric J.. J. Coll. Inṫ Sci. [J ], 1968, 28: 315 324 2 Tom H., Hennie S., A rend H. et al.. EP, 0 336 207 A 1[P ], 1989 3 F reund E. F.. J. Crysṫ Grow th [J ], 1976, 34: 11 23 4 CHAO Zi2Sheng. Post Ph. D. D issertation[d ], Research Institute of Petroleum P rocessing, S INO PEC, 1998: 1 26 5 Pu S. B., Inui T.. Zeolites[J ], 1996, 17: 334 339 6 Herrm ann C., Haas J., Fetting F.. App l. Catal. [J ], 1987, 35: 299 310 7 V an der PolA. J. H. P., V erduyn A. J., V an der Hooff J. H. C. ; Edṡ, Ballmoos R. Von, H iggins J. B., T reacy M. M. J.. P roceedings of the 9th International Zeolite Conference[M ], M obtreal: Butterworth2Heinem ann, 1992: 607 614 8 A guiar E. F. S., V alle M. L. M., Silva M. P. et al.. Zeolites[J ], 1995, 15: 620 623 9 Thom as C. L., Barm by D. S.. J. Catal. [J ], 1968, 12: 341 346 10 M aselli J. M., W. Peters A.. Caṫ Rev. Sci. Eng. [J ], 1984, 26: 525 554 11 Rajagopalan K., Peters A. W., Edw ards G. C.. App l. Catal. [J ], 1986, 23: 69 80 12 Cam blorm M. A., Corm a A., M artinez A. et al.. App l. Catal. [J ], 1989, 55: 65 74 13 Pachovsky R. A., W ojchiechow skib. W.. A IChe J. [J ], 1973, 19: 1 121 1 125 14 Shiralkar V. P., Joshi P. N., Eapen M. J. et al.. Zelolites[J ], 1991, 11: 511 516 15 M yatt G. L., Budd P. M., P rice C.. Zeolite[J ], 1994, 14: 190 197 16 Bodart P., N agy J. B., Gabelica Z. et al.. J. Chim. Phyṡ [J ], 1986, 83: 777 790 17 L indner T., L echert H.. Zeolites[J ], 1996, 16: 196 206 18 M aher P. K., Scherzer J.. U S Patent 3516786[P ], 1970 19 Am bsw. A., Sw arthmore Pa.. U S Patent 4372931[P ], 1983 20 Dutta P. K., PuriM., Bow ers C. ; Edṡ, O ccellim. L., Robson H. E.. Zeolites Synthesis, ACS Sym. Seṙ, ACS[M ], 1989, 398: 98 109 21 Dutta P. K., Bow ers C.. Zeolits[J ], 1991, 11: 507 510 22 YAN G Cui2D ing ( ), GU Kan2Ying ( ), WU W en2hui( ). A nalysis M ethod in Petrochem ical Industry2R IPP Norm ( 2R IPP ) [M ], Bejing: Science P ress, 1990: 412 415
N o. 1 : N ay (g ) 15 23 klinow aki J., Ram das S., Thom as J. et al.. J. Chem. Soc., Faraday T ranṡ g [J ], 1982, 78: 1 025 1 050 24 Sano T., O kabe K., Kohtoku Y. et al.. Zeolites[J ], 1985, 5: 194 198 25 Gonthier S., Thomp son R. W. ; Edṡ, Jansen J. C., StockerM., Garge H. G. et al.. A dvanced Zeolite Science and App lications, Study in Surḟ Sci. & Catal. [M ], Am sterdam: E lsevier, 1994, 85: 43 73 26 Schoem an B. J., Sterte J., O tterstedt J. E.. Zeolite[J ], 1994, 14: 208 216 27 L echert H., Kacirek H.. Zeolite[J ], 1991, 11: 720 728 28 Cundy C. S., Low e B. M., Sinclair D. M.. Faraday D iscusṡ [J ], 1993, 95: 235 252 29 Kuhi G. H.. A dv. Chem. Seṙ [J ], 1971, 101: 63 83 Syn thesis of Ultraf ine Zeol ite NaY (g ) Effect of Com plex ing Agen t CHAO Zi2Sheng 3, L IN H ai2q iang, CH EN Guo2Zhou, WU T ing2h ua, WAN H ui2l in (Chem istry D ep artm ent and S tate K ey L aboratory f or P hy sical Chem istry of S olid S urf ace, X iam en U niversity, X iam en 361005, Ch ina) M IN En2Ze (R esearch Institute of P etroleum P rocessing, S IN O P EC, B eij ing 100083, Ch ina) Abstract U ltrafine zeolite N ay w as hydrotherm ally synthesized w ith silica sol and A l2 (SO 4) 3 as silica and alum ina sources, respectively, by adding com p lex ing agen t such as citrate, acetate o r editate to syn thesis batch. T he effect of the amount of citrate on the crystallization rate, SiO 2gA l2o 3 ratio and crystal size of as2synthesized zeolite N ay w as investigated. W hen the relatively low er amount of citrate [ n (citrate) n (A l2o 3) 2 1 ] w as added, both the crystallization rate and the SiO 2gA l2o 3 ratio increased w h ile the crystal size reduced obviously com paring w ith that in the absence of citrate. T h is indicates that the nucleation and crystallization of zeo lite N ay w as p rom o ted by com p lex ing agen ṫ W hen the relatively h igher amount of citrate [ n ( citrate ) n (A l2o 3 ) > 2 1 ] w as added, the above p romotion effect dim in ished. T he crystallization rate w as found to reduce com paring w ith that in the absence of citrate, although the crystal size w as still sm aller than that in the later case. T he op tim um amount of citrate added to batch appears to be at the citrate A l2o 3 molar ratio of 1. 5 1. T he sim ilar p romotion effect w as also observed both for the addition of editate and acetate w ith the molar ratio of editate A l2o 3 and acetate A l2o 3 equal to 1. 5, respectively. T he p rom o tion effect of com p lex ing agen ts to the nucleation and crystallization of zeolite N ay w as related w ith their comp lexing ability to alum inum. Keywords U ltrafine zeolite; N ay; Synthesis; C rystal size; Comp lexing agent (Ed. : F, G)