14 2 V o l. 14,N o. 2 2000 4 JOU RNAL O F M OL ECULA R CA TAL YS IS (CH INA ) A p r. 2000 : 100123555 (2000) 0220111208 WO 3gZrO 2 - g. ZrO 2,,, 1) (, 130022) : ZrO 2 WO 3gZrO 2 SO 4 2- gzro 2 M oo 3gZrO 2, XRD D TA 2 T G H 22T PR N H 32T PD, ZrO 2 T 2, Zr (OH ) 4, ZrO 2 T 2,,, ZrO 2, 2, Zr (OH ) 4,,, C 5 C 7, C 8 0 : WO 3gZrO 2 ; ZrO 2; 2 : O 643. 32 : A (M ) W O 3g ZrO 2 2 ( 100% ) C 8 0 (> 80% ) [1 ]. (Β2 SO 4 2- [2 ]. gzro 2 ),, [3 ]., ZrO 2 W O 3gZrO 2, ZrO 2 [4 ]., ( Zr (OH ) 4 ) ( SO 4 2- ), Zr (OH ) 4 SO 4 2- M xo y, ZrO 2 T (T etragonal) 2 T 2 M (M onoclin ic) 2, T 2 [ 5 ], (SCFD T ) ZrO 2 T 2 ( 700 ). ZrO 2, SO 4 2- W O 3 M oo 3,, T 2 ZrO 2 1 1. 1 1. 1. 1 ZrO 2 [5 ] 500 ml (0. 17 mo l L - 1 ) ZrOC l2, (28% ), ph 10. 30, Zr (OH ) 4 2 h,, C l - ( 0. 1 mo l. L - 1 A gno 3 ), 500 ml, Zr (OH ) 4 (0. 043 mm ),, 400 ml,,, : 1999210218; : 1999212227. : ( 29792076). :,, 38,, 1)
112 14 (T = 533 K, p = 7. 5 M Pa), 0. 5 h,,,,, ZrO 2 ( ZO ). 1. 1. 2 W O 3gZO SO 4 2- gzo M oo 3gZO ZrO 2 [ (N H 4) 5H 5 [H 2 (W O 4) 6 ] H 2O ] 0. 5 mo l H 2SO 4 [ (N H 4) 6M o 7O 24 4H 2O ], 368 K 24 h, 4 h, ZrO 2 W O 3gZO SO 4 2- gzo M oo 3gZO 3 W ZO SZO M ZO. Zr (OH ) 4 [1 ],, Zr (OH ) 4 W O 3gZrO 2 SO 4 2- IM 2W IM 2S IM 2M. 1. 2 gzro 2 M oo 3gZrO 2 JEQL JXA 2840 (SEM ), 20 kv. BET XRD, R igaku D gm ax2g X2 (CuKΑg, N i ), 2Η 10 80, X 40 kv 20 ma. R igaku 2 (T G2D TA ), 10 Kgm in, 50 ml gm in. ( T PR ), W O 3 SO 4 2- M oo 3 0. 1000 g 6 mm, ( 30 ml gm in), 923 K 1 h,, (5%H 2), (10 gm in) 1 073 K,, N H 32T PD,, 0. 1000 g 6 mm, ( 30 ml gm in), 923 K, 1 h, (288 K) 1 h, 100 m in,,, H amm ett, (pkbh + = - 13. 16) 2, 42 (pkbh + = - 13. 75) 2, 42 (pkbh + = - 14. 52) 1, 3, 52 (pkbh + = - 16. 12), 1. 3 [1 ]. 10 mm, 20 cm. 0. 40 0. 20 mm 2 g, 573 K 3 h, 353 K,, ( g 8), (L SHV ) 2,, 1. 4 M Pa. 103, 3 mm, 10 m, 6201 Β, Β 2, 200 K, GC2 112, ( 50 m, 0. 25 mm, SE254). 303 K, 473 K, 5 Kgm in, (V G2Q uattro H P25890A ) 2 2. 1 2. 1. 1 1 SEM, Zr (OH ) 4 (393 K) (A ),, ; 923 K, (C) ; ZrO 2 (B ),,, 2, Zr (OH ) 4 (a) ; ZrO 2 T 2 (b)., (T = 533 K, P = 7. 5 M Pa) Zr (OH ) 4 T 2, ZrO 2 923 K, M 2 (c), Zr (OH ) 4 923 K, ( ). Zr (OH ) 4 ( ) 923 K, T 2 (d). T 2 ZrO 2,, T 2 ( 2 e g).
2 : WO 3gZrO 2 2 g. 113 1 SEM F ig. 1 SEM im ages of different carriers (A ) Zr (OH ) 4 ( 3 000); (B ) superfine ZrO 2 ( 10 000); (C) ZrO 2 (923 K) ( 1 000) 2 XRD F ig. 2 XRD patterns of M 2ZrO 2 and T 2ZrO 2 samp les, W O 3gZrO 2 W O 3 0. 189 0. 265 g, T 2 ZrO 2 79. 2% 82. 6% ( 1).,, W O 3, ZrO 2 M 2, T 2 SZO M ZO, 923 K 1 023 K, SZO, T 2 ZrO 2 75. 7% 40. 7% ; M ZO, T 2 ZrO 2 77. 7% 70. 7%., W ZO T 2 SZO M ZO 2. 1. 2 1. ZrO 2 275 m 2 g - 1, [ 6 ] (923 K), ZrO 2 M 2, 44 m 2 g - 1, Zr (OH ) 4 (923 K) ZrO 2 36 m 2 g - 1 ZrO 2 W ZO SZO M ZO, IM,. ZrO 2,, ( ) ZrO 2 T 2 ;,, ZrO 2, ZrO 2 W ZO, W O 3 0. 189 g W O 3g g ZrO 2 0. 265 g W O 3 g ZrO 2, 195 216 m 2 g - 1, T 2 ZrO 2, W ZO SZO M ZO,,, T 2 ZrO 2, SZO (1 023 K),, T 2 ZrO 2 40. 7%, 48 m 2 g - 1.
114 14 1 T able 1 Physicochem ical p roperties and catalytic activities of catalysts Com po sition Calcination T 2ZrO 2 Specific A cid amound A cid Initial Catalyst tem perature surface area (283 923 K) strength activity (g g ZrO 2) (K) (% ) (m 2 g) (mmo l N H 3 g) (pkbh ) (% ) ZO 0-85. 2 275 - - - - ZO 0 923 7. 8 44 1. 0 - - - W ZO 0. 189 923 79. 0 195 9. 87-16. 12 100 65. 00 0. 227 923 81. 6 207 11. 7-16. 12 100 63. 84 0. 265 923 82. 6 216 12. 1-16. 12 100 61. 56 0. 265 973-210 9. 9-16. 12 100 61. 34 0. 265 1 023 78. 3 186 6. 43-16. 12 100 59. 46 SZO 0. 5 mo l H 2SO 4 923 75. 7 154 8. 3-14. 52 99. 5 69. 40 0. 5 mo l H 2SO 4 1 023 40. 7 48 3. 1-14. 52 71. 3 84. 87 M ZO 0. 115 923 77. 7 173 8. 7-13. 75 92. 5 83. 89 0. 115 1 023 70. 7 140 7. 2-13. 15 80. 0 85. 00 C 8 (% ) 2. 1. 3 2 2 (T G2D TA ) ( 3), ZrO 2, 3 T G2D TA F ig. 3 T G2D TA curves of samp les 423 K, 7. 7% ( 3 (A ) T G (ZO ) ), ; 473 K 773 K,, 5. 8%, ZrO 2 D TA ( 3 (A ) D TA (ZO ) ), 373 K 723 K,. Zr (OH ) 4 D TA ( 3 (A ) ), 633 K 713 K, T 2 ZrO 2 M 2 ZrO 2,, ZrO 2, ZrO 2 ( 3 (A ) W ZO ), 473 K,, ; 473 K 793 K,, ZrO 2, 578 K, Zr (OH ) 4, 90 K, ZrO 2 (T 2 ) SZO, 833 K,, M ZO W ZO, 573 K, Zr (OH ) 4 IM 2M, D TA IM 2W 823 K
2 : WO 3gZrO 2 2 g. 115 ZrO 2 T 2 M oo 3 Zr (M oo 4) 2, M o- O - Zr 2. 2 2. 2. 1 H 22T PR ( 4), Zr (OH ) 4 ( 4 a), 873 K 4 H 22T PR F ig. 4 H 22T PR p rofiles of samp les a: Zr (OH ) 4; c: ZO (923 K); d: IM 2W (0. 227, 923 K); e: W ZO (0. 189, 923 K); f: W ZO (0. 227, 923 K); g: W ZO (0. 265, 923 K); h: W ZO (0. 265, 1 023 K); i: SZO (1 023 K); j: SZO (1 023 K); k: M ZO (0. 115, 923 K); l: M ZO (0. 115, 1 023 K) 1 073 K ( 1 053 K ), [7 ]. ZrO 2, 673 K 1 123 K (c),,, Zr (OH ) 4 IM 2W, 773 1 073 K 2 ( 4 (A ) d). (770 870 K) W O 3 ; W (g ) ZrO 2 W ZO (923 K), ( 4 (A ) e f),, W O 3, 0. 265 g W O 3 g ZrO 2 ( 4 (A ) g), W O 3,, ( 4 (A ) g h), W O 3 XRD W O 3, 2 ; Zr (OH ) 4, 0. 227 g W O 3 g ZrO 2 ( 1 023 K ), XRD W O 3, ZrO 2,. T 2 ZrO 2 W ZO, IM 2W,, W ZO, W O 3 SZO ( 4 (B ) i j), 710 K 1 000 K, SO 2 [6, 7 ]. 923 K, SZO (1 073 K) ( 4 (B ) j),, 1 000 K M ZO W O 3gZrO 2, 2, 773 K M oo 3, W O 3, 860 K M o (g )., M oo 3, 2. 2. 2 N H 32T PD,, 5 ZrO 2 ( 533 K ),
116 14 420 K ( 5 b) ; 923 K, ( 5 c). T 2 ZrO 2 5 N H 32T PD F ig. 5 N H 32T PD p rofiles of samp les b: ZO ; c: ZO (923 K); d: IM 2W (0. 227, 923 K); e: W ZO (0. 189, 923 K); f: W ZO (0. 227, 923 K); g: W ZO (0. 265, 923 K); h: W ZO (0. 265, 1 023 K); i: SZO (923 K); j: SZO (1 023 K); k: M ZO (0. 115, 923 K); l: M ZO (0. 115, 1 023 K) ZrO 2 W ZO, (383 923 K ) IM 2W ( 1), W ZO (0. 265 g W O 3 g ZrO 2), T 2ZrO 2, SZO, SZO (1 023 K ), T 2ZrO 2% 40. 7%,, SZO (923 K) IM 2S (923 K), M ZO, W ZO SZO, H amm ett 1. ZrO 2, IM, IM 2W (1 023 K), W O 3, ; W ZO (1 023 K ), W O 3, 1, 3, 52, W ZO,, 0. 115 g M oo 3 g ZrO 2 (923 K) IM 2M, 2. 3 2. 3. 1, C 4 =, (, % ) : 1. 46 12 + 9. 97 82. 96 22 0. 65 4. 51 22 0. 50 88. 93 11. 12 C 4 0 gc 4 = 8. 0; ic 4 0 gc 4 = = 7. 4 923 K, 2 2, W ZO, 0. 189 0. 265 g W O 3 g ZrO 2,, ZrO 2,, IM 2W, 0. 189 0. 227 g W O 3 g ZrO 2, ; 0. 265 g W O 3g g ZrO 2, IM 2W, 0. 227 g W O 3 g ZrO 2,, 60 m in, W ZO IM 2W SZO IM 2S M ZO IM 2S,, 6. W ZO, 0. 265 g W O 3 g ZrO 2 973 K 1 023 K,,
118 14 W O 3gZrO 2 ( ), W O 3, 3. 3, ZrO 2 C 5 C 7, C 8 0 [1 ],,,. WO 3gZrO 2 2 ( I). W [J ]., 2000, 21 (3) [2 ] Co rm a A, M artinez A. Chem istry, Catalysts and P rocesses fo r Isoparaffin2o lefin A lkylation: A ctual Situation and Future T rend [J ]. Catal R ev2s ci E ng, 1993, 35 (4): 483 [3 ],,,. WO 3gZrO 2 2 ( II). [J ]., [4 ] A rata K. P reparation of Superacid by M etal O xides fo r R eaction of Butanes and Peutanes[J ]. A pp l Catal A General, 1996, 146: 3 [5 ],,,. [J ]., 1995, 11 (1): 46 [6 ] Sayari A, D icko A. T he State of P latinum in P t on Sulfated Zirconia Supperacid Catalysts [J ]. 1994, 146: 561 J Catal, [7 ] M o rterra C, Cerrato G. P latinum 2P romo ted and U np rom eted Sulfated Zirconia Catalysts P repared by a O ne2step A erogel P rocedure[j ]. J Catal, 1997, 165: 172 Study of the A lkylation of Isobutane with n-butenes over WO 3gZrO 2 Strong Solid Ac id g. Effect of Superf ine ZrO 2 Carr ier on Physico-chem ical Properties and Catalytic Behav iours of the Catalyst SUN W en2dong, ZHAO Zhen2bo, L IU yu, W U Yue (Chang chun Institu te of A pp lied Chem istry. T he Ch inese A cad em y of S ciences, C hang chun 130022) Abstract: A series of W O 3gZrO 2, SO 4 2- gzro 2, and M oo 3gZrO 2 strong so lid acids w ere p repared. T heir crystal structu re, su rface state and acidity w ere determ ined by XRD, T G2D TA, H 22T PR and N H 32T PD. T he resu lts revealed that superfine ZrO 2 m ain ly ex ists in tetragonal phase, how ever, the amoun t of T 2 phase ZrO 2 decreases, bu t it has a larger specific area, acid amoun ts and loading capacity as compared w ith catalyst p repared by traditional app roach u sing Zr (OH ) 4 as carrier. A cid strength of the catalyst increases w ith the calcination temperatu re, w h ich indicates that its su rface state has changed sign ifican tly. T he isobu tane alkylation of n2bu tene catalysed by variou s catalysts has been investigated. Experim en tal resu lts indicated that better o lefin conversion s are reached than that over catalyst p repared by traditional Zr (OH ) 4 as carrierṡ C 8 0 selectivity decreases due to the fo rm ation of mo re crack ing p roducts of C 5 C 7. Key words: W O 3gZrO 2; Strong so lid acid; Superfine ZrO 2; Isobu tanegbutene alkylation