Preparation and Application of Amorphous Alloy Catalyst

Transcript

1 PROGRESS IN CHEMISTRY Vol. 17 No. 4 Jul., ( ), XRD EXAFS DSC SEM TEM XPS : O ; TQ42618 : A : X(2005) Preparation and Application of Amorphous Alloy Catalyst Xiong Zhongqiang Mi Zhentao Zhang Xiangwen 3 ( Key Laboratory for Green Chemical Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin , China) Abstract The development and applications of amorphous alloy catalyst are summarized. The most widely used techniques for the preparation of amorphous alloy catalyst are classified into rapid quenching method, chemical reduction method and impregnation2chemical reduction method. The reaction activity of the catalyst can be adjusted by changing the preparing condition, which including the calcination temperature, the metal load and the carrier. The amorphous structure, surface morphology and activity center can be determined and characterized by XRD, EXAFS, DSC, SEM, TEM and XPS. A detailed discussion of amorphous alloy catalyst in hydrogenation of unsaturated compound is presented. Key words amorphous alloys ; catalysts ; rapid quenching methods ; chemical reduction methods [2 4 ] : +, Fe2B Pd2Si Co2B2Si Ni2Fe2P2B ; +,, Ni2Zr Cu2Zr Pd2Zr, 1934, ;,, 1nm, 15nm 1980 Simth [1 ] 1nm,, 5 15nm : , : e2mail tpt. tj. cn

2 4 615, ; (2),, ; (3),, ; (4), 011 1m 2 Πg, Ni2Al2P [8,9 ],,,, Ni2P Ni2B Ni2Cu2B 2.,,, PdΠC, 1986 van Wonterghem,, [5 ] 2 2,Ni2B : BH H 2 O BO H 2 (1), BH Ni H 2 O - 3 : 2Ni + BO 2 + 4H + + 2H 2 (2) BH H 2 O B + OH H 2 (3) 11 (2) (3) 1960 Duwez, Willens [6 ],, 106 Πs Al 2 O 3 Au 70 Si 30, (3) (2), B, [10 ] ; [11, ] Ni 2 B Ni 3 B, :, 2BH Ni H 2 O 30mΠs 5mm 30m Ni 2 B + HBO 2 + 2H H 2 (4), [7 ] 5BH Ni H 2 O 2Ni 3 B + 7H H 2 (5) : (1) : ; (2), 2H 2 PO Ni H 2 O ; (3) 2H 2 PO Ni + H 2 (6) : (1) Ni2B 200m 2 Πg,

3 [12 ] NaH 2 PO 2 6H 2 O CH 3 COONa, 10gΠL,, 90, 2h,,, NiCoB Ni2BΠSiO 2 (10nm),,, SiO 2 NiCl 2, 8 ; Ni2B KBH 4,, 100 % 98 %,, PdΠC [18,19 ] (3) Ni2Co2B, : (1), [20 24 ], ; (2), ; (3) Ni2Co2B KBH 4 NiCl 2 CoCl 3,, KBH 4 = 5 2 (mol),,,, Deng [13 ] 1988, (4) Pd2BΠSiO 2,,,,, Yu [25 ] Pd2BΠSiO 2, PdCl 2 3., ( 100 ) ( 200 ), KBH 4, KBH 4, ( KBH, 4 Pd 2 + = 5 1 (mol) ) ( KBH 4 NaH 2 PO 3 ),,, (1) R2Ni2P Ni2Al2P,Li, [14 ] Ni :4812 %, Al :4817 %, P :311 %, 5mm 10 20nm , Ni2BΠSiO 2, - Al BH 4 Ni 2 + Π [26, SiO 2, ] 17 ] (2) Ni2B (P) (110g SiO 2, 198mΠg, ) [15,Ni2BΠSiO 2 NiCl 2, ,200

4 4 617, 1 1 Fig. 2 Effect of annealing temperature on conversion for benzene Fig. 1 Dependence of hydrogenation activity of hydrogenation over ultrafine NiP and NiB amorphous acrylonitrile on calcination temperature alloys XPS,, %,, NiP 200,, ,,400,Ni 2 + SiO 2 20 %, X (XAFS) X ;,Ni 2 + (XRD) (DTA) SiO 2,, ; NiB :, Ni 2 + SiO 2, 320 Ni 2 + BH - 4, NiB Ni 3 B 200 Ni 2 B ; Ni, Ni 3 B Ni [29 ] Table 1 Dependence of mol ratio of surface Ni on NiP,300 calcination temperature calcination temperature ( ) mol ( %) Ni Ni [27 ], Ni, ; NiP NiB NiP [28 ] :2gNiB, NiP 300 NiP, Ar, Ni 3 P Ni,, 2h 2 2 NiP NiB, NiP Ni Ni 3 P, 360 Ni 3 P Ni, Ni 3 B Ni 2 B NiB, 400, NiB 3.,NiB Ni 2 + BH - 4 Ni2B,350 Ni %, 1 ;,3 Ni2BΠSiO 2

5 618 17, 3 Ni Fig. 3 Dependence of reduction percent on Ni content,, Ni 2 + ;,3. Ni 2 + BH - 4 X 614 % : 614 % (XPS),,,, Ni2B B Ni,Ni2P Ni, : P 34 ] ;Beilin [35 ] Ni P ; ; Tamaki [36 ] X ( XRD) X Ni2P RF :Ni2P ( EXAFS) ; P,P (DSC) ( TPR) 25 %, P Ni,P ; X 25 %,P Ni, Ni2B (XPS) B Ni ; (SEM2EDX) ( HRTEM) ; [5,11,30,31 ] 1. 2, 1. 3 : ; ( RDF) (3) (SAED), 1 2. (1) XRD XRD,, ;,, (2) EXAFS Wang, [39 ] Pd Pt Ni K,, [32,

6 Table 2 Amorphous catalyst in different hydrogenation reactions reaction reaction condition catalyst conversion( %) selectivity( %) benzene2cyclohexane liquid,150,4. 0MPa,4. 0h Ni2BΠAl 2 O 3 (1. 0g,20 %) phemethylol2methylbenzene liquid,120,1. 0MPa,ethanol,4. 0h Ni2BΠSiO 2 (1. 0g,20 %) adipic dinitrile2hexamethylene diamine [37,38 ] liquid,120,410mpa,ethanol,4. 0h Ni2Co2BΠSiO 2 (1. 0g,20 %) cyclopentadiene2cyclopentene [39,40 ] gas2solid,120,s. V. 10h - 1 Ni2BΠSiO 2 (1. 0g,5 %) 100 > 96 cyanobenzene2benzoic amine liquid,110,4. 0MPa,ethanol,4. 0h Ni2Co2BΠSiO 2 (1. 0g,20 %) nitrobenzene2aniline liquid,110,1. 0MPa,ethanol,4. 0h Ni2BΠSiO 2 (1. 0g,20 %) glucose2sorbitol [41,42 ] liquid,100,4. 0MPa,water,4. 0h 10 %Ni21 %W2BΠSiO 2 (1. 0g) ,, 10h - 1, [39,43 47 ] Ni2BΠSiO 2 3, : Ni2BΠSiO 2 Table 3 Properties of the amorphous Ni2BΠSiO 2 catalysts on cyclopentadiene hydrogenation samples S active (m 2 Πg Ni) S BET (m 2 Πg) V pore (cm 3 Πg) d pore (nm) Ni cont. (wt. %) B cont. (wt. %) conversion ( %) selectivity ( %) Ni2BΠSiO Ni2BΠSiO 2 a a catalyst used for 700h, Al 2 O 3 [48,49 ], Ni2P Ni2PΠSiO 2 Ni2BΠ SiO 2 94 %, 100 % [ ] 10gΠg,, Pd2BΠSiO 2 [24,58 ] [59 ] 110MPa 30 [50 ] Ni 80 P 20 Pd2BΠSiO 2,, 98 % 95 %, 200,400, 90 % 8719 [51 ] Li [14 ], Ni2B Ni2Al2P, :C 2 H %, C 2 H 4 Al, 110MPa %, H %, MPa SiO 2,Cu Al 2 O 3 3.,Raney Ni h %

7 [14,16,18,60 63 ] Ni2P, :015ml 10ml 012g 210MPa,100 4h 3017 %,, Ce :Ni = 0108 :1 62 % Ni2Co2B Ru2BΠSiO 2 [17], : ; 115 : ,,, [ 1 ] Smith G V, Brower W E. Proc. Int. Congr. Catal. 7th, Tokyo, [ 2 ] ( Tang Z). ( Chemical Industry and Engineering Progress), 2001(2) : [ 3 ] (Lv Z G), ( Guo Z M). ( Chemical Industry and Engineering Progress), 2002, 21(8) : [ 4 ] ( Tang Z). ( Advances in Fine Petrochemicals), 2000, 1(2) : [ 5 ] (Min E Z), (Li C Y). [30] Deng J F, Chen H Y, Bao X H, et al. Applied Surface Science, ( Science and Engineering Foundation of Green Petrochemical Technology). (Beijing) : [31] (Shen B R), ( Fang Z G), ( Fan K N) (China Petrochemical Press), (Acta Chimica Sinica), 1999, 57 : [ 6 ] Duwez P, Willens R H. TMS2AIME, 1963, 227 : 362 [ 7 ] Deng J F, Li H X, Wang W J. Catalysis Today, 1999, 51 : [ 8 ] (Zong B N), (Min E Z), ( Zhu Y S). CN , 1993 [ 9 ] Ma A Z, Lu W Z, Zong B N, et al. Research in Chinese Univ., 2000, 16 : 15 [10] Li H X, Li H, Dai W L, et al. Applied Catalysis A : General, 2003, 238 : [11] (Ma A Z). ( Chinese Journal of Catalysis), 1999, 20(6) : [12] ( Yang J), (Chai L), (Deng J F). (Acta China Sinica), 1994, 52 : [13] Deng J F, Zhang X P, Min E Z. Applied Catalysis, 1988, 37 : [14] Li H X, Wang W J, Zong B N, et al. Chem. Lett., 1998, 4 : [15] Deng J F, Zhang X P. Applied Catalysis A : General, 1988, 37 : [16] Deng J F, Zhang X P. Solid State Ionics, 1989, 32 : (Deng J F), (Zhang X P), (Li D J). (Acta Chimica Sinica), 1991, 49(3) : [18] Wang H M, Yu Z B, Chen H Y, et al. Applied Catalysis A : General, 1995, 129 : L143 L149 [19] Yu Z B, Qiao M H, Li H X, et al. Applied Catalysis A : General, 1997, 163 : 1 13 [20] Zhang R B, Li F Y, Zhang N, et al. Applied Catalysis A : General, 2003, 239 : [21] (Shi Q J), (Li F Y), (Luo L T). (Journal of Molecular Catalysis), 1999, 13(1) : 9 14 [22] Baiker A. Journal of Molecular Catalysis A : Chemical, 1997, [23] Takahashi T, Inoue M, Kai T. Applied Catalysis A : General, 2001, 218 : [24] Takahashi T, Kai T. Materials Science and Engineering, 1999, A267 : [25] Yu X B, Wang M H, Li H X. Applied Catalysis A : General, 2000, 202 : [26] Li H, Li H X, Dai W L, et al. Applied Catalysis A : General, 2001, 207 : [27] (Wei S Q), (Wang X G), ( Yin SL). (Chinese Journal of Catalysis), 2001, 22 (2) : [28] (Wang X G), ( Zhang X Y), (Li Z R). ( Chinese Journal of Catalysis), 2001, 22 (4) : [29] Li H X, Chen H Y, Dong S Z, et al. Applied Surface Science, 1998, 125 : , 81 : [32] Okamoto Y, Nitta Y, Imanaka T, et al. J. Catal., 1980, 64 : [33] Hou YJ, Wang Y Q, He F, et al. Materials Letters, 2004, 58 : [34] Hou YJ, Wang YQ, He F, et al. Applied Catslysis A : General, 2004, 259 : [35] Beilin E, Traverse A, Szasz A, et al. J. Phys. F : Met. Phys., 1987, 17 : [36] Tamaki J, Imanaka T. Chem. Lett., 1986 : [37] Li H X, Xu Y P, Deng J F. New J. Chem., 1999, 23 (11) : [38] Yu X B, Li H X, Deng J F. Applied Catalysis A : General, 2000, 199 :

8 4 621 [39] Wang W J, Qiao M H, Yang J, et al. Applied Catalysis A : General, 1997, 163 (1Π2) : [40] Wang W J, Qiao M H, Li H X, et al. J. Chem. Tech. Biotech., 1998, 72(3) : [41] Li H, Li H X, Wang WJ, et al. Chem. Lett., 1999, 7 : [42] (Qiao M H), (Xie S H), (Dai WL). (Acta Chimica Sinica), 2000, 58(7) : [43] Wang W J, Qiao M H, Li H X, et al. Applied Catalysis A : General, 1998, 166 : L243 L247 [44] Wang W J, Qiao M H, Li H X, et al. Applied Catalysis A : General, 1998, 168 : [45] Wang W J, Li H X, Xie S H, et al. Applied Catalysis A : General, 1999, 184 : [46] Wang W J, Li H, Li H X, et al. Applied Catalysis A : General, 2000, 203 : [47] Wang W J, Li H X, Deng J F. Applied Catalysis A : General, 2000, 203 : [48] (Chen H Y), (Deng J F), (Sheng S S). (Acta Chimica Sinica), 1994, 52 : [49] Varga M, Mulas G, Cocco G, et al. Materials Science and Engineering, 2001, A304Π306 : [50] (Song Z), (Hao Z X), ( Tan D L). (Chinese Journal of Catalysis), 1999, 20(3) : [51] (Ma A Z), (Lu W Z), (Min E Z). (Petrochemical Technology), 2000, 29(3) : [52] Guo H B, Li H X, Zhu J, et al. Journal of Molecular Catalysis A : Chemical, 2003, 200 : [53] Guo H B, Li H X, Xu Y P, et al. Materials Letters, 2002, 57 : [54] Chen X F, Li H X, Luo H S, et al. Applied Catalysis A : General, 2002, 233 : [55] Li H X, Wu Y D, Luo H S, et al. Journal of Catalysis, 2003, 214 : [56] Li H, Li H X, Deng J F. Applied Catalysis A : General, 2000, 193 : 9 15 [57] Xie S H, Li H X, Li H, et al. Applied Catalysis A : General, 1999, 189 : [58] ( Yu X B), (Wang M H), ( Ye L M). (Journal of Molecular Catalysis), 1999, 13(1) : 3 8 [59] ( Yu X B), (Wang G H), (Li H X). (Journal of Molecular Catalysis), 1999, 13 (5) : [60] (Cheng Q Y), (Li W), ( Zhang M H). (Chinese Journal of Catalysis), 2001, 22 (4) : [61] (Chen C R), (Jiang M), (Wan X H). (Chinese Journal of Catalysis), 1999, 20 (6) : [62] (Li J), (Qiao M H), (Deng J F). ( Chemical Journal of Chinese Universities), 2001, 22(6) : [63] Xie S H, Qiao M H, Li H X, et al. Applied Catalysis A : General, 1999, 176 :