1、 l : 2000-01-04Y “ : cI|: 1001-8719( 2000) 05-0036-05Al2O3Zn/ HZSM-5Yb4Y林 洁, 尹双凤, 于中伟( F S,100083)K1: Al2O3F ZnHZSM -5b4 ?Ybs( TEM -EDS)b4 u Fs,1 Al2O 3aZn/ Al2O 3aHZSM -5#Zn/ Al2O 3+ HZSM -5b4Y ?Zns,i) YZnFsy bTV ,F Al2O 3ZnHZSM -5b4V# ) , )s0 ZnFs %MAl2O 3 , Y4, ;ss0 V ZnF, ?r HZSM -5s0 Y ?b1oM: Z
2、n/ HZSM -5; Al2O 3;s0 ;Y;b4ms |: TE 624. 4; TQ426. 95DS M : A M 7?ZSM -5s0 b4$ QY/ ,A aB QQ , H9YQ 3 7B BHrobQHZSM -5 YQ Q ls0Q,Q B Qa _,K 3YQ,Q BV1 1bZnHZSM-5y Y4aZnN 7 “bX Zn QYT,1 9 _ ?is0 ? 3xT,V7 HZSM -5s0 Y4 1j3bs0 b4 H1FAl2O3 T4b3?C,F Al2O3i# ) Zn/ HZSM-5b4 ZnFs? 3 M, Al2O3 Znc 9F,7)HZSM -5m
3、F Znc bZn %MZn/ HZSM -5b4Y ?YnD,3N)Al2O3Zn/ HZSM -5Y ?#ZnsYaZn/ Al2O3YbTaYZnFVHZSM -5 %MA l2O3V y b1 Ls1. 1b4!| g rn( SiO2) / n( Al2O3)50HZSM-5x2b Aa# ,Bs ),Zn/ HZSM-5b4(eZS) ;Bs _ hB1 ,V# a ),cAl2O3Zn/ HZSM -5b4,:Al2O3+ Zn/ HZSM -5(eZS-Al)b b4s0 Znc a#!V# ) HqMb1. 2b4 ZnsVJEM -2000FXs( TEM -EDS) kb
4、4 Znsb1OsO q0i( T EM )a1 N1 X L ? N( EDS)Fbs Hb4x E“, 0 30 nm, ? N lX LS0j2104 eV, Be3 gb ?0 v “ B u H,00 s, % V?+X L, l + , V uAlaSiaZn s b 2000 M10F( FF)AC TA PETROLEI S INICA ( PET ROLE UM PROCES SING SE CTION)16 5 V L, b4“ |30 usbyn( SiO2) / n( Al2O3)50BZSM -5s0 SiO2c 96% , s uSiO2c v90% H, u Fs
5、0 F,yN |t uZnc (THZSM -5 Znc b7Al2O3 u , h“ ZnO s0 (l5%), Al2O3c v85%,yN |Al2O3c v85% uZnc (TAl2O3 Znc b BZnc ( |Znc 10 us (b1. 3-Y-YQ %5Q ,b4 40j60 “, A 1. 5 g,Q500j600, b 1j4 h- 1(HZSM -5)bQ b ,s AMsY9 ,i M s F, BBQ9sb2T) 2. 1Al2O3F Zn/ HZSM-5b4YV1am1Znc (2. 8%ZSZS-Alb4 -YQTbV1 V,Al2O3,- q47Y/,/WC
6、2jC4Qada#C5+dYQ44,7KJaYaYQ _ 4bm1 V,MQHW =, ZS-AlYQ q/1ZSl,b4 A bm2 T EM -EDSb4ZS-Al ZnHZSM -5Al2O3 sbm2 V A, Al2O3 Znc 1HZSM-5s0 ,V 5HZSM -5 ZnF Al2O3iV# ) ,MvBs %MAl2O3 , Zn/ HZSM -5b4b ?M V ?ZnF %M1bV1-ZSZS-Al QsTable 1Product distribution of n-C6 aromatizationover ZS and ZS-Al catalystsZeolite w
7、 ( Zn) / % y / %C01jC02 C =2jC=4 C03jC04 C 5+ Aromatics H 2x( n-C 6)/ %ZS 2. 8 24. 77 7. 31 20. 17 0. 49 44. 49 2. 76 94. 02ZS -Al 2. 8 13. 34 14. 56 27. 27 1. 71 37. 74 2. 50 98. 62H= 530, MHSV = 2. 54 h- 1( Based on HZSM-5)2. 2Al2O3 ZnFYT k bVs0 V %MAl2O3 ZnF YT s0 V 3xT,1 Al2O3ZnAl2O3Y ?(nV2)bVV2
8、 V,= (B ? Y, OZn/ Al2O31Al2O3, Y ? bV2-+ yb4 QTTable 2Results of hexanereaction on several special catalystsCatalyst MHS V/ h- 1 y/ %C01jC02 C=2jC=4 C03jC04 C 5+ Aromatics H 2x( n-C 6)/ %Al2O3 1. 5 1. 92 5. 61 1. 80 6. 18 1. 16 0. 05 16. 7Zn/ Al2O3 1. 5 3. 06 6. 77 2. 15 10. 00 3. 56 0. 11 25. 60HZS
9、M-5 1. 5 7. 30 22. 23 35. 31 6. 46 10. 42 0. 40 82. 10HZS M-5+ Zn/ Al2O3 1. 51) 9. 19 23. 09 36. 35 7. 14 11. 47 0. 45 85. 60H= 530; w ( Zn ) is 1. 8% on Zn/ Al2O3.1) Based on HZSM-5375 Al2O 3Zn/ HZSM -5Yb4Ym1ZSZS-AlYFig. 1Difference in stability between ZSand ZS-Al catalystsReaction con ditions are
10、 th e same as in T able 1.( 1) ZS ; ( 2) ZS -Alm2ZnHZSM-5Al2O3 sFig. 2Zn distribution onHZSM-5 andAl2O3|# Zn/ Al2O3HZSM -5,# # ) , ) HZSM-51 -Yb ?(nV2am3)bVV2m3 V A,|Zn/ Al2O3HZSM -5, A HZSM-5Y,Qs9 AMb 6,Zn/ Al2O3+HZSM -5“ZnsVTV , Al2O3 Znc 1. 5% ,s0 + ,ZnF =Al2O3 ,7 %Ms0 V b Zn/ Al2O3i AMHZSM -5b4?
11、y,9 ss0 V ZnF V ?s0 V 3xT,V74H ZSM -5Y,7Al2O3 ZnF !NxTbm3Zn/ Al2O3HZSM-5s0 YFig. 3Effect of Zn/Al2O3 onstability of HZSM-5 zeolite( 1) HZSM -5+ Zn/ C-Al2O3; ( 2) HZSM-52. 3YZnsy )YVs,?CAl2O3ZnF TTa*Ha# a ) #s0 ZnFc y Yb4 Zns1yb2. 3. 1Al2O3 TTAl2O3ZnO ()/ U FZnAl2O4, W TTbV2. 12. 2 V,5H ZSM -5ZnvsAl2
12、O3 %M,75)Al2O3 ZnF5HZSM -5s0 %M,V Al2O3ZnF TTvHZSM -5s0 b|cZn 1. 5%Zn/ HZSM -52VZ Al2O3*H,V# ) ,HZSM -5 Znc 1. 0%, Al2O3 1. 2%bV MgO(a1ZnO )Al2O3MT, Al2O3ZnO ? ,V7 Zn_Al2O3 %Mb2. 3. 2*Ha# ) V3*HZn/ HZSM -5b4!V“ ZnFs bVV3 V A,*HiV i|, ZnFX 7 S %_Al2O3, V ? *H HF Ps0 V sZnF 7 %MAl2O3b# ) ,Al2O3 %MZnF?
13、938 F( FF)16 , F ) VZnFAl2O3 %MbV3F ) ZnsYTable 3Effect of thermal or hydrothermal treatment on zincdistributionw ( Zn ) / %HZSM-51) Al2O32)Zn/ HZSM -5 2. 80Zn /HZSM -5+ Al2O3 extruded, dried in the air 1. 88 4. 22Dried at 1151. 60 4. 72Calcined at 5800. 96 5. 60Hydrothermal treated at 5500. 80 5. 9
14、21) Based on HZSM -5; 2) Based on Al2O32. 3. 3Znc V3ZE|3Znc sY0. 5 %a1. 8%a2. 8%Zn/ HZSM-5s0 “ ( ZS-1aZS-2aZS-3)Al2O3*H! 3Al2O3+ Zn/ HZSM -5b4ZS-Al-1aZS-Al-2ZS-Al-3,1 *H -b4Zns-YasaZ Y(nV4)bVV4 V,s0 Zn , Zn Al2O3 %MbZS-1Znc 0. 5% ,*HHZSM-5Znc Mv,*H -b4QT9Mb “b49Znc 4,QTY AFvbN,b4ZS-Al-2ZS-Al-3ZnHZSM
15、 -5s0 c M,=-QYQ q# 91 ,B ss0 ZnF ?s0 3xT,MZn/ HZSM -5b4Y ?bb49Znc Y Zn %M,7KsHZSM -5s0 Znc %b4 ?1oy bV4Znc Zns-QsYTable 4Effect of Zn content on Zn distribution andproduct selectivity %Catalystw ( Zn)HZSM -51) Al2O32)sC01jC02 C=2jC=4 C03 C04 C 5+ Aromatics H2x ( n-C6) $y 3)ZS -1 0. 5 12. 32 15. 28 2
16、6. 48 10. 37 2. 28 31. 41 1. 84 95. 42 1. 20ZS-Al-1 0. 41 0.45 12. 30 14. 73 27. 28 10. 49 2. 13 31. 33 1. 74 97. 74 1. 11ZS -2 1. 8 21. 91 10. 07 15. 30 6. 30 0. 10 42. 98 2. 47 95. 63 7. 70ZS-Al-2 0. 75 3.10 13. 69 11. 88 23. 61 8. 64 1. 37 38. 78 2. 03 98. 10 3. 35ZS -3 2. 8 24. 77 7. 31 15. 23 4
17、. 94 0. 49 44. 49 2. 76 94. 02 18. 42ZS-Al-3 0. 80 5.92 13. 34 14. 56 18. 52 8. 75 1. 71 37. 74 2. 50 98. 62 3. 601) Based on HZSM -5; 2) Based on Al2O3; 3) Difference in aromatics yield after 60 h reaction .3 ( 1)FAl2O3!*HZn/ H ZSM -5b4,sZnFVHZSM -5s0 %MAl2O3, PZn/ HZSM -5YQ ,b44b( 2) Al2O3ZnO TT P
18、sZnVHZSM -5s0 Al2O3 %M1y b( 3)“ b4!V2a# ) y VF yZn %M, Zn %M “Zns0 c 47Fvb( 4)Al2O3 ZnF Y,7 Os0 3xT,s0 Y ?+ Y;ss0 ZnF ?s0 V 3xT,4HZSM -5Y4b395 Al2O 3Zn/ HZSM -5Yb4Y: F S i F YT , E iY qVb4 ZnsZ f,NBiV Ub ID: 1 Giuseppe, M onque, Gauasso. Trasform ation of LPG into aromat ic hydrocarbon and hydrogen
19、over zeolite cat alysts J . Cat al Rev Sci Eng, 1994, 36( 2) : 271- 304. 2E, . Zn/ HZSM -5dYQ ?T J . F, 1996, 25( 7) : 458- 462. 3 Ono Y, et al. The role of metal cations in the t ransformation of low er alkanes into aromat ic hydrocarbons A . Inui T.Successful Design of Catalysts C . Amsterdam: Els
20、evier Science Publishers B V, 1998. 279- 290.Te:( 1944- ) , o,) =, V,1V Y Fb4;( 1973- ) , 3,p V 3,1V Yb ;( 1966- ) , 3(B) ,) =,p V,1V Y Fb4bTHE EFFECT OF Al2O3 ON THE AROMATIZATION BEHAVIOUROF Zn/HZSM-5 CATALYSTLIN Jie, YIN Shuang-feng, YU Zhong-w ei( Research Institute of Petroleum Pr ocessing, Bei
21、jing 100083, China)Abstract: The effect of Al2O3 on properties of Zn/ H ZSM -5 w as studied. T he results indicate that Zn/HZSM -5+ Al2O3 has low er arom atization activity and better stability than Zn/ HZSM -5 w ith the sam ezinc content, w hich is attributed to the zinc on HZSM -5 migrated to Al2O
22、3. It is also show n that Zn/Al2O3 has very w eak aromatization activity and little effect on the catalytic pr operties of HZSM -5. It isonly the zinc component on HZSM -5 zeolite that can m odify the catalytic performance of HZSM -5. Fac-tors w hich affect zinc migration have been discussed.Key words: Zn/ HZSM -5; zeolite; Al2O3; aromatization; catalyst40 F( FF)16
