6 2001 NiO Ξ ( ) 5 6 MPa 220 NiO/ SiO 2 (NiO/ SiO 2 (imp. ) ) NiO/ Al 2 O 3 (NiO/ Al 2 O 3 (imp. ) ) NiO/ SiO 2 (NiO/ SiO 2 (ex. ) ) (MA) NiO/ SiO 2 (ex. ), NiO/ SiO 2 (imp. ) TPR,NiO/ SiO 2 (ex. ) NiO/ SiO 2 (imp. ), NiO/ Al 2 O 3 (imp. ) NiO,, NiO, NiO (MA),, (MF), MF MA CO MA [1 ], MF CO, MF CO [2 5 ],, [6 7 ], MF MA,,,,,, 1 1. 1 1. 1. 1 - Al 2 O 3 60 80,500 5 h, BET 285 m 2 / g 60 80, ( 1/ 1) 2 h,, 120 4 h, 500 5 h - Al 2 O 3, 90,,120 2 h,500 5 h, NiO/ SiO 2 (imp. ) NiO/ - Al 2 O 3 (imp. ) 1. 1. 2 ph = 11,, 24 h,, 120 2 h,500 5 h, NiO/ SiO 2 (ex. ) 1. 2, WGP - 6 ( ), ( 0. 78 cm 40 cm), DCT - 2T -, 220, 5 6 MPa GC - MS( HP6890/ 5973), SC - 1001, GDX103,, 155 1. 3 g(60 80 ), 1. 3 TPR Ξ 29703008
30 1 NiO 7 ( TPR) ) NiO NiO 102G ZWK- 1 C - RIB 1. 4 TPR,, 60 80 U TPR ( 1),,, 50 / min NiO, 500, 30 min 350, 560 680, ( 5 %, NiO, ), 26 ml/ min,, 15 / min NiO NiO [8 ] 900 TPR NiO H 2 - TPR NiO - Al t M, 2 O 3,, 12 %, NiO, 2 %, NiO, 1. 5,, NiO ( 4),, (R) NiO NiO R = Q/ Q 0,Q,Q 0 Q 0 = (m NiO %/ 74. 4) 22. 4 10 3 (ml),m,nio % NiO, NiO,, NiO,t M = 345, R = 1. 0, Al 2 O 3, NiO, NiO, NiO 1. 6 XPS XPS NP - 1X, MgK, 15 kv, 8 ma, C1s = 284. 6 ev 2 XPS NiO/ - Al 2 O 3 (imp. ) Ni/ Al NiO, 2 2. 1 NiO NiO/ - Al 2 O 3 ( imp. ) 630 h - 1,C 2 H 2 / MF(mol ) 0. 5 0. 9/ 1, 5 6 MPa, 220, NiO NiO/ - Al 2 O 3 (imp. ) 1 1 NiO NiO/ - Al 2 O 3 ( imp. ) NiO,wt % TPR M1, TPR M2, MF, % MA, % 0. 84 / 650 52. 77 18. 7 2. 3 / 662 56. 12 16. 3 9. 92 358 650 60. 78 24. 4 12. 16 356 568 80. 18 22. 3 14. 18 352 579 72. 31 19. 4 18. 71 355 564 54. 10 20. 3 1, NiO,, NiO/ - Al 2 O 3 (imp. ) 500,NiO, NiO (NiO 2, NiO,NiO/ - Al 2 O 3 Ni/ Al, NiO 12 %, Ni/ Al NiO, Al 2. 2 NiO NiO/ SiO 2 ( imp. ) 630 h - 1,C 2 H 2 / MF (mol ) 1 1. 56/ 1, 5 6 MPa, 220,NiO NiO/ SiO 2 (imp. ) 2
8 2001 2 NiO NiO/ SiO 2 ( imp. ) NiO,wt % TPR, MF, % MA, % 1. 4 350 51. 8 6. 38 4. 7 348 53. 2 8. 27 9. 0 364 57. 2 18. 6 12. 8 352 50. 1 16. 1 14. 5 355 47. 8 15. 2 2, NiO, TPR 350, NiO, NiO/ SiO 2 (imp. ), SiO 2 NiO, NiO XRD, NiO 12. 8wt % NiO ( 4), NiO SiO 2, 3, NiO/ SiO 2 (imp. ) Ni/ Si NiO NiO,Ni/ Si Ni/ Si NiO/ SiO 2 (imp. ) NiO, NiO NiO/ - Al 2 O 3 (imp. ) NiO/ SiO 2 (imp. ) SiO 2 NiO, NiO SiO 2, NiO/ SiO 2 (ex. ), 3 3,NiO/ SiO 2 (ex. ), NiO 20 30, NiO/ SiO 2 (imp. ), NiO/ SiO 2 (ex. ), SiO 2 NiO, NiO 3 NiO NiO/ SiO 2 (ex. ) NiO,wt % TPR, MF, % MA, % 3 365 52 25. 9 7. 8 370 74 22. 9 10. 6 375 73 35. 9 22 376 64. 7 26. 1 TPR,, [Ni (NH 3 ) 6 ] 2 + SiO 2 Ni 2 + NiO ; NiO SiO 2, NiO SiO 2 XPS NiO/ SiO 2 (ex. ) Ni/ Si NiO, 5 5,NiO/ SiO 2 (ex. ) Ni/ Si NiO NiO/ SiO 2 NiO/ SiO 2 (ex. ) Ni 2 + SiO 2, SiO 2 NiO,, 3 2. 3 NiO NiO/ SiO 2 ( ex. ) 630 h - 1,C 2 H 2 / MF (mol ) 1 1. 56/ 1, 5 6 MPa, 220, NiO (1), NiO,, (2) TPR XRD, ( 11 )
30 1 11 SRK [6 ], 7 ;, : T = T h - f ( T h ) T h - T 0 f ( T h ) - f ( T 0 ) ; f ( T) = 0 - T H 0 + C p ( T - T 0 ) RT 0 T 0 RT 2 dt + P V R T dp + 6 2 N c i ln (1-6 ij ) - ln ( f w / f 0 w) (7) i = 1 3 j = 1,, 3 4 5, 4,, 3 ( ) CH 4 H 2 S P (kpa) T( ) 4 P 0 0. 989 0. 011 3240 278. 3 277. 68 277. 95 0. 989 0. 011 4610 282. 2 281. 36 281. 66 0. 989 0. 011 6690 284. 7 285. 13 285. 44 0. 969 0. 031 2820 278. 6 276. 21 279. 71 0. 969 0. 031 4265 282. 8 280. 56 284. 19 0. 969 0. 031 6740 287. 5 285. 20 288. 71 0. 47 % 0. 33 % 5 ( ) P,kPa T( ) 4 T,K T,K 1 2 3 1378. 9 279. 82 280. 71 279. 78 2757. 9 285. 87 286. 54 286. 04 5515. 8 290. 65 292. 04 291. 60 10342 294. 26 296. 26 294. 60 1034. 2 275. 98 277. 71 275. 83 1723. 6 280. 26 281. 37 280. 31 2757. 9 284. 46 285. 21 284. 52 1378. 9 276. 32 277. 82 276. 59 2068. 4 279. 65 280. 71 280. 21 2757. 9 281. 98 283. 38 282. 77 4 2240. 8 283. 15 283. 89 283. 20 0. 39 % 0. 113 % 1. /.,1996 2 Munck J,et al. Computations of the formation of gas hydrates. Chem Eng Sci, 1988,43 (10) 3,. I. ( ),1988,4(3) 4,.., 1992,21 (4) 5,..,1990 6..,1993 7,,..,1990 4 CH 4 C 2 H 6 C 3 H 8 ic 4 H 10 nc 4 H 10 C 5 H 12 CO 2 H 2 S 1 0. 8641 0. 0647 0. 0357 0. 0099 0. 0114 0. 0078 0. 0 0. 0064 2 0. 7516 0. 0595 0. 0333 0. 005 0. 0005 0. 0051 0. 002 0. 143 3 0. 674 0. 037 0. 019 0. 006 0. 006 0. 0 0. 0 0. 25 4 0. 789 0. 06 0. 036 0. 005 0. 019 0. 0 0. 002 0. 094 : 1974,, : (710065) 98 254 :2000-05 - 15 : ( 8 ),, (3) NiO, ( ), (4) NiO/ SiO 2 (ex. ), Ni 2 + SiO 2,,, NiO, NiO/ SiO 2 (imp. ) 1 US Patent. 2806040,1957 3023237,1962 2 Patrick P,Marc F, Yves C,et al. Applied Catalysis A : General,1996,135 : 329 3 Christophe L, Yves C,Andre M,et al. J Chem Soc Chem Commun,1994, 1173 4 Guy L,Noel L,Philippe K,et al.j Am Chem Soc,1992,114 :10669 5 Bassam E A,Howard A.J Mol Catal,1992,77 :7 6,,.,1998,23(2) :30 7 Yang Xiangui, Zhang Jiaqi,Liu Zhaotie. Applied Catal. A : General,1998, 173 :11 8,,.,1999,15(7) :613 618 :,1971, : (610041) :2000-06 - 23 ; :2000-07 - 04 ; :
Feb. 2001, Vol. 30, No. 1 CHEMICAL ENGINEERING OF OIL AND GAS 1 ABSTRACTS DEVELOPMENT STRATEGY OF NATURAL GAS CHEMICAL ENGINEERING Zhang Xinzhi ( PetroChina Company Limited). CHEMI2 CAL ENGIN EERING OF OIL AND GAS, VOL. 30, NO. 1, p1,2001 ( ISSN 1007-3426, IN CHIN ES E) ABSTRACT : According to the natural gas resources characteristics and market demand status in China, the strategic aim of products development is to prepare environ2 mentally friendly liquid fuels, oxygenated compounds and major resin monomers via synthesis gas with lower cost and high efficiency downstream synthetic process,and finish the technical retrofit of exist methanol unit for expanding capaci2 ty and improving efficiency with low cost,and progressively form the new processes and new technologies with own knowledge property,which will lay a foundation for develop2 ment of domestic natural gas engineering in an all - round way in the 21 century. SUBJECT HEADINGS : natural gas, chemical engi2 neering,development,strategy STUDY ON THE REACTION OF METHANOL CON2 VERSION TO OLEFIN OVER SAPO - 34 MOLECU2 LAR SIEVE Jin Liwen,Li Chunyi,Yu Changchun et al ( Key Labora2 tory of Catalysis,University of Petroleum(Beijing),CNPC). CHEMICAL ENGIN EERING OF OIL AND GAS, VOL. 30, NO. 1, p2 5,2001 ( ISSN 1007-3426, IN CHIN ES E) ABSTRACT: In this work, distribution of MTO (methanol conversion to olefin) products over SAPO - 34, catalytic activity and selectivity of SAPO - 34 are investigat2 ed at different reaction temperature using on - line MS. The selectivities of ethylene and propylene are optimal in the re2 action temperature range from 450 to 500,and the cat2 alyst exhibits the longest activity at 470. Temperature programmed coke - burning shows that the coke contains hy2 drogen. The activity time of the regenerated catalyst keeps longer than that of the fresh catalyst. SUBJECT HEADINGS : SAPO - 34 molecular sieve, methanol, ethylene, MTO ( methanol conversion to olefin), temperature programmed coke - burning EFFECT OF SUPPORT AND METHOD OF LOADING ON THE CATALYTIC PERFORMANCE OF SUP2 PORTED NICKEL CATALYST FOR ACETYL ENE HYD ROESTERIFICATION TO METHYL ACRYLATE Huang Xinhan, Yang Xiangui, Zhang Jiaqi,et al (labo2 ratory of Natural Gas Conversion, Chengdu Institute of Or2 ganic Chemistry,Chinese academy of Sciences). CHEMICAL ENGIN EERING OF OIL AND GAS, VOL. 30, NO. 1, p6 8,2001 ( ISSN 1007-3426, IN CHIN ES E) ABSTRACT : The catalytic hydroesterification of acetylene over supported NiO/ Al 2 O 3 and NiO/ SiO 2 catalysts prepared by impregnation and ion - exchange (NiO/ Al 2 O 3 (imp. ), NiO/ SiO 2 (imp. ),and NiO/ SiO 2 (ex. ) ) has been studied in a fixed bed reactor at the conditions of 220 and 5 6 MPa. The results show that the NiO/ Al 2 O 3 (imp. ) cat2 alyst is very active and selective to methyl acrylate,but the NiO/ SiO 2 (imp. ) catalyst is less active and selective than that prepared by ion - exchange NiO/ SiO 2 (ex. ). TPR re2 sults show that NiO/ Al 2 O 3 ( imp. ), NiO/ SiO 2 ( imp. ) and NiO/ SiO 2 (ex. ) have different reduction temperature,which suggests that the dispersion degree of NiO over support is different. SUBJECT HEADINGS : acetylene, methyl formate, methyl acrylate,hydroesterification,nickel catalyst STUDY ON SIMULATION TECHNIQUE OF THE HY2 D RATE FORMATION PREDICTION Fan Youhong, Pu Chunsheng ( Petroleum Engineering Department,Xi an Petroleum Institute). CHEMICAL ENGI2 N EERING OF OIL AND GAS, VOL. 30, NO. 1, p9 11, 2001 ( ISSN 1007-3426, IN CHIN ES E) ABSTRACT : The gas including vapor isn t often sep2 arated in gas production pipeline. Because of the changing of temperature and pressure of fluid in pipeline,vapor will con2 dense under conditions of high pressure and low tempera2 ture. So gas hydrate will form in gas production pipeline. In this paper,a simple model of phase equilibrium calculation for predicting the formation of gas hydrate is described based on Van der Waals - Platteeuw s theory of ideal solid solu2 tion. The acid gas and nonacid gas are calculated with estab2 lished model. The calculated results show that the average relative deviation of temperature for acid gas hydrate produc2 tion is 0. 33 % ;for nonacid gas,the relative deviation is 0. 113 %. SUBJECT HEADINGS : hydrate, formation, predic2 tion,model,algorithm