PETROCHEMICAL TECHNOLO GY. 99 %) Pd/ C, 2,7 - - Al 2 O 3 ] TQ [ , Angilent

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1 200 PETROCHEMICAL TECHNOLO GY , (11, ; 21, ) [ ] 2,7 -, - Al 2 O 3 1 -,2,7-88 %( 99 %) Pd/ C, 2,7-100 % - Al 2 O 3 1 -,,, - Al 2 O 3, 1 3 h % 96 %,1-87 %, 83 % [ ] ; ;1 - ; ; - Al 2 O 3 [ ] (2003) [ ] TQ [ ] A 1 -, ; ( Ph 3 P) ;, 3A ; Pd/ C [1 ] Ni/, ; - Al 2 O (, - Al 2 O 3-1 Al 2 O 3-2 Al 2 O 3-3),SiO 2 Al (NO 3 ) %Al/ SiO 2 5 %Al/ SiO 2, , < 6 mm 3 mm 300 mm, -,C 8 3 ml, N 2 10 % 20 %, 1992,Dow 2 h, [2 1 - ],, Angilent GC N - [3 6 ] SE , X ( XRD) Dmax -, - Al 2 O 3 RB12 X ; Philips, 100 ml Magix601 X ;, 300, ( N H 3 - TPD) Micromeritics [2 1 - ] ( Autochem 2910 ; 330 ) Micromeritics ASAP ,3 -, 9918 % ; ( Pd (acac) 2 ),, [7 ] [ ] ;[ ] [ ] ( ),,,,, ,

2 3 : Table 1 The main physical - chemical properties of catalysts Al 2 O 3-1 Al 2 O 3-2 Al 2 O %Al/ SiO 2 5 %Al/ SiO 2 BET surface area/ m 2 g Pore volume/ cm 3 g Average pore diameter/ nm NH 3 - TPD method test Peak temperature/ Peak area ,7 - ( ) 011 MPa,,, (BDE), 2, 916 kpa , (MODE) ( 99 % ) 80 n ( CH 3 OH) / n ( Ph 3 P) / 114 MODE n ( Pd (acac) 2 ) / n (BDE) = 2177/ / 1142 MODE, 10-5 / 110 MPa 3, 115 MPa 315 h 2 2 MODE Table 2 Effect of catalyst promoter on yield of MODE CH 3 ONa/ BDE mole ratio/ Yield of MODE/ % , ,315 h 212 ;, (1 mol) ( mol),, 3 n (CH 3 OH) / mol n ( Pd(acac) 2 ) / mmol n ( Ph 3 P) / mmol 3 Table 3 Design of orthogonal test Time/ h Temperature/ Conversion of BDE/ % Yield of MODE/ % , 2177 mol, : 1 mol 2177 mol Pd (acac) mol Ph 3 P mol CH 3 ONa 100 %,MODE mol 1 h %,, MODE 8911 % ( 8214 %), (80 ), 3,

3 202 PETROCHEMICAL TECHNOLO GY O TE 4 h 87 %,,VCHE 4 -,3 - MODE, ,7 -, 70, 2 L 4, 70 Reaction time/ h 4 Table 4 Effect of reaction time on telomerization reaction Product mass distribution/ % Methanol Others OTE VCHE 3 - MODE MODE ( 40 min) ; 115 h, MODE Pd/ C 3 4, ;,,, 100 %, : n ( Ph 3 P) / n ( Pd ( acac) 2 ) / n ( CH 3 ONa) / n (BDE) / n (CH 3 OH) = / / / 1/ 2177, 70, 115 h,2,7-88 % ( 99 %) 213 2,7 - MODE 1/ MODE Table 5 MODE hydrogenation on different catalysts Temperature/ Catalyst Reaction 115 MPa MODE MOOA ,Ni/ 260 WHSV = 1 h - 1,, 6,Ni/ 2 h Pd/ C, 1 6, - Al 2 O 3, : Al 2 O 3-1,,, time/ h Yield of MOOA/ % 210 %Ni/ Diatomite %Ni/ Diatomite %Pd/ C %Pd/ C Table 6 Catalytic performance of different catalysts for MOOA cracking Catalyst Conversion of MOOA/ % Product mass distribution/ % 1 - Octene 2 - Octene 3 - Octene 4 - Octene Others Al 2 O Al 2 O Al 2 O %Al/ SiO %Al/ SiO

4 3 : Al 2 O 3-3 Al 2 O 3-7,, Al 2 O 3, ; 300,, Al 2 O 3-3, 1 -,,1 -,, 1 - ;,, 3 - Al 2 O 3 Al 2 O 3-1 ; Al 2 O Al 2 O 3-3, Al 2 O 3-1 (< 2 mm (3 4 ) mm), 1 300, 100 ml -, Al 2 O 3-2 Al 2 O 3-3 (< 60 mm 8 mm 900 mm),, 2 h 8, 8,, 1 - (N H 3 - TPD 17714, ) ;,, WHSV = 1 h h Conversion of Selectivity to Selectivity to 7 Al 2 O 3-1 WHSV/ h - 1 MOOA/ % octenes/ % 1 - octene/ % Table 7 Effect of reaction temperature on MOOA cracking over Al 2 O 3-1 catalyst Reaction Conversion temperature/ of MOOA/ % Selectivity to octenes/ % Selectivity to 1 - octene/ % Table 8 Effect of WHSV on MOOA cracking , 300,, 1 - : h Table 9 Pilot plant of MOOA cracking Reaction time/ h Temperature/ WHSV/ h - 1 Conversion of MOOA/ % Selectivity to octenes/ % Selectivity to 1 - octene/ %

5 204 PETROCHEMICAL TECHNOLO GY (3) - Al 2 O g (710 mol),, 873 g ( ) 76 g ( 213 g, - Al 2 O 3,, 137 g) ; 48 g ( 9512 %) ;1-619 g ( 1 3 h g, %) ; 94 % 96 %,1-38 g ; 42 g ; 50 g 87 %, 83 % 3 (1) n ( Ph 3 P) / n ( Pd (acac) 2 ) / n (CH 3 ONa) / n (BDE) / n ( CH 3 OH) = / / / 1/ , 115 h, 2,7-1975,14 (11) : %( 99 %) (2) 2,7 -,018 % Pd/ C, h ( MODE 1/ 500) 100 % [1 ],,. [ M ]1 :, [ 2 ] Bohley R C,Jacobsen GB,Pelt H L,et al1process for Producing 1 - Octene [ P]1WO 10450, [ 3 ] Wade L G1Organic Chemistry[ M ]12nd ed,new Jersey : Prentice - Hall Inc, [ 4 ] Kalinowski H O,Seebach D,Crass G1[J ]1 A ngew Chem Int Ed, [ 5 ] Merz A1[J ]1 A ngew Chem Int Ed,1973,12 (10) : [ 6 ] Bethmont V,Fache F,Lemaipe M1[J ]1 Tet rahedron Lett,1995, 36 (24) : [ 7 ] Okeya S,Ooi S, Matsumoto K,et al1 [J ] 1 B ull Chem Soc Jpn, 1981,54 (4) : Producing 1 - Octene from 1,3 - Butadiene via 1 - Methoxyoctane W A N G Hua 1, ZHA N G Jin - ling 1, S U N Cheng - lin 1, L IU Zhong - min 1, W A N Hai - shun 2, HA O Qing - xin 2 (11Natural Gas Utilization and Applied Catalysis Laboratory, Dalian Institute of Chemical Physics,CAS, Dalian Liaoning ,China ;21Fushun Petrochemical Corp1,CNPC,Fushun Liaoning ,China) [ Abstract] 1 - Octene was prepared via steps of (1) reacting 1, 3 - butadiene with methanol in presence of Ph 3 P,Pd (acac) 2 and CH 3 ONa to form 1 - methoxy - 2,7 - octadiene ; (2) hydrogenating 1 - methoxy - 2,7 - octadiene in presence of a hydrogenation catalyst to form 1 - methoxyoctane and (3) cracking of 1 - methoxy - octane to produce 1 - octene1 Yield of 1 - methoxy - 2,7 - octadiene in step (1) was about 88 % with purity more than 99 % under the conditions of n ( Ph 3 P) / n ( Pd ( acac) 2 ) / n ( CH 3 ONa) / n ( 1, 3 - butadiene) / n (methanol) = / / / 1/ 2177, t = 70 and time 115 h1 The rectified 1 - methoxy - 2,7 - octadiene was hydrogenated in step (2) in presence of 018 %Pd/ C under conditions of m (1 - methoxy - 2,7 - octadiene) / m (catalyst) = 500, t = 100 and time 1 h1in step (3),a series of - Al 2 O 3 and improved SiO 2 catalysts were investigated in the process of 1 - methoxyoctane cracking to produce 1 - octene1 - Al 2 O 3 catalyst with large pore size and pore volume possessed high catalytic activity1 Selectivity was closely correlated with its acidity and pore size1 Yield of 1 - octene and conversion of 1 - methoxyoctane on - Al 2 O 3 catalyst were about 83 % and 94 % 96 % respectively, under the conditions of WHSV = 1 3 h - 1, t = [ Keywords] 1,3 - butadiene ;1 - methoxyoctane ;1 - octene ;cracking ; - Al 2 O 3 ( )