CN87105159A - 烯烃的齐聚 - Google Patents
烯烃的齐聚 Download PDFInfo
- Publication number
- CN87105159A CN87105159A CN87105159.1A CN87105159A CN87105159A CN 87105159 A CN87105159 A CN 87105159A CN 87105159 A CN87105159 A CN 87105159A CN 87105159 A CN87105159 A CN 87105159A
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- China
- Prior art keywords
- chalkogenide
- dagger
- gram
- hours
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims 1
- 150000001457 metallic cations Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 53
- 239000000463 material Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000007788 liquid Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000011229 interlayer Substances 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 13
- -1 oxonium ion Chemical class 0.000 description 13
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- 150000002892 organic cations Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000002288 cocrystallisation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GEYBMYRBIABFTA-UHFFFAOYSA-N O-methyltyrosine Chemical compound COC1=CC=C(CC(N)C(O)=O)C=C1 GEYBMYRBIABFTA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/049—Pillared clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/145—After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/42—Sulfides or polysulfides of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
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Abstract
烯烃齐聚的方法是使含烯烃的原料在100至500℃和10至20000千帕的压力下,与含有热稳定的层状硫属化物的催化剂相接触。层状硫属化物相邻层片之间被硫属化物撑柱分开。
Description
本发明是关于烯烃的齐聚。
在例如美国专利3,960,978号中已经披露,C2-C5烯烃在硅酸铝沸石,特别是ZSM-5和ZSM-11上齐聚而生成汽油馏份,这种汽油馏份主要是烯烃,芳烃含量不大于20%(重量)。这种工艺是原料烯烃与沸石接触,条件为260-482℃,重时空速(WHSV)0.1到25,烃分压为50-4050千帕。
在例如EP-B-20017中也披露,含烯烃(主要是C+ 6烯烃)至少50%(重量)以上的含烯汽油,通过与沸石接触,可以转化成燃料油和改善了胶质稳定性的汽油。所用的沸石限制性指数为1-12,氧化硅与氧化铝的摩尔比不小于12,最好是用ZSM-5,反应条件为:温度177-316℃,压力790-7900千帕,液时空速(LHSV)0.2-10。
现已发现,含有在层间起分离作用的硫属化物撑柱的热稳定层状硫属化物,可用于烯烃的齐聚。当原料为C3-C5烯时,可生成沸点在汽油和轻馏份油范围(66-260℃)的烃类;当原料为C6-C20烯时,可生成沸点在重馏份油到润滑油范围(260-566℃)的烃类。
因此,本发明属于一种烯烃齐聚法。该方法是使含烯原料与一种催化剂接触,此催化剂含有热稳定的层状硫属化物,其相邻各层被硫属化物撑柱分开,反应条件为:温度100-500℃,压力10-20000千帕。
层状硫属化物以层状氧化物较好,最好是层状的钛酸盐或层状的硅酸盐。
撑柱以多聚氧化物较好,最好是多聚氧化硅。
现已知道,许多层状材料具有三维结构,但只在二维方向上显出最强的化学键合作用。在这类材料中,较强的化学键在二维平面内形成,而三维固体的形成是通过这些平面一层一层堆叠起来,不过平面间的相互作用比起把各单个平面结合在一起的化学键来要弱。这种较弱的键,一般是由层间的引力,如范德华力、静电相互作用和氢键而产生的。在电中性的薄片形成的层状结构的情况下,这时各层之间仅通过范德华力相互作用,由于各平面之间相对滑动不会遇到象层间有强的键合时出现的能垒,所以呈现高度的润滑性。石墨就是这类材料的一个例子。许多粘土材料的硅酸盐层片之间是由位于层片间的离子所提供的静电吸引力而结合在一起的。此外氢键的作用能直接发生于在相邻各层上的互补部位之间,或者由层间的桥连分子所产生。
层状材料,如粘土,可以通过改性以增加其表面积。特别是能通过吸收各种溶胀剂,如水,乙二醇,胺类和酮类,而增加层间距离。这些溶胀剂进入层间的空间并把各层片撑开。但是,当占据着层间空间的分子被除去时,例如把粘土在高温下焙烧,这种层状材料的层间空间就容易塌陷。因此,当把这类增加了表面积的层状材料用于化学处理时,即使在中等苛刻的条件下使用,也是不适宜的。
层间分离的程度可以用标准的方法,如X光衍射来测定以确定基线间距,亦称为“重复距离”或“d-间距”。这个数值表明了这么一个距离,例如某层片的最上部边缘到与其相邻的那一层片最上部边缘之间的距离。如果已知层厚,则可以通过从基线间距减去层厚来测定层间距离。
本发明的方法是使用一种烯烃齐聚催化剂,这种催化剂是从一种层状起始材料制备的。这种层状材料含有在那里与层间阳离子结合的阴离子交换位置。阳离子可以包括氢离子、水合氢离子和碱金属阳离子。起始材料先用“柱撑剂”处理,目的在于与起始材料中的层间阳离子交换或掺入到层间阳离子,从而把起始材料的各层片撑开,柱撑剂通常包括一种有机阳离子的原料化合物,如有机胺离子。例如,当层间阳离子是氢或水合氢离子时,有机阳离子的原料化合物,可以是中性化合物,如有机胺。当进行“柱撑”处理时,有机胺被转化成对应的阳离子。上述处理导致生成一种层间分离被增大的层状材料,增大的程度则取决于夹入的有机阳离子的大小。在一个实例中,进行了一系列有机阳离子交换。例如,一种有机阳离子可以被更大的有机阳离子所交换,从而逐级地增大了层间的距离。层状材料与柱撑剂的接触最好在水相介质中进行,以便把水封闭在柱撑产物的层间空间里。
离子交换之后,进行了有机“柱撑”的产物用一种化合物处理,最后是通过水解,这种化合物能转化成硫属化物,最好是转化成多聚氧化物。柱撑的层状材料含有硫属化物的前体,然后经处理生成硫属化物撑柱,它把层片分开。在此处理方法包括水解,它可以利用例如存在于有机柱撑的层状材料中的水来进行。
沉积在各层片间的有机阳离子,最好是能从经过撑柱后的材料中除去,而同时又基本上不会破坏或者除去硫属化物撑柱或其前体。例如有机阳离子,如正辛基铵离子可以通过焙烧或化学氧化而除去,通过焙烧较好,最好还是在其前体化合物已经转化成硫属化物撑柱之后。
生成的撑柱产品具有很高的表面积,例如,可大于200,400或600米2/克,并具有热稳定性。
用于制备本发明所用催化剂的层状材料,是原子序数从13到15、21到33、39到51、57到83或大于90的元素的层状的硫属化物,最好是氧化物。层状氧化物最好是“非膨胀性的”,它不同于通常的粘土,通常的粘土含有与氧化硅四面体薄片结合的八面体金属氧化物薄片。而当氧化硅薄片以非化合量与水接触时会发生膨胀。正如在层状氧化物中已经使用过的,“非膨胀性的”这一术语,其定义为:当每克层状氧化物在23℃与至少10克水接触24小时,其d-间距的增加与无水物比较不大于5
。这种材料包括H2Ti3O7,Na2Ti3O7,和KTiNbO5以及某些层状钙钛矿,金属代钛酸盐和硅酸盐,例如,偏硅酸盐、麦羟硅钠石、硅钠石、水羟硅钠石、马水硅钠石和水硅钠石。其它可用的起始材料包括层状粘土,如膨润土,虽然它在水中是可以膨胀的。已经发现,使用某些层状起始材料如层状硅酸盐,最好在用有机阳离子化合物交换之前或交换的时候,用一种或多种极性溶剂来处理硅酸盐。所用的极性溶剂在气相时的偶极距至少为3.0迪拜(D),最好不少于3.5D,大于3.8D则更好。可用的溶剂如水,二甲亚砜(DMSO)和二甲基甲酰胺(DMF)。可供选择的有机化合物及其偶极距可见于CRC化学物理手册,第61版,1980-1981第E-64到E-66页。人们相信,用一种或多种高极性溶剂处理起始材料氧化物,可以促进有机阳离子化合物进入到起始材料的层间去。
在一个较好的实施例中,起始材料是一种ⅣA族金属,如钛、锆、铪的层状氧化物。而使用层状钛酸盐,例如三钛酸盐,如Na2Ti3O7是最好的。三钛酸盐是可商品化销售的材料,它的结构由与层间碱金属阳离子相结合的钛八面体的阴离子片所组成。制造这种材料的方法可见美国专利2,496,993。在另一个较好的实例中,起始材料是一种具有麦羟硅钠石结构的层状硅酸盐。
如前所述,在引入撑柱之前,层状起始材料用一种有机化合物处理,这种有机物可以生成阳离子,如有机鏻或有机铵离子。有机阳离子插入到相邻的两层之间,足以使两层物理地分开。通过这种方法,硫属化物的前体容易进入层状氧化物的层间,硫属化物的前体是电中性的,而且是可水解的。已经发现,烷基铵阳离子特别适用于本发明。因此,C3及C3以上的烷基铵,如正辛基铵的阳离子,特别容易与层状氧化物的层间物质相结合。其作用是用前述的方法把层片撑开,以便容许多聚氧化物前体的掺入。层间距离的大小可以由所使用的有机铵离子的大小来控制。例如,以三钛酸盐作为层状氧化物的起始材料,使用正丙基铵阳离子,层间距离可以达到2-5
,使层间距离达到10-20
就需要使用正辛基铵或长度相当的阳离子。确实有机阳离子的大小和形状能直接影响它是否完全地被结合在层状氧化物的结构之中。例如,大块状(bulky)的阳离子,如四丙基铵阳离子,一般不希望用在本方法中。反之,正烷基铵阳离子,如正烷基伯胺和R3R′N+阳离子的衍生物则比较好。其中R是甲基或乙基,R′是至少五个碳原子的烷基。使氧化物层分离的有机铵阳离子可以通过中性胺与层状起始材料层间的氢离子或水合氢离子反应就地生成。另一方面,如果层状起始材料的层间阳离子是碱金属阳离子,则可以先通过胺和酸性水溶液,如盐酸反应,然后用生成的有机铵离子水溶液,处理层状氧化物以生成有机铵阳离子。在上述两种情况下,都是在水介质中进行处理,为的是在这之后水可以用于多聚氧化物前体的水解,随后生成“撑柱的”产物。该多聚氧化物是电中性的,可水解的。
在氧化物起始材料层间形成的硫属化物的撑柱最好是一种氧化物,多聚氧化物就更好。与氧化合的元素是选自元素周期表(Fisher Scientific Co,Cat.No.5-702-10,1978)中ⅠB.ⅡB.ⅢA.ⅢB.ⅣA.ⅣB.ⅤA.ⅤB.ⅥA.ⅦA和ⅧA中的至少一种元素。在一个较好的实例中,撑柱包括锆、钛或选自周期表ⅣB族(除碳以外)的至少一种元素的氧化物,而最好包括多聚氧化硅。这里,层状起始材料是硅酸盐,如麦羟硅钠石撑柱最好是多聚氧化硅和氧化铝。多聚氧化物撑柱是从前体物质形成的,前体物质最好是以阳离子形式引入到有机柱撑物的层间,或是以所需元素的化合物形式引入,这些化合物是电中性的、可水解的。
前体物最好是一种有机金属化合物,它在常温常压条件下是液体。可用的多聚氧化硅前体物包括原硅酸四丙基酯,原硅酸四甲基酯,而最好是原硅酸四乙基酯。此处撑柱也可按需要包括多聚氧化铝-一种可水解的铝化物,它在层状起始材料与硅化合物接触之前、之后或同时,能与有机“柱撑”物质接触。所用可水解的铝化合物最好是烷氧基铝,如异丙氧基铝。
水解之后生成多聚氧化物的撑柱,经焙烧除去有机柱撑剂,最终的撑柱产物可以含有残余的可交换的阳离子。例如,含多聚氧化硅撑柱的钛酸钠可以含有2~3%(重量)的残余的钠。这种剩余的阳离子可以用其它阳离子按已知的方法进行离子交换,以提供或改变层柱产物的催化活性。可用的取代阳离子包括铯、钴、镍、铜、锌、锰、铂、镧、铝及它们的混合物。
在一个较好的实例中,其中层状起始材料是钛酸盐,撑柱是由氧化硅形成的,得到的硅钛酸盐产物其特征的X-光衍射图如表1所示。
表1 硅钛酸盐主要X光粉末衍射峰
组 合 表*
线数 2ν-2ν 100I/I0
(最小 最大) (相对强度)范围
1 小于或等于8.7 很强到弱
2 11.1-14.3 强到弱
3 11.8-15.2 中到弱
4 24.5-25.0 很强到弱
5 25.0-25.4 中到弱
6 28.5-30.2 很强到弱
7 29.8-30.6 强到弱
8 33.0-33.5 强到弱
9 43.2-43.5 中到弱
10 44.2-44.7 中到弱
11 48.5-48.9 很强到中
12 52.7-52.9 弱
*2θ最小-2ν最大=观察到的八个具体的撑柱硅钛酸盐的2ν值的范围。
这些数值是用标准方法测定的。放射线是铜靶的双重k-α线,并使用闪烁计数器光谱仪。峰高、I和位置都是2θ的函数。其中,θ是测得的布拉格(Bragg)角。由此可以计算出相对强度I/IO和面间距d。其中I。是最强线或峰的强度,d是以埃(
)表示的与记录下的谱线相应的晶面间距。表中的相对强度表示如下:
相对强度 100I/I0
Vs(很强) 60-100
S(强) 40-60
M(中) 20-40
W(弱) 0-20
离子交换硅钛酸盐组成的变化或焙烧,都能引起面间距和相对强度的改变。
做为本齐聚法的催化剂,在使用之前,撑柱的钛酸盐各层之间含有可交换的阳离子(如碱金属离子,如钠离子),这些阳离子可以用以下的离子进行交换处理:(1)铵离子(2)氢离子(3)焙烧后生成的质子交换物质。这些物质可部分地被下列阳离子交换,这些阳离子如铯、铈、钴、镍、铜、锌、锰、铂、镧、铝、铵、水合氢离子及它们的混合物。Ni(Ⅱ)和Al(Ⅲ)阳离子做为取代阳离子是特别重要的。在没有碱金属存在的条件下制备的层状钛酸盐,例如,用酸把碱金属交换掉,对于本齐聚过程也是特别有用的。这种物质的碱金属含量小于1%(重量),最好低于0.5%(重量)。
用于本发明的层状硅酸盐最好是高氧化硅的碱金属硅酸盐,其各层没有八面体薄片,它是由氧化硅和苛性碱的水性反应混合物,在相对温和的温度和压力下,通过水热的方法制备的。层状硅酸盐在层中可以含有除硅以外的四配位骨架原子,它们可以通过在非硅的四价元素存在下,以共结晶的方法引入。四配位骨架原子可从Al,B,Co,Cr,Fe,Ga,In,Ni,Zr以及任何其它这种元素中选用。当它们结合到硅酸盐结构中去时就能起催化作用。换句话说,已经存在于层状硅酸盐中的非硅骨架元素,可以被不同的四配位体元素所置换。例如:骨架中含硼的水羟硅钠石当用硝酸铝处理时,生成一种在其骨架中含铝的水羟硅钠石。共结晶和置换层状高氧化硅碱金属硅酸盐这两种处理方法,都能得到含有层间氧化物撑柱的层状物质。
最好的层状硅酸盐是合成的取代麦羟硅钠石。合成的麦羟硅钠石很容易用水热法从廉价的含有SiO2的材料和苛性碱反应混合物中得到。四配位体元素X(硅除外)例如Al,B,Co,Cr,Fe,Ga,In,Ni,Zr最好是Al或Fe,可以添加到反应混合物中作为有机导向剂R。对于如此合成麦羟硅钠石型物质的反应混合物,可用分子比表示如下:
SiO2/X2O3=10到无穷大,其中X可以是Al,B,Co,Cr,Fe,Ga和/或Ni及其它有催化作用的金属。
M+OH-/SiO2=0到0.6(最好0.1-0.6)
M=任何碱金属
H2O/SiO2=8-500
R/SiO2=0-0.4
其中R可以是一种有机化合物,如苯基三乙基氯化铵、苯基三甲基氯化铵、二苯基二甲基氯化铵,N,N′-二甲基哌嗪,三乙胺或其它季铵化合物或杂环胺类。
反应混合物在任意容器中于100-200℃保持1到150天,以生成具有下列组成的产物:
% N=0-3 例如0到0.3
SiO2/X2O3=10到无穷大
其中X是在四面体或八面体位置
M2O/SiO2=0到0.5 例如0.05-0.1
如此制得的合成层状硅酸盐表面积很低。按照本发明的方法引入层间多聚氧化物可以增加材料的表面积。一般来说,合成的麦羟硅钠石型物质可以用任何适当的方法酸化。例如,在用“柱撑”剂单独处理或与适当的极性溶剂共同处理前,用0.1N的Hcl水溶液处理。
应用本发明的方法可以实现低分子量(C3-C5)烯烃的齐聚。烯烃的沸点在汽油或轻柴油的范围(66-260℃,或最好在93-232℃),转化通常以气相进行,例如在固定床催化剂反应段内,烯烃原料与催化剂接触,有效的转化条件为,温度150-430℃,最好是260-400℃,压力100-10000千帕,最好是100-3200千帕。重时空速(WHSV)可保持在0.2-20小时-1,最好从0.5到4小时-1。此外,水也可以与烯烃一起共同进料,加料比以每克分子烯烃加入0到5克分子水为好。其中,温度和压力条件的范围将在很大程度上根据平衡的需要、确切的加料情况、有无稀释剂(例如,C1-C4烷烃,如甲烷、乙烷、丙烷、异丁烷和正丁烷以及硫化氢)而改变。稀释剂的量可以是烯烃重量的0-90%,最好是20-60%。这个过程可以根据操作人员的需要采用间歇的或流动床的方式进行操作。
本发明的方法也可用于中间分子量的烯烃,例如,C6到C20,最好是C10到C16的烯烃。它们经过齐聚可生成沸点在重馏份油到润滑油范围(260~566℃,最好是316-454℃)的烃类,即C20以上的烃类。在密闭的反应器中,当烯烃与层状钛酸盐于自生的压力下接触时,根据烯烃进料情况采用合适的反应温度(140到285℃),以利于C20以上烃类的生成。当使用1-癸烯为原料时,最佳的温度范围是140到160℃。当使用1-十六碳烯时,反应温度以265℃到285℃为最佳。中间分子量烯烃齐聚成重馏份油到润滑油馏份时,齐聚反应条件可以在美国专利4,542,297号中找到。
本发明可以进一步通过以下的实例来描述。在这些实例中,当出现α值时,应注意到α值是与标准催化剂相比较时,测试催化剂催化裂化活性的近似指标,它还给出了与高活性氧化硅氧化铝裂化催化剂相比的相对速度常数,速度常数是单位时间内在单位体积催化剂上转化正己烷的速度,后者的α值取为1,速度常数=0.16秒-1。α值的测定方法见美国专利3,354,078号和催化杂志(The Journal of Catalysis)第Ⅳ卷522-529页(1965年8月)。
实 施 例 1
500克Na2Ti3O7、427克正辛胺、309.7克37.8%的盐酸和7000克水的混合物回流22小时。澄清反应产物溶液,过滤,然后在过滤器上于室温下干燥过夜。然后将产物用无水乙醇和水按以下方法处理两次:固体产物在2升乙醇中再成浆,过滤,并在室温下空气干燥6小时。然后将此物质在1.5升水中成浆,在2升的聚丙烯瓶中于100℃加热17小时,过滤,然后在室温下干燥24小时。
把450克干燥产物放到一个装有穿孔铝箔盖的10升烧瓶中并加入3000克原硅酸四乙基酯进行机械搅拌,于室温下反应68小时,然后过滤,在空气中于室温下干燥大约4天。把这种物质在氮气中510℃(950°F)焙烧2小时,再在空气中于同样温度下焙烧1小时。得到的硅钛酸盐产物表面积为405米2/克,其组成如下(重量%):
TiO251.7
SiO239.9
Na 1.8
灰份 98.1
此物质的α值等于3。
把5.0克撑柱的硅钛酸盐样品加到450毫升高压釜中,同时加入大约150毫升液态丙烯,把温度升到150℃,同时压力迅速地升到7272千帕(1040磅/英寸2)。总反应时间24小时,搅拌速率为1000转/分。反应结束后,未反应的丙烯从高压釜排出,共得到液体产物3.4克。该液体产物的气相色谱分析表明其产物分布如下(重%):
组分 重%
C625.2
C953.5
C1216.7
C154.3
C180.3
C+ 210
实 施 例 2
500克Na2Ti3O7、770克正辛胺、559克37.8%的盐酸及5升水的混合物回流22小时。溶液冷却到70℃,加入281克37.8%的盐酸。产物过滤,用10升热水洗涤,并在室温下干燥过夜。固体产物在3升乙醇中于室温下成浆1小时,过滤,并在室温下空气干燥24小时。把900克的这种物质在4升水中成浆,并在室温下搅拌23小时,过滤,在室温下干燥24小时。在用穿孔铝箔封盖的10升烧瓶中把825克干燥的产物于机械搅拌下加到5.5公斤的原硅酸四乙基酯中,反应72小时,然后过滤,并在室温下于空气中干燥大约24小时。将此物质于氮气中950F°焙烧2小时,然后再在950°F于空气中焙烧1小时。得到的硅钛酸盐产物表面积为299米2/克,组成如下(重量%):
TiO270.2
SiO221.7
Na 3.3
灰份 100.0
把7.5克撑柱的硅钛酸盐产物加入到0.5M的Ni(NO3)2溶液中进行镍交换,0.5M Ni(NO3)2溶液的制备是通过在1升烧瓶中把72.5克的Ni(NO3)2·6H2O溶解到500毫升去离子水中。得到的溶液在室温下搅拌68小时。然后从溶液中过滤出催化剂,用去离子水洗涤,然后在烘箱中保持100℃干燥1小时。再把催化剂压成14到25目的片。之后将压成片的催化剂精心地进行焙烧,即以1.5℃/分的升温速度,从室温加热到400℃,并在400℃保持4小时。
把5.0克这种催化剂加入到300毫升的高压釜中,加入大约150毫升液体丙烯。把温度调节到150℃。高压釜中的压力迅速增加到10030千帕(1440磅/英寸2)。反应可延续到24小时。此时,将未反应的丙烯从高压釜放空。从反应器得到大约8.8克液体产物。经气体色谱分析具有下列组成:
组分 重量%
C616.6
C956.7
C1217.7
C156.7
C182.0
C+ 210.4
实 施 例 3
在2升烧瓶中把80克NH4NO3溶解在1升去离子水中制成1.0M的NH4NO3溶液。把15克实施例1制备的撑柱的硅钛酸盐加入到NH4NO3溶液中,在室温下把混合物搅拌大约70小时。从溶液中过滤出催化剂,用去离子水洗涤,再在100℃烘箱中烘干1小时。把7克这种催化剂进一步以1℃/分的升温速度从室温加热到250℃,然后在250℃维持4小时。把5克催化剂加到300毫升高压釜中。再加入大约150毫升液体丙烯,调节温度到150℃。压力迅速升到9930千帕(1425磅/英寸2)。在1000转/分的搅拌速度下反应22.5小时。反应结束后,从高压釜放出未反应的丙烯,得到大约3.7克液体产物。经气相色谱分析组成如下:
组分 重%
C622.1
C960.3
C1214.1
C153.4
C180.1
C+ 210
把另外7克此催化剂进行焙烧,即以2℃/分的升温速度从室温加热到500℃,再在此温度下保持12小时,把5克得到的催化剂加到300毫升高压釜中,再加入150毫升液体丙烯。然后把反应温度增加到150℃。压力达到9860千帕(1415磅/英寸2)。在自生压力及1000转/分的搅拌速度下反应进行24小时。反应终了,从高压釜排出未反应的丙烯得到4.6克液体产物。气相色谱分析其产物分布如下:
组分 重量%
C615.4
C960.1
C1218.6
C154.9
C181.1
C+ 210
实 施 例 4
把300克由实施例2制得的硅钛酸盐产物(未经镍交换的)用3升0.5M的Al(NO3)3·9H2O溶液于室温下搅拌24小时交换三次。将产物过滤,用3升水洗涤,并在第一次和第二次交换后在120℃干燥1小时。在第三次交换后,滤出产物,用10升水洗涤,在120℃干燥1小时,再在空气中于427℃(800F)焙烧1小时。产物的表面积为223米2/克,组成如下(重量%):
TiO266.7
SiO223.6
Na 2.5
Al2O30.65
灰份 97.96
把5.0克此催化剂装入到300毫升高压釜中。加入大约150毫升液体丙烯,把反应温度调节到150℃。压力升到9860千帕(1415磅/英寸2)。在1000转/分的搅拌下反应进行24小时。反应完了,未反应的丙烯从反应器放空而得到总共14.5克液体产物。气相色谱分析表明含有下列组成:
组分 重%
C613.3
C952.3
C1224.4
C158.0
C182.0
C+ 210
实 施 例 5
把1千克的Na2Ti3O7用16升的1.0M盐酸于77℃(170°F)搅拌24小时,如此交换三次以把碱金属离子交换掉。在前两次交换后过滤出固体并用4升水洗涤。在第三次交换后,过滤出产物,用水洗至无氯化物,并在真空中于77℃(170°F)干燥1小时。把700克这种产物与700克正辛胺和10.5升水混合于搅拌下回流23小时。产物过滤,用10升热水洗涤,在室温下干燥3天。将600克这种产物于室温下加到4千克原硅酸四乙基酯中搅拌67小时,过滤并在室温下干燥24小时。把800克干燥的产物在氮气中510℃(950°F)焙烧2小时,再在同样温度下于空气中焙烧1小时。最终的硅钛酸盐产物具有394米2/克的表面积和下列组成(重%):
TiO265.2
SiO237.3
Na 0.34
灰份 97.61
把5.0克催化剂加到300毫升高压釜中。加入大约150毫升液体丙烯并升温至150℃。压力增加到9580千帕(1375磅/英寸2)。在自生压力及1000转/分的搅拌下反应连续进行23.5小时。在反应终了,从高压釜放出未反应的丙烯而得到大约69.3克液体产物。气体色谱分析表面其组成如下(重量%):
组分 重量%
C64.2
C948.7
C1236.5
C1510.5
C180.1
C+ 210
实 施 例 6(对照例)
10克致密状的Na2Ti3O7(购自Alfa的产品)用与实施例2相同的步骤以Ni(NO3)2·6H2O交换。把5克得到的催化剂加到300毫升高压釜中,加入大约150毫升液体丙烯,升温至150℃。起始压力为10445千帕(1500磅/英寸2),在此条件下经16小时后,未观察到压力下降。此时终止反应。这一结果说明,对于这种催化剂的催化活性,撑柱是必要的。
实 施 例 7
把5克在实施例5中制备的催化剂与75克1-十六碳烯一道加入300毫升的高压釜中。1-十六碳烯是在使用之前刚从氧化铝渗滤过的。高压釜被加热到275℃,在950转/分的速度搅拌下,以液相连续反应68小时。68小时终了,打开反应器,用气相色谱分析产物。分析表明,液体产物含有18.7%(重量)润滑油馏份的二聚物C32。未反应的单体经蒸馏从二聚物分出。测得C32的粘度指数(Ⅵ)为138,100℃的运动粘度为4.5厘斯。
实 施 例 8
把5克实施例5中制备的催化剂和75克1-癸烯一起加到300毫升高压釜中。1-癸烯在使用前刚从氧化铝渗滤过。高压釜升温至150℃,在此条件下,以1000转/分的速度搅拌,连续反应28小时。液体样品分析结果表明1-癸烯的转化率为26.1%(重量)。观察到的齐聚物的选择性如下:C20=88.1%,C30=10.5%,C40=1.4%。然后,温度提高到200℃,再继续反应118小时。然后终止反应。液体产物分析表明1-癸烯转化率为65.5%。对各种齐聚物的选择性如下:C20=83.7%,C30=14.8%,C40=1.6%。
蒸馏反应生成的液体,除去未反应的1-癸烯和大部分二聚产物后,得到的液体产物有如下的产物分布:C20=27.2%,C30=62.3%,C40=10.4%。这种产物的粘度指数(Ⅵ)为94.3,100℃的运动粘度为4.9厘斯。
实 施 例 9
把5克由实施例2制得的催化剂与75克1-十六碳烯加到300毫升高压釜中,1-十六烯使用前是新从氧化铝滤过的。升温到275℃,反应16小时。分析液体产物,表观转化率为14.7%。升温到325℃再反应100小时,然后中止反应。分析液体产物表明有14%转化成二聚物C32。未反应的单体经蒸馏与C32分开。测得润滑油馏份的粘度指数(Ⅵ)为115,100℃的运动粘度为4.2厘斯。
实 施 例 10
把200克NaOH(纯度98.6%)溶解在8升蒸馏水中,制成NaOH水溶液。把1350克HiSil233(98.8%的固体)加到此溶液中,强力打浆40分钟以形成淤浆(PH=12.4)。然后,淤浆于150℃(300°F)及自生压力下结晶70.5小时,过滤,用过量的20升蒸馏水洗涤,然后空气干燥。生成的麦羟硅钠石用0.5N的HCl在PH=2.0的条件下于室温交换24小时,过滤,并在空气中干燥。以500克酸交换的麦羟硅钠石样品用辛基胺(530克;Aldrich化学公司产品)的蒸馏水(109.7升)溶液于室温下处理24小时。淤浆用布氏漏斗过滤,并用大约10升蒸馏水洗涤,然后于88℃真空干燥12小时。把120克干燥产物研成细粉,再与含有19克异丙醇铝(AIP)(ALFA无机物公司产)溶于747克原硅酸四乙基酯(TEOS)的溶液接触。溶在TEOS中的AIP在与粉末接触之前先在100℃加热3小时。于室温下接触64小时之后,过滤出产物,空气干燥,并在538℃焙烧(在氮中焙烧1小时,空气中焙烧2小时)。撑柱产物的性质列于表2。
表2
表面积,米2/克 497 元素分析
吸附量 C1重量% 0.05
水,克/100克 20.0 Na,P.P.m 50
环己烷 14.4 SiO2,重量% 93.4
正己烷 14.7 Al2O3,重量% 2.9
灰分,重量% 97.3
(1000°F) 5
SiO2/Al2O3=55
把5克得到的催化剂与75克1-十六碳烯一起加入到450毫升高压釜中,1-十六碳烯是使用前新从活性氧化铝渗滤过的。升温到275℃,在搅拌下连续反应68小时,反应完毕,从高压釜中取出液体产物。气相色谱分析表明,麦羟硅钠石催化剂使57%的十六碳烯转化成产品。其中有49%是二聚物C32。其余51%液体产物是轻组分,它们可能是由于麦羟硅钠石的裂解活性产生的。把这种液体产物蒸馏以分出润滑油馏分。得到的产物其粘度指数Ⅵ为98.2 100℃的运动粘度为8.6厘斯。
实施例 11
再把5克实施例10的催化剂与75克1-十六碳烯一起加入到450毫升高压釜中,(十六碳烯要在使用前新用活性氧化铝处理过),升温至200℃,在搅拌下反应90小时。反应结束,从高压釜中回收液体。气相色谱分析表明有57%的十六碳烯转化成二聚物。蒸馏液体产物分出二聚物。得到的产物Ⅵ=125.8,100℃的运动粘度为6.6厘斯。
实施例 12
把5克实施例10的催化剂与大约150毫升液体丙烯一起加到450毫升高压釜中。反应温度升到150℃,反应压力迅速升到7168千帕(1025磅/英寸2)。以1000转/分的转速搅拌反应混合物,在150℃及自生压力下连续反应24小时。反应终了,未反应的丙烯从高压釜放空。用气相色谱分析产物组成为:
组分 重%
C65.6
C966.8
C1222.4
C154.3
C180.9
C210
Claims (10)
1、一种烯烃齐聚的方法,此方法包括:使一种含烯原料与一种催化剂在温度100-500℃及压力10-20000千帕下接触,此催化剂含有热稳定性的层状硫属化物,此硫属化物的相邻各层被硫属化物的撑柱分开。
2、根据权利要求1的一种方法,其中层状硫属化物是层状氧化物。
3、根据权利要求1的一种方法,其中层状硫属化物是层状钛酸盐。
4、根据权利要求3的一种方法,其中撑柱是多聚氧化物。
5、根据权利要求3的一种方法,其中,撑柱是氧化硅。
6、根据权利要求1的一种方法,其中层状硫属化物是层状硅酸盐。
7、根据权利要求6的一种方法,其中撑柱是氧化硅和氧化铝。
8、根据权利要求1的一种方法,其中,催化剂含有金属阳离子,它们选自铯、铈、钴、镍、铜、锌、锰、铂、镧和铝。
9、根据前面任一项权利要求的一种方法,其中原料包括C3-C5烯烃,并在150-140℃的温度和100-10000千帕的压力下被转化成沸点在汽油或轻馏分油范围的烃类。
10、根据权利要求1到6的任何一项的一种方法,其中,原料包括C6-C20烯烃,并在140-285℃的温度下被转化成沸点在重馏份油到润滑油范围的烃类。
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Cited By (4)
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CN107185560A (zh) * | 2017-06-02 | 2017-09-22 | 钦州学院 | 一种烯烃齐聚催化剂及制备方法 |
CN107185560B (zh) * | 2017-06-02 | 2019-05-17 | 钦州学院 | 一种烯烃齐聚催化剂及制备方法 |
CN111744543A (zh) * | 2020-06-08 | 2020-10-09 | 太原理工大学 | 烯烃叠合制备航空煤油催化剂及其制备工艺、烯烃叠合工艺 |
CN111744543B (zh) * | 2020-06-08 | 2023-03-31 | 太原理工大学 | 烯烃叠合制备航空煤油催化剂及其制备工艺、烯烃叠合工艺 |
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