WO2005047218A1 - Process for producing 1-octene from butadiene in the presence of titanium catalysts - Google Patents
Process for producing 1-octene from butadiene in the presence of titanium catalysts Download PDFInfo
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- WO2005047218A1 WO2005047218A1 PCT/EP2004/011461 EP2004011461W WO2005047218A1 WO 2005047218 A1 WO2005047218 A1 WO 2005047218A1 EP 2004011461 W EP2004011461 W EP 2004011461W WO 2005047218 A1 WO2005047218 A1 WO 2005047218A1
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- WIPO (PCT)
- Prior art keywords
- process according
- octadiene
- butadiene
- catalyst
- ranges
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010936 titanium Substances 0.000 title claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 3
- 229910052719 titanium Inorganic materials 0.000 title description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims abstract description 66
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000003003 phosphines Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 239000000852 hydrogen donor Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- -1 palladium carboxylate Chemical class 0.000 claims description 6
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 claims description 5
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229940086542 triethylamine Drugs 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 claims description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000386 donor Substances 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims 2
- GONFBOIJNUKKST-UHFFFAOYSA-N 5-ethylsulfanyl-2h-tetrazole Chemical compound CCSC=1N=NNN=1 GONFBOIJNUKKST-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 229910052733 gallium Inorganic materials 0.000 abstract description 3
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- PAGZTSLSNQZYEV-UHFFFAOYSA-L 2,2-dimethylpropanoate;palladium(2+) Chemical compound [Pd+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O PAGZTSLSNQZYEV-UHFFFAOYSA-L 0.000 description 1
- DLCAQAYRHDYODB-UHFFFAOYSA-N 8-octa-2,7-dienoxyocta-1,6-diene Chemical compound C=CCCCC=CCOCC=CCCCC=C DLCAQAYRHDYODB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- RDOHPVPONNHSPH-BQYQJAHWSA-N [(2e)-octa-2,7-dienyl] acetate Chemical compound CC(=O)OC\C=C\CCCC=C RDOHPVPONNHSPH-BQYQJAHWSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- UGVSFVJLBBWBRE-UHFFFAOYSA-N octane oct-1-ene Chemical class CCCCCCCC.CCCCCCC=C UGVSFVJLBBWBRE-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
- C07C2/40—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
- C07C2/403—Catalytic processes
- C07C2/406—Catalytic processes with hydrides or organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0012—Galenical forms characterised by the site of application
- A61K9/0053—Mouth and digestive tract, i.e. intraoral and peroral administration
- A61K9/006—Oral mucosa, e.g. mucoadhesive forms, sublingual droplets; Buccal patches or films; Buccal sprays
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
- C07C2/40—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
- C07C2/40—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
- C07C2/403—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
Definitions
- WO 92/10450 describes the catalytic telomerization of butadiene with an alcohol such as methanol or ethanol to give 2,7-octadienyl ether.
- the latter in a second step, is hydrogenated to octyl ether which, in turn, in a third step, is pyrolyzed to 1-octene.
- this type of process is also jeopardized by the high number of reaction steps and an lower overall selectivity.
- WO 03/31378 describes the synthesis of 1- octene in only two steps starting from butadiene according to the scheme of equations (1) and (2) + HCOOH _ ⁇ ⁇ ⁇ ⁇ _ _ + c ⁇ 2 (1)
- the first step of the process of WO 03/31378 is carried out according to a reaction known in literature, i.e. the bis-hydrodimerization of butadiene in the presence of formic acid and catalysts based on palladium and phosphines.
- the reaction described is, in all cases, scarcely selective, with the formation of mixtures of 1,6- octadiene and 1, 7-octadiene or 1, 3 , 7-octa.triene, and the yields and catalytic efficiency, moreover, are low.
- the concentration of catalyst is reduced to lower values, the selectivity to 1, 7-octadiene decreases. From what is specified above, it would appear necessary to avail of a more efficient process for the hy- drodimerization of butadiene which allows high conversions and selectivities to 1, 7-octadiene to be reached, also when operating with reduced concentrations of noble metal.
- the second step of the process described in WO 03/31378 consists in the partial hydrogenation of 1,7- octadiene to 1-octene.
- the present invention relates to a process in two steps for the preparation of 1-octene starting from butadiene which comprises: ** a first step (a) in which the bis-hydrodimerization of butadiene to 1, 7-octadiene is effected in the presence of a catalyst based on palladium containing one or more tri- substituted monodentate phosphines, the molar ratio palla- diu /phosphines ranging from 3 to 50, more preferaJoly from 5 to 30, in an aprotic polar solvent optionally containing an organic base; the above first step being carried out in the presence of a hydrogen donor, preferably formic acid, preferably in a stoichiometric ratio of 1:2 molar with respect to the butadiene; ** a second step (b) in which the partial catalytic hydro- genation of 1, 7-octadiene, recovered at the end of the first step, to 1-octene, is
- aprotic polar solvents are disubstituted amides, for example dimethyl formamide, or disubstituted cyclic ureas, for example dimethyl ethylene urea or dimethyl propylene urea and the relative mixtures.
- organic base typically examples are pyridines, N-alkyl morpholines, tarialkyl amines.
- the organic base is triethyl amine .
- the first step is carried out in the presence of a hy- drogen donor, preferably in a stoichiometric ratio of 1:2 molar with respect to the butadiene, see equation (1), or slightly lower.
- the hydrogen donor is preferably foxrmic acid.
- the butadiene is used in an initial weight ratio ranging from 1:10 to 10:1 with respect to the solvent, more preferably from 1:5 to 5:1.
- the molar ratio between the organic base, for example triethyl amine and the hydrogen donor, for example forrmic acid can vary from 0 to 1.5, more preferably from 0.2 to 1.3, and even more preferably from 0.4 to 0.8.
- the reaction is carried out at temperatures rancing from 50 to 120°C, preferably from 70 to 100°C, preferably under a nitrogen pressure ranging from 0.5-2 MPa, more preferably from 0.8 to 1.5 MPa.
- the duration of the reaction of step (a) ranges from 10 to 180 minutes, more preferably from 15 to 120 minutes.
- the reaction product is separated by demixing, exploiting the fact that 1, 7-octadiene is not miscible in all ratios in the pre-selected solvent, for example dimethyl formamide, whereas the lower phase, comprising the solvent, optional organic base and catalyst, can be recycled to the reaction.
- the upper hydrocarbon phase prevalently consisting of 1, 7-octadiene, can be purified from the non- hydrocarbon residues by washing with water; the 1,7- octadiene is subsequently purified with conventional meth- ods, for example by distillation.
- the carbon dioxide, co-produced in a stoichiometric quantity when formic acid is used as hydrogen donor, can be hydrogenated again to formic acid with hydrogen, to be then recycled to the reaction.
- the hydrogenation of carbon dioxide to formic acid is carried out, for example, as described in Nature, vol . 368, March 17, 1994 , page 231 .
- the second step of the process i.e. the partial catalytic hydrogenation of 1, 7-octadiene to 1-octene, is carried out in the presence of a catalyst consisting- of a titanium compound activated with one or more metal alkyls of group 13 (i.e.
- the hydrocarbon solvent is preferably selected from those in which the catalyst and relative activator are both soluble.
- solvents suitable for the hydrogenation are: C 5 -C 14 aliphatic hydrocarbons, C 5 -C ⁇ cyclo-aliphatic hydrocarbons, C ⁇ -C ⁇ 2 aromatic or alkyl aromatic hydrocarbons, or their mixtures .
- the diene is contained in the solvent in a ratio of 5 to 90% by weight, more preferably from 10 to 80% by weight.
- the products are left in contact for about 30 minutes in an inert atmosphere and the whole mixture is then trans- ferred to a Hastelloy C autoclave having a volume of 300 ml, equipped with heat exchange devices and a mechanical stirring system, leaving a slight overpressure of argon.
- the autoclave is heated to the desired temperature (see Table 2), hydrogen is then introduced at a pressure of 2 MPa and the autoclave is connected to a make-up system of the hydrogen used up.
- a representative sample of the contents of the autoclave is taken at pre-fixed times and is subjected to gas chro atographic analysis, using the internal standard method, to determine the residual 1, 7-octadiene, the 1-octene product, the 1-octane co-product and diene and monoene isomers.
- the selectivities refer to the 1,7- octadiene converted. The results are indicated in Table 2.
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602004025600T DE602004025600D1 (en) | 2003-10-27 | 2004-10-11 | PROCESS FOR THE PREPARATION OF 1-OCT FROM BUTADIENES IN THE PRESENCE OF TITANKATALATORS |
BRPI0415698-6B1A BRPI0415698B1 (en) | 2003-10-27 | 2004-10-11 | TWO STEP PROCESS FOR THE PREPARATION OF 1-OCTENE FROM BUTADIENE |
AT04790336T ATE457967T1 (en) | 2003-10-27 | 2004-10-11 | METHOD FOR PRODUCING 1-OCTENE FROM BUTADIENE IN THE PRESENCE OF TITANIUM CATALYSTS |
EA200600678A EA010129B1 (en) | 2003-10-27 | 2004-10-11 | Process for producing 1-octene from butadiene in the presence of titanium catalysts |
US10/576,463 US7368623B2 (en) | 2003-10-27 | 2004-10-11 | Process for producing 1-octene from butadiene in the presence of titanium catalysts |
KR1020067008033A KR101122399B1 (en) | 2003-10-27 | 2004-10-11 | Process for producing 1-octene from butadiene in the presence of titanium catalysts |
EP04790336A EP1678104B1 (en) | 2003-10-27 | 2004-10-11 | Process for producing 1-octene from butadiene in the presence of titanium catalysts |
CA2543068A CA2543068C (en) | 2003-10-27 | 2004-10-11 | Process for producing 1-octene from butadiene in the presence of titanium catalysts |
NO20061761A NO337313B1 (en) | 2003-10-27 | 2006-04-21 | Process for the preparation of 1-octene from butadiene in the presence of titanium catalysts |
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ITMI2003A002084 | 2003-10-27 | ||
IT002084A ITMI20032084A1 (en) | 2003-10-27 | 2003-10-27 | PROCEDURE FOR PRODUCING 1-GETS FROM BUTADIENE IN THE PRESENCE OF TITANIUM CATALYZERS. |
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WO2005047218A1 true WO2005047218A1 (en) | 2005-05-26 |
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PCT/EP2004/011461 WO2005047218A1 (en) | 2003-10-27 | 2004-10-11 | Process for producing 1-octene from butadiene in the presence of titanium catalysts |
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US (1) | US7368623B2 (en) |
EP (1) | EP1678104B1 (en) |
KR (1) | KR101122399B1 (en) |
CN (1) | CN100439300C (en) |
AT (1) | ATE457967T1 (en) |
BR (1) | BRPI0415698B1 (en) |
CA (1) | CA2543068C (en) |
DE (1) | DE602004025600D1 (en) |
EA (1) | EA010129B1 (en) |
ES (1) | ES2340771T3 (en) |
IT (1) | ITMI20032084A1 (en) |
NO (1) | NO337313B1 (en) |
WO (1) | WO2005047218A1 (en) |
ZA (1) | ZA200603292B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US8722953B2 (en) | 2006-07-05 | 2014-05-13 | Evonik Degussa Gmbh | Method for producing dienes by hydrodimerization |
Families Citing this family (1)
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CN115007217B (en) * | 2022-06-21 | 2023-06-16 | 中国科学院青岛生物能源与过程研究所 | Polymer palladium catalyst, preparation method thereof and method for preparing 2, 7-octadiene methyl ether by catalyzing butadiene telomerization by using same |
Citations (5)
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---|---|---|---|---|
EP0008139A1 (en) * | 1978-07-24 | 1980-02-20 | Shell Internationale Researchmaatschappij B.V. | A process for preparing 1,7-octadiene |
US4229605A (en) * | 1978-12-13 | 1980-10-21 | Shell Oil Company | 1,7-Octadiene process |
US4243829A (en) * | 1976-10-04 | 1981-01-06 | Charles U. Pittman, Jr. | Production of 1,7-octadiene from butadiene |
EP0704417A2 (en) * | 1994-09-28 | 1996-04-03 | Kuraray Co., Ltd. | Process for producing octadienes |
WO2003031378A1 (en) * | 2001-10-06 | 2003-04-17 | Oxeno Olefinchemie Gmbh | Method for the production of 1-octene by reductive telomerisation |
-
2003
- 2003-10-27 IT IT002084A patent/ITMI20032084A1/en unknown
-
2004
- 2004-10-11 CA CA2543068A patent/CA2543068C/en not_active Expired - Fee Related
- 2004-10-11 ZA ZA200603292A patent/ZA200603292B/en unknown
- 2004-10-11 EP EP04790336A patent/EP1678104B1/en not_active Not-in-force
- 2004-10-11 ES ES04790336T patent/ES2340771T3/en active Active
- 2004-10-11 EA EA200600678A patent/EA010129B1/en not_active IP Right Cessation
- 2004-10-11 DE DE602004025600T patent/DE602004025600D1/en active Active
- 2004-10-11 KR KR1020067008033A patent/KR101122399B1/en active IP Right Grant
- 2004-10-11 US US10/576,463 patent/US7368623B2/en active Active
- 2004-10-11 CN CNB2004800317425A patent/CN100439300C/en not_active Expired - Fee Related
- 2004-10-11 WO PCT/EP2004/011461 patent/WO2005047218A1/en active Application Filing
- 2004-10-11 BR BRPI0415698-6B1A patent/BRPI0415698B1/en not_active IP Right Cessation
- 2004-10-11 AT AT04790336T patent/ATE457967T1/en active
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2006
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Patent Citations (5)
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US4243829A (en) * | 1976-10-04 | 1981-01-06 | Charles U. Pittman, Jr. | Production of 1,7-octadiene from butadiene |
EP0008139A1 (en) * | 1978-07-24 | 1980-02-20 | Shell Internationale Researchmaatschappij B.V. | A process for preparing 1,7-octadiene |
US4229605A (en) * | 1978-12-13 | 1980-10-21 | Shell Oil Company | 1,7-Octadiene process |
EP0704417A2 (en) * | 1994-09-28 | 1996-04-03 | Kuraray Co., Ltd. | Process for producing octadienes |
WO2003031378A1 (en) * | 2001-10-06 | 2003-04-17 | Oxeno Olefinchemie Gmbh | Method for the production of 1-octene by reductive telomerisation |
Non-Patent Citations (2)
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M F SLOAN ET AL: "Soluble catalysts for the hydrogentaion of olefins", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 85, no. 24, 1963, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC., US, pages 4014 - 4018, XP002279518, ISSN: 0002-7863 * |
P ROFFIA ET AL: "Catalysis by palladium salts IV selective hydrogenation with formic acid in the palladium catalysed dimerisation of 1,3-butadiene; synthesis of 1,7-octadiene", JOURNAL OF ORGANOMETALLIC CHEMISTRY., vol. 55, 1973, ELSEVIER-SEQUOIA S.A. LAUSANNE., CH, pages 405 - 407, XP002279516, ISSN: 0022-328X * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8722953B2 (en) | 2006-07-05 | 2014-05-13 | Evonik Degussa Gmbh | Method for producing dienes by hydrodimerization |
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BRPI0415698B1 (en) | 2013-11-19 |
ZA200603292B (en) | 2007-09-26 |
US7368623B2 (en) | 2008-05-06 |
BRPI0415698A (en) | 2006-12-26 |
KR20060107526A (en) | 2006-10-13 |
ATE457967T1 (en) | 2010-03-15 |
EP1678104A1 (en) | 2006-07-12 |
EA010129B1 (en) | 2008-06-30 |
NO337313B1 (en) | 2016-03-07 |
NO20061761L (en) | 2006-07-27 |
CN1874976A (en) | 2006-12-06 |
ES2340771T3 (en) | 2010-06-09 |
CN100439300C (en) | 2008-12-03 |
DE602004025600D1 (en) | 2010-04-01 |
KR101122399B1 (en) | 2012-03-09 |
EP1678104B1 (en) | 2010-02-17 |
US20070179327A1 (en) | 2007-08-02 |
CA2543068C (en) | 2012-06-12 |
CA2543068A1 (en) | 2005-05-26 |
EA200600678A1 (en) | 2006-10-27 |
ITMI20032084A1 (en) | 2005-04-28 |
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