CN117466722A - Preparation method of dialdehyde - Google Patents
Preparation method of dialdehyde Download PDFInfo
- Publication number
- CN117466722A CN117466722A CN202311419856.8A CN202311419856A CN117466722A CN 117466722 A CN117466722 A CN 117466722A CN 202311419856 A CN202311419856 A CN 202311419856A CN 117466722 A CN117466722 A CN 117466722A
- Authority
- CN
- China
- Prior art keywords
- dialdehyde
- hydrogen
- catalyst
- alkyl
- cycloalkyl
- 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.)
- Pending
Links
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 69
- 239000001257 hydrogen Substances 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 51
- 239000008346 aqueous phase Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- 239000012071 phase Substances 0.000 claims abstract description 22
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 109
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 95
- 239000003446 ligand Substances 0.000 claims description 84
- 229910052703 rhodium Inorganic materials 0.000 claims description 67
- 239000010948 rhodium Substances 0.000 claims description 56
- 238000000605 extraction Methods 0.000 claims description 49
- 229910052763 palladium Inorganic materials 0.000 claims description 33
- YHYGSIBXYYKYFB-VOTSOKGWSA-N (2e)-octa-2,7-dien-1-ol Chemical compound OC\C=C\CCCC=C YHYGSIBXYYKYFB-VOTSOKGWSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 19
- -1 alicyclic tertiary amine Chemical class 0.000 claims description 18
- 150000003512 tertiary amines Chemical class 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 16
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 15
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000003021 water soluble solvent Substances 0.000 claims description 6
- ZTZSFURMTBFRBA-UHFFFAOYSA-N deca-2,9-dien-1-ol Chemical compound OCC=CCCCCCC=C ZTZSFURMTBFRBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 150000003623 transition metal compounds Chemical class 0.000 claims description 5
- DBYJIWYDEHDKJS-SNAWJCMRSA-N (2e)-hexa-2,5-dien-1-ol Chemical compound OC\C=C\CC=C DBYJIWYDEHDKJS-SNAWJCMRSA-N 0.000 claims description 4
- CCRUWKGRGWGPNE-BQYQJAHWSA-N (2e)-nona-2,8-dien-1-ol Chemical compound OC\C=C\CCCCC=C CCRUWKGRGWGPNE-BQYQJAHWSA-N 0.000 claims description 4
- RVBHRZGEKZXATJ-UHFFFAOYSA-N 2-methyldecanedial Chemical compound O=CC(C)CCCCCCCC=O RVBHRZGEKZXATJ-UHFFFAOYSA-N 0.000 claims description 4
- CWKFJIKZLSKLPM-UHFFFAOYSA-N 2-methylnonanedial Chemical compound O=CC(C)CCCCCCC=O CWKFJIKZLSKLPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229940006460 bromide ion Drugs 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- ZNWNWEHQFXOPGK-UHFFFAOYSA-N decanedial Chemical compound O=CCCCCCCCCC=O ZNWNWEHQFXOPGK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- HWUMVJBWKZMIKH-AATRIKPKSA-N (2e)-hepta-2,6-dien-1-ol Chemical compound OC\C=C\CCC=C HWUMVJBWKZMIKH-AATRIKPKSA-N 0.000 claims description 3
- CEWCLVWWMXFUQL-UHFFFAOYSA-N 2-methylheptanedial Chemical compound O=CC(C)CCCCC=O CEWCLVWWMXFUQL-UHFFFAOYSA-N 0.000 claims description 3
- NICDGFIIDLQPAF-UHFFFAOYSA-N 2-methylhexanedial Chemical compound O=CC(C)CCCC=O NICDGFIIDLQPAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical group OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 235000013599 spices Nutrition 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 150000004808 allyl alcohols Chemical group 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 87
- 239000000047 product Substances 0.000 description 76
- 238000011084 recovery Methods 0.000 description 68
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 43
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 26
- 239000012295 chemical reaction liquid Substances 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 238000009835 boiling Methods 0.000 description 24
- 239000010410 layer Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- DAGXMELQLQNAGN-UHFFFAOYSA-N octa-5,7-dienal Chemical compound C=CC=CCCCC=O DAGXMELQLQNAGN-UHFFFAOYSA-N 0.000 description 17
- FWMKRIYREKTLSC-UHFFFAOYSA-N 9-hydroxynon-7-enal Chemical compound OCC=CCCCCCC=O FWMKRIYREKTLSC-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000284 extract Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 7
- 125000000746 allylic group Chemical group 0.000 description 7
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- LIINGNMKNRSOGW-UHFFFAOYSA-N oct-7-enal Chemical compound C=CCCCCCC=O LIINGNMKNRSOGW-UHFFFAOYSA-N 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- GROOSSLNHYKEFI-UHFFFAOYSA-N 2-methyloctanedial Chemical compound O=CC(C)CCCCCC=O GROOSSLNHYKEFI-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 3
- LEMKWEBKVMWZDU-UHFFFAOYSA-N nonanedial Chemical compound O=CCCCCCCCC=O LEMKWEBKVMWZDU-UHFFFAOYSA-N 0.000 description 3
- YHYGSIBXYYKYFB-UHFFFAOYSA-N octa-2,7-dien-1-ol Chemical class OCC=CCCCC=C YHYGSIBXYYKYFB-UHFFFAOYSA-N 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 150000003284 rhodium compounds Chemical class 0.000 description 3
- ONYJRUXYOCZIAW-BLWKUPHCSA-N (2e,6e)-octa-2,6-dien-1-ol Chemical compound C\C=C\CC\C=C\CO ONYJRUXYOCZIAW-BLWKUPHCSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- VTWGBBLEMMTQOT-UHFFFAOYSA-N 8-hydroxy-2-methyloct-6-enal Chemical compound O=CC(C)CCCC=CCO VTWGBBLEMMTQOT-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- DBNOWWUOVUIBSU-UHFFFAOYSA-N 9-hydroxynon-6-enal Chemical compound OCCC=CCCCCC=O DBNOWWUOVUIBSU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- DBYJIWYDEHDKJS-UHFFFAOYSA-N hexa-2,5-dien-1-ol Chemical compound OCC=CCC=C DBYJIWYDEHDKJS-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 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 2
- 229910006400 μ-Cl Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- HCSCWJCZRCSQFA-UHFFFAOYSA-N 1-methylpyrrolidin-2-one;hydrate Chemical compound O.CN1CCCC1=O HCSCWJCZRCSQFA-UHFFFAOYSA-N 0.000 description 1
- NMOLZWLFORPIME-UHFFFAOYSA-N 10-acetyloxydecyl acetate Chemical compound CC(=O)OCCCCCCCCCCOC(C)=O NMOLZWLFORPIME-UHFFFAOYSA-N 0.000 description 1
- BENPUORLYFCUJH-UHFFFAOYSA-N 2-methylheptane-1,7-diol Chemical compound OCC(C)CCCCCO BENPUORLYFCUJH-UHFFFAOYSA-N 0.000 description 1
- DYHGIZFXHVQIEA-UHFFFAOYSA-N 2-methylhexane-1,6-diol Chemical compound OCC(C)CCCCO DYHGIZFXHVQIEA-UHFFFAOYSA-N 0.000 description 1
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- IVRHVKUPGOJDGR-UHFFFAOYSA-N OCC=CCCCCCCC=O Chemical compound OCC=CCCCCCCC=O IVRHVKUPGOJDGR-UHFFFAOYSA-N 0.000 description 1
- 229910006067 SO3−M Inorganic materials 0.000 description 1
- RHKGZYVYKXVQSD-MECAPONASA-N [Rh].[O+]#[C-].C\C(O)=C\C(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Rh].[O+]#[C-].C\C(O)=C\C(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RHKGZYVYKXVQSD-MECAPONASA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical group C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- HWUMVJBWKZMIKH-UHFFFAOYSA-N hepta-2,6-dien-1-ol Chemical compound OCC=CCCC=C HWUMVJBWKZMIKH-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- DRECBBFIAREDAS-UHFFFAOYSA-N methoxymethane;hydrate Chemical compound O.COC DRECBBFIAREDAS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- CCRUWKGRGWGPNE-UHFFFAOYSA-N nona-2,8-dien-1-ol Chemical compound OCC=CCCCCC=C CCRUWKGRGWGPNE-UHFFFAOYSA-N 0.000 description 1
- OADYBSJSJUFUBR-UHFFFAOYSA-N octanedial Chemical compound O=CCCCCCCC=O OADYBSJSJUFUBR-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YDJTVHXQNJVWPL-UHFFFAOYSA-N thiolane 1,1-dioxide;hydrate Chemical compound O.O=S1(=O)CCCC1 YDJTVHXQNJVWPL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- SQWWBKIIYGLKHE-UHFFFAOYSA-N undecanedial Chemical compound O=CCCCCCCCCCC=O SQWWBKIIYGLKHE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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Abstract
The invention provides a preparation method of dialdehyde, which comprises the following steps: s1: subjecting non-conjugated diolefin having alkenyl groups with carbon-carbon double bonds and allyl alcohol groups at each molecular end to hydroformylation with carbon monoxide and hydrogen in an aqueous phase under the action of a catalyst to generate a reaction mixture; s2: extracting the reaction mixture obtained in the step S1; s3: and (3) rectifying the extracted oil phase containing the dialdehyde obtained in the step (S2) at least twice to obtain a dialdehyde product. The invention has the beneficial effects that: the method for preparing the dialdehyde has the characteristics of low catalyst cost, mild reaction condition, high catalytic activity, low product separation cost, obvious energy consumption advantage, high production efficiency and the like, and can realize the raw material conversion rate of 95-99%, the dialdehyde selectivity of 95-99% and the normal/isomerism ratio of 8.5-24:1.
Description
Technical Field
The invention belongs to the technical field of compound synthesis, and particularly relates to a preparation method of dialdehyde.
Background
Long carbon chain dialdehydes are key intermediates for the preparation of long carbon chain nylons, long carbon chain polyesters and polyurethanes. Taking 1, 9-nonanediol as an example, the downstream products thereof include 1, 9-nonanediamine, 1, 9-nonanediol, 1, 9-azelaic acid, nylon 9T, nonanediol-based polyester polyol, polyurethane epoxy resin, UV light-curable monomer, essence and perfume, etc.
The presently disclosed synthesis process of long carbon chain dialdehydes (exemplified by 1, 9-nonanediol) includes the following:
1. oleic acid decomposition method
The method is that azelaic acid ester obtained after oleic acid is subjected to ozonolysis and esterification is partially reduced by taking lithium aluminum hydride as a reducing agent, and finally, the nonanediol is obtained. However, this method has disadvantages of high costs of raw materials and reducing agents, incomplete reduction depth, etc., and is therefore impractical from a commercial point of view.
2. Hydroformylation of 7-octene-1-aldehyde
CN105050996a and EP1489087a disclose that catalysts composed of rhodium and a bisphosphine ligand catalyze the hydroformylation of 7-octene-1-aldehyde with hydrogen and carbon monoxide to obtain 1, 9-nonanal and 2-methyl-1, 8-octanedioaldehyde with selectivities of 80-92% and 5-16%, respectively, and normal/heterogeneous ratios of 4-6:1. However, the above patent does not disclose the recycling capability of the catalytic system. CN101415717a discloses that 2, 7-octadiene-1-methyl ether is used as raw material to catalyze the hydroformylation reaction by rhodium-biphosphine catalyst, and that only more than 90% of the hydroformylation products of terminal double bonds can be obtained due to the existence of methoxy.
Since rhodium catalysts are very expensive, it is desirable that they are used as hydroformylation catalysts in industry in as small an amount as possible, while it is necessary to recover these catalysts for recycling at high recovery rates. In order to separate the rhodium catalyst from the product by distillation, the reaction mixture must be heated to a high temperature until the high boiling long carbon chain dialdehyde product is distilled off, in contrast to low carbon olefins such as propylene, which have a very high boiling point in the long carbon chain nonconjugated dienes and their hydroformylation products. In this process, the rhodium catalyst is extremely susceptible to pyrolysis, resulting in formation of rhodium clusters and precipitation of metals, degradation, oxidation, etc. of the catalyst to form high boiling compounds, making it difficult to recycle the catalyst over a sufficiently long period of time, resulting in a drastic increase in cost.
CN1538971a discloses that 7-octene-1-aldehyde is subjected to a hydroformylation reaction in the presence of rhodium, a water-soluble phosphine ligand having a sulfonic acid group and polyethylene glycol, then water is added to the reaction solution to extract and separate a catalyst component, water of a separated water layer is removed, and the obtained polyethylene glycol containing the catalyst component is returned to the hydroformylation reactor to be recycled, and 1, 9-nonanal is obtained from an organic layer. However, from the information disclosed in this patent, the molar ratio of ligand to Rh used in the reaction is high (80:1), and the normal/heterogeneous ratio in the reaction product is only 4 to 5:1. In addition, although the recovery rate of Rh in this process is 97 to 98%, the recovery rate of ligand is only 82 to 83%, and periodic replenishment of phosphine ligand is required. It is well known that the cost of phosphine ligands is also high, which tends to increase the running cost of the device and reduce its technical competitiveness.
3. Hydroformylation of 2, 7-octadien-1-ols
US4420640a discloses the synthesis of 1, 9-nonanediol by hydroformylation of 2, 7-octadien-1-ol with rhodium and triphenylphosphine as catalysts. The technology directly obtains the 1, 9-nonanediol from the 2, 7-octadien-1-ol without preparing 7-octene-1-aldehyde through isomerization. However, from the information disclosed in this patent, this process has several problems: (1) the selectivity of the 1, 9-nonanal produced by the reaction is only 18-43%, the main product is mainly 9-hydroxy-7-octene-1-aldehyde (the terminal allyl alcohol group does not carry out iso-constitution aldehyde), the selectivity is 51-76%, and the rest byproducts are 9-hydroxy-6-nonenal, 8-hydroxy-2-methyl-6-octenal, 2-methyl-1, 8-octadienal, 2, 6-octadien-1-ol, n-octanol and the like. Although it is mentioned in the patent that 9-hydroxy-7-octene-1-aldehyde can be isomerized to generate 1, 9-nonanal by a copper-chromium catalyst, in the research process of the inventor, it is found that the 9-hydroxy-7-octene-1-aldehyde is extremely unstable when isomerized by the copper-chromium catalyst at high temperature, various byproducts such as acetal and internal double bond migration are extremely easy to form, the structure and boiling point are extremely close, and separation by a conventional rectifying means is difficult, which also results in more complicated industrial equipment and higher purification cost, thereby reducing the product competitiveness; (2) the patent adopts high-boiling-point 1, 10-decanediol diacetate and dioctyl phthalate as solvents, products are still separated by adopting a conventional rectification method, and the occurrence of metal precipitation and thermal degradation of rhodium catalyst in the high-temperature rectification process still cannot be avoided, so that the catalytic activity of the catalyst can be reduced due to accumulation of high-boiling-point byproducts. Therefore, the cost of the catalyst inevitably represents a large part of the production cost. And the patent does not disclose the recycling of the catalytic system; (3) the molar ratio of phosphine ligand to Rh used in the reaction is up to 100-600:1, which also increases the cost of production, which is disadvantageous for industrial reduction of production costs.
To overcome the limitations of the prior art, the following problems need to be addressed: (1) higher reaction rates are achieved from commercially acceptable rhodium catalyst concentrations; (2) the high selectivity of the 1, 9-nonanal is obtained, the occurrence of other side reactions including double bond migration and other isomerization is reduced as much as possible, and the separation difficulty of reaction products is reduced; (3) the activity of the rhodium catalyst is kept for a long time; (4) effectively separating the 1, 9-nonanediol from the reaction mixture without causing a significant decrease in the activity of the rhodium catalyst; (5) the recovery rate of the rhodium catalyst and the ligand thereof is improved, and the use cost of the catalyst is effectively reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a process for producing a dialdehyde having a linear dialdehyde content of 88 to 93wt% by hydroformylating a non-conjugated diolefin having 6 to 12 carbon atoms and having a carbon-carbon double bond alkenyl group and an allyl alcohol group at each molecular end, respectively, to solve the above-mentioned problems.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for preparing dialdehyde, comprising the following steps:
s1: subjecting non-conjugated diolefin having alkenyl groups with carbon-carbon double bonds and allyl alcohol groups at each molecular end to hydroformylation with carbon monoxide and hydrogen in an aqueous phase under the action of a catalyst to generate a reaction mixture;
S2: extracting the reaction mixture obtained in the step S1, and recycling the raffinate water phase containing the catalyst obtained after the extraction to the hydroformylation reaction step S1;
s3: and (3) rectifying the extracted oil phase containing the dialdehyde obtained in the step (S2) at least twice to obtain a dialdehyde product.
The catalyst in the step S1 consists of a ligand and at least one VIII transition metal compound, wherein the ligand comprises at least one compound selected from the general formula (I);
wherein:
R 1 、R 2 、R 3 、R 4 is hydrogen or alkylCycloalkyl, heterocycloalkyl, aryl, heteroaryl, COOR a 、COO - M + 、SO 3 R a 、SO3-M + 、NE 1 E 2 alkylene-NE 1 E 2 、NE 1 E 2 E 3+ X - Alkylene NE 1 E 2 E 3+ X - 、OR a 、SR a Any one of halogen, trifluoromethyl, nitro, acyl and cyano; r is R 1 、R 2 、R 3 、R 4 Are identical or different groups;
wherein R is a 、E 1 、E 2 And E is 3 R are identical or different radicals a 、E 1 、E 2 And E is 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl; m is M + Is a cation, X - Is an anion;
preferably M + Comprises Li + 、Na + 、K + Or a cation HN + F 1 F 2 F 3 Any one of, wherein F 1 、F 2 And F 3 Are identical or different radicals F 1 、F 2 And F 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl;
X - including any one of fluoride ion, chloride ion or bromide ion;
A 1 、A 2 o, S, siR of a shape of O, S, siR b R c 、NR d Or CR (CR) 5 R 6 Any one of A 1 、A 2 Are identical or different groups;
wherein R is b 、R c 、R d 、R 5 And R is 6 Each independently is any one of hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl;
R 7 、R 8 、R 9 、R 10 is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl or heteroarylAny one of (3);
R 7 、R 8 、R 9 、R 10 the substituents on the two are the same or different;
preferably, R 7 、R 8 、R 9 、R 10 With one, two or three substituents, which are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, COOR f 、COO - U + 、SO 3 - R f 、SO 3 U + 、NE 4 E 5 alkylene-NE 4 E 5 、NE 4 E 5 E 6+ V - Alkylene NE 4 E 5 E 6+ V - 、OR f 、SR f Any one of halogen, trifluoromethyl, nitro, acyl and cyano; u (U) + Is a cation, V-is an anion;
preferably U + Comprises Li + 、Na + 、K + Or a cation HN + F 1 F 2 F 3 Any one of, wherein F 1 、F 2 And F 3 Are identical or different radicals F 1 、F 2 And F 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl;
V - including any one of fluoride ion, chloride ion or bromide ion;
wherein R is f 、E 4 、E 5 、E 6 Are identical or different radicals R f 、E 4 、E 5 、E 6 Is any one of hydrogen, alkyl, cycloalkyl or aryl.
Further, the VIII transition group metal element in the VIII transition group metal compound is selected from one or two of rhodium and palladium;
preferably, the VIII transition group metal element in the VIII transition group metal compound is rhodium or palladium, wherein the molar ratio of palladium atoms to rhodium atoms is (0.01-0.5): 1;
preferably, the allylic group is a non-conjugated diolefin having 6 to 12 carbon atoms;
preferably, the molar ratio of rhodium atoms to the unconjugated diolefin raw material having a carbon-carbon double bond alkenyl group and an allyl alcohol group at each molecular end is (0.00001-0.01): 1.
Further, the ligand is a compound of the general formula (I-1) or the general formula (I-2);
wherein:
R 1 、R 3 is hydrogen, C 1 -C 4 Alkyl, C 5 -C 8 Cycloalkyl, aryl, heteroaryl, OR a 、SR a Any one of halogen, trifluoromethyl, nitro, acyl and cyano, R 1 And R is 3 Are the same or different groups;
R a is any one of hydrogen, alkyl, cycloalkyl or aryl;
A 1 for O, S or CR 5 R 6 Any one of R 5 、R 6 Is hydrogen, C 1 -C 4 Any one of alkyl groups, R 5 、R 6 Are the same or different groups;
R 11 、R 12 、R 13 、R 14 is hydrogen, substituted or unsubstituted C 1 -C 4 Alkyl, substituted or unsubstituted C 5 -C 8 Any one of cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; r is R 11 、R 12 、R 13 、R 14 Are the same or different groups;
preferably, R 11 、R 12 、R 13 、R 14 With one, two or three substituents, including alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, COOR f 、COO - Y + 、SO 3 - R f 、SO 3 Y + 、NE 4 E 5 alkylene-NE 4 E 5 、NE 4 E 5 E 6+ Z - Alkylene NE 4 E 5 E 6+ Z - 、OR f 、SR f Any one of halogen, trifluoromethyl, nitro, acyl and cyano;
wherein R is f 、E 4 、E 5 And E is 6 Is the same or different and is selected from any one of hydrogen, alkyl, cycloalkyl or aryl respectively;
R 11 、R 12 、R 13 、R 14 the substituents on the two are the same or different;
Z - is an anion, Y + Is a cation, Y + Is Li + 、Na + 、K + Or a cation HN + F 1 F 2 F 3 Any one of, wherein F 1 、F 2 And F 3 Are identical or different radicals F 1 、F 2 And F 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl.
Z - Including any of fluoride, chloride, or bromide.
Further, the number of carbon atoms of the non-conjugated diene raw material having a carbon-carbon double bond alkenyl group and an allyl alcohol group at each molecular end in the step S1 is 6 to 12;
preferably, the non-conjugated diene comprises one of 2, 5-hexadien-1-ol, 2, 6-heptadien-1-ol, 2, 7-octadien-1-ol, 2, 8-nonadien-1-ol, 2, 9-decadien-1-ol.
Further, the hydroformylation reaction involved in step S1 is carried out in an aqueous phase comprising a water-soluble solvent and water;
the water-soluble solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, acetone, tetrahydrofuran, dioxane, heptanone, sulfolane, polyethylene glycol and polyethylene glycol dimethyl ether; and/or
The water content of the aqueous phase is 25-60 wt%.
Further, in the hydroformylation reaction in the step S1, organic tertiary amine is added, wherein the added mass of the organic tertiary amine is 0.1-10wt% of the mass of the unconjugated diene;
preferably, the organic tertiary amine comprises one or more of trialkylamine, trialkylalcohol amine, alicyclic tertiary amine, pyridine; the organic tertiary amine serves several functions: (1) accelerating the catalytic cycle of rhodium and palladium and improving the reaction rate of the hydroformylation reaction; (2) promoting the further isomerization of terminal allyl groups in the palladium catalytic raw material molecules into aldehyde, thereby obtaining a dialdehyde product; (3) preventing the phenomenon that acetal is easy to form due to trace acid in the reaction process.
Preferably, the reaction temperature of the hydroformylation reaction is 40 to 150 ℃, and the mixed gas H of hydrogen and carbon monoxide 2 The composition mole ratio of the catalyst/CO is 0.1-10, and the reaction pressure is 0.1-10 MPa.
Further, the step S2 comprises extracting the reaction mixture obtained in the step S1 with a saturated aliphatic hydrocarbon or a saturated alicyclic hydrocarbon, and separating it into an extracted oil phase containing dialdehydes and a raffinate water phase;
preferably, the saturated aliphatic hydrocarbon comprises at least one of n-pentane, n-hexane and n-octane;
preferably, the saturated alicyclic hydrocarbon comprises at least one of cyclopentane, cyclohexane, methylcyclohexane, decalin and ethers, wherein the ethers are selected from any one of dibutyl ether, diisopropyl ether, ethylphenyl ether and methyl tert-butyl ether.
Preferably, the extraction separation in the step S2 is performed in inert atmosphere, the extraction temperature is 20-80 ℃, and the extraction pressure is 0.1-5 MPa.
Preferably, the inert atmosphere gas comprises one or more of helium, neon, argon, krypton, xenon or nitrogen.
The product prepared by the method comprises one of straight-chain alkane dialdehyde and methyl alkane dialdehyde.
Preferably, the straight chain alkanedialdehyde comprises one of 1, 7-heptanedioal, 1, 8-octanednal, 1, 9-nonanediol, 1, 10-decanedialdehyde, 1, 11-undecadipaldehyde;
Preferably, the methylalkane dialdehyde comprises one of 2-methyl-1, 6-hexanedial, 2-methyl-1, 7-heptanedial, 2-methyl-1, 8-octanednal, 2-methyl-1, 9-nonanedial, 2-methyl-1, 10-decanedialdehyde.
Specific examples of the general formula (I) include, but are not limited to, compounds represented by the following structures:
in step S1, a catalyst comprising a ligand having at least one compound selected from the group consisting of compounds of formula (I) and at least one compound of a transition group VIII metal selected from rhodium is provided. The rhodium compound may be selected from Rh (NO 3 ) 2 、Rh(OAc) 2 、Rh(acac)(CO) 2 、Rh(acac)(CO)(PPh 3 )、HRh(CO)(PPh 3 ) 3 、RhCl(CO)(PPh 3 ) 2 、RhBr(CO)(PPh 3 ) 2 、RhCl(PPh 3 ) 3 、[Rh(μ-OAc)(CO) 2 ] 2 、[Rh(μ-OAc)(COD)] 2 、[Rh(μ-Cl)(COD)] 2 、[Rh(μ-Cl)(CO) 2 ] 2 、Rh 4 (CO) 12 、Rh 4 (CO) 8 (PPh 3 ) 4 And Rh 6 (CO) 16 (wherein OAc represents acetyl, acac represents acetylacetonate, ph represents phenyl, COD represents 1, 5-cyclooctadiene) and the like. Wherein the reaction is easily performed in a mixed gas atmosphere containing carbon monoxide and hydrogenFrom the viewpoint of preparing rhodium catalyst, rh (acac) (CO) is preferably used 2 And Rh (OAc) 2 。
In step S1, the catalyst comprising at least one ligand selected from the compounds of formula (I) and at least one VIII transition metal compound is provided, wherein the VIII transition metal compound comprises a rhodium compound and a palladium compound. The palladium compound may be selected from PdCl 2 、Pd(NO 3 ) 2 、Pd(OAc) 2 、Pd(acac) 2 、[Pd(allyl)Cl] 2 、[Pd(allyl)OAc]2、PdCl 2 (PPh 3 ) 2 、[PdCl 2 (COD)]、Pd(OAc) 2 (PPh 3 ) 2 Bis (benzonitrile) palladium (II) dichloride, pd (PPh) 3 ) 4 And Pd (Pd) 2 (dba) 3 (wherein OAc represents acetyl, acac represents acetylacetone, ph represents phenyl, COD represents 1, 5-cyclooctadiene, dba represents dibenzylideneacetone). Pd (acac) is preferred 2 、Pd(OAc) 2 And Pd (Pd) 2 (dba) 3 。
Further, the molar ratio of the rhodium atom to the non-conjugated diolefin raw material having 6 to 12 carbon atoms each having a carbon-carbon double bond alkenyl group and an allyl alcohol group at the end of each molecule in the step S1 is (0.00001 to 0.01): 1, preferably (0.0001 to 0.005): 1, and particularly preferably (0.0001 to 0.001): 1; the molar ratio of palladium to rhodium is (0.01-0.5): 1, preferably (0.05-0.2): 1; the amount of the water-soluble phosphine ligand represented by the general formula (I) used is in the range of 10 to 200 moles, preferably 10 to 100 moles, more preferably 15 to 80 moles per gram atom of rhodium.
The inventors have unexpectedly found during the course of the study that by adding a small amount of palladium to the rhodium catalyst, the Rh-Pd bimetallic complex formed exhibits a higher synergistic catalysis in catalyzing the hydroformylation reaction, enabling higher reaction selectivities and normal/heterogeneous ratios to be obtained. Meanwhile, palladium can catalyze the terminal allyl in the raw material molecule to further isomerize into aldehyde under the condition of adding a small amount of auxiliary organic tertiary amine, so as to obtain a dialdehyde product.
In step S1 according to the present invention, for preparing a catalyst comprising a ligand having at least one compound selected from the group consisting of the compounds of the general formula (i) and at least one compound of the group VIII transition group metal, a solution of at least one compound of the group VIII transition group metal, i.e., a compound of rhodium and palladium, dissolved in a solvent and a solution of the ligand of the compound of the general formula (i) dissolved in a solvent are separately supplied to a hydroformylation reaction system to form a catalyst in the reaction system; or dissolving rhodium and palladium compounds and compounds of the general formula (I) in a solvent under an inert gas atmosphere, and then stirring preferably under an inert gas such as nitrogen, argon, helium or a mixed gas containing carbon monoxide and hydrogen to prepare a catalyst solution, and then supplying the catalyst solution to the hydroformylation reaction system.
The non-conjugated diene raw material having 6 to 12 carbon atoms and having an alkenyl group having a carbon-carbon double bond and an allylic group at each molecular end in the step S1 of the present invention is any compound selected from the group consisting of 2, 5-hexadiene-1-ol, 2, 6-heptadiene-1-ol, 2, 7-octadiene-1-ol, 2, 8-nonadiene-1-ol and 2, 9-decadiene-1-ol, preferably 2, 7-octadiene-1-ol. The starting material 2, 7-octadien-1-ol for carrying out the hydroformylation reaction of the invention can be prepared by any method. Preference is given to using 2, 7-octadien-1-ol having a purity of from about 90 to 99.9%, particularly preferably from about 95 to 99.9%.
Further, the addition amount of the organic tertiary amine is 0.1 to 10wt%, preferably 0.2 to 5wt%, particularly preferably 0.5 to 3wt% of the raw material. The organic tertiary amine serves several functions: (1) accelerating the catalytic cycle of rhodium and palladium and improving the reaction rate of the hydroformylation reaction; (2) promoting the further isomerization of terminal allyl groups in the palladium catalytic raw material molecules into aldehyde, thereby obtaining a dialdehyde product; (3) preventing the phenomenon that acetal is easy to form due to trace acid in the reaction process.
The reaction temperature of the hydroformylation reaction of step S1 of the present invention is preferably from 40 to 150℃and particularly preferably from 60 to 100℃from the viewpoint of suppressing deactivation of the catalyst.
The hydroformylation reaction may be carried out continuously, semi-continuously or batchwise, preferably continuously.
In the process according to the invention, the dialdehyde-containing reaction mixture obtained in step S1 is extracted in a further step S2. As the extraction device, general-purpose extraction devices such as extraction columns and centrifugal extractors can be used.
Further, in order to achieve effective extraction of the dialdehyde product, the dissolution or migration of the catalyst component, the water-soluble solvent and the auxiliary organic tertiary amine in the extraction layer is minimized, the volume ratio of the amount of the extractant to the reaction mixture of step S1 is 0.3-3:1, preferably 0.5-2:1. If the amount of extractant is too low, the extraction yield of the desired product is too low; conversely, if the amount of extractant exceeds 3 times the volume of the reaction mixture, a large amount of extractant must be recovered in separating the product, which tends to increase the separation energy consumption, and is industrially uneconomical.
The extraction separation temperature in step S2 of the present invention is in the range of 20 to 80℃and preferably 30 to 60 ℃. Too low a temperature can reduce the efficiency of extracting the dialdehyde product; although there is no clear upper limit for the extraction temperature, the extraction temperature generally does not exceed the reaction temperature of step S1, taking into account the pressure relationship between the temperature and the inert gas and/or the mixed gas of hydrogen and carbon monoxide in the extraction system. The extraction separation is preferably performed in an inert gas which does not adversely affect the extraction process, such as nitrogen, helium, argon, carbon dioxide, etc., and in a mixed gas of hydrogen and carbon monoxide in which the molar ratio of hydrogen to carbon monoxide is 0.1 to 10, preferably 1 to 3. The extraction and separation pressure is 0.1-5 MPa, preferably 0.1-2 MPa. The extraction separation is preferably carried out continuously, but also batchwise.
In the extraction process of step S2 according to the present invention, the dialdehyde product and unreacted raw materials are extracted into an extraction layer (oil phase), and the catalyst component, the water-soluble solvent, the organic tertiary amine auxiliary agent, and the like are separated into a raffinate layer (aqueous phase). In a preferred embodiment of the invention, a small amount of water is added into the extraction layer for back extraction, so that a small amount of catalyst components and organic tertiary amine auxiliary agents dissolved or migrated in the original extraction layer can be further effectively extracted, and the recovery rate of the catalyst and the organic tertiary amine auxiliary agents is improved. The stripping aqueous phase may be recycled to the hydroformylation reaction step S1, i.e. step S2 recycle step as described herein, either after combining with the raffinate layer or after a known catalyst activation procedure. The extraction layer is rectified at a liquid phase temperature of not higher than 100deg.C. The distilled low-boiling extraction solvent can be recycled to the step S2 again for reuse in the extraction operation. Further rectifying the rectification residue to obtain dialdehyde product with purity over 99%.
The dialdehyde product of the present invention having 7-13 carbon atoms each having an aldehyde group at the end of the molecule is selected from straight-chain alkanedialdehydes such as 1, 7-heptanediol, 1, 8-octanednal, 1, 9-nonanediol, 1, 10-decanedialdehyde, 1, 11-undecanedialdehyde, etc.; methylalkanedialdehyde such as 2-methyl-1, 6-hexanedialdehyde, 2-methyl-1, 7-heptanedialdehyde, 2-methyl-1, 8-octanedioaldehyde, 2-methyl-1, 9-nonanedialdehyde, 2-methyl-1, 10-decanedialdehyde, preferably 1, 9-nonanedialdehyde and 2-methyl-1, 8-octanedioaldehyde.
1, 9-nonanediol may be converted by oxidation to 1, 9-azelaic acid, which is commercially useful as a raw material for the production of lubricants, polyesters, plasticizers, and the like; 1, 9-nonanediol can also be converted into 1, 9-nonanediol by hydrogenation, and is used for producing long-carbon polyesters, polyurethanes and the like; in addition, 1, 9-nonanedialdehyde can be converted into 1, 9-nonanediamine by reaction with ammonia and hydrogen, and can be used for producing long carbon chain high temperature nylon and the like.
Compared with the prior art, the preparation method of the dialdehyde has the following advantages:
1. the invention adopts non-conjugated diolefin with carbon atoms of 6-12 and each molecular end having carbon-carbon double bond alkenyl and allyl alcohol group as raw material, prepares dialdehyde directly by one-step method under the catalysis of water-soluble rhodium-palladium, and can obtain raw material conversion rate of 95-99%, dialdehyde selectivity of 95-99% and normal/isomerism ratio of 8.5-24:1. Taking 1, 9-nonanal as an example, the invention adopts 2, 7-octadien-1-ol as a raw material to directly carry out hydroformylation reaction to prepare the 1, 9-nonanal, and under the synergistic catalysis of rhodium-palladium bimetallic catalyst, organic tertiary amine is matched, and the hydroformylation of terminal olefin can be carried out while the direct iso-formation of aldehyde by the allyl alcohol group at the other terminal can be realized, thereby effectively improving the selectivity (88-92%) and the normal/heterogeneous ratio (8.5-24:1) of straight-chain 1, 9-nonanal.
2. The preparation method of the dialdehyde has obvious cost advantage of the catalyst. On one hand, the rhodium-palladium catalyst used in the invention has extremely low dosage, and the ratio of the water-soluble phosphine ligand to rhodium atoms is lower than or close to that in the prior art, so that the input cost of the catalyst is reduced from the source; on the other hand, the water-soluble catalyst system and the extraction process adopted by the invention can realize high recovery rate of noble metal and phosphine ligand in the catalyst and can keep the catalytic activity of the catalyst system for a long time. In a preferred embodiment of the present invention, a rhodium atom recovery of greater than 95%, a palladium atom recovery of greater than 96%, and a water-soluble phosphine ligand recovery of greater than 95% can be achieved by the extraction process. After the catalyst is recycled and continuously reused for 30 times, the higher reaction conversion rate and selectivity can be still maintained. This greatly reduces the cost of catalyst use, increases the technical competitiveness, and is very advantageous for control of industrial costs.
3. The preparation method of the dialdehyde has the advantages of low separation operation difficulty and low energy consumption. Compared with the prior art, the method has the advantages that the reaction conditions are mild, the extraction and separation are easy to operate, and the catalyst is not required to be recovered by adopting high-temperature rectification, so that the problems of rhodium catalyst metal precipitation and thermal degradation in the high-temperature rectification process are avoided, and the activity of the catalyst can be effectively maintained for a long time. In addition, the higher reaction selectivity and yield can further effectively avoid the generation of high-boiling-point byproducts such as double bond migration isomerism with similar functional groups and carbon atoms, greatly reduce the difficulty of separating the byproducts and the operation difficulty, have obvious energy consumption advantage and are suitable for industrial production.
4. The preparation method of the dialdehyde has strong universality and can be used for preparing various dialdehydes with different carbon atoms.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The present invention will be described in detail with reference to examples. The following examples serve to illustrate the invention without limiting it.
In the following examples, regarding the concentrations of rhodium atoms, palladium atoms and phosphine ligand compounds contained in the aqueous phase obtained by the extraction operation, analysis and quantification were performed by an inductively coupled plasma mass spectrometer of agilent. In addition, the organic tertiary amine auxiliary, raw material and product dialdehyde contained in the hydroformylation reaction liquid or the aqueous phase containing the catalyst are analyzed and quantified by gas chromatography under the following measurement conditions. The conversion of the reactants, the selectivity of the product and the yield were calculated on the basis of this.
The gas chromatographic analysis conditions were as follows:
chromatographic column: agilent DB-Wax (30 m 0.32mm 0.25 mm); sample inlet temperature: 300 ℃; split ratio: 30:1; column flow rate: 1.5mL/min; column temperature: 100 ℃ for 0.5min; heating program: raising the temperature to 300 ℃ at 15 ℃/min, and keeping for 8min; detector temperature: 300 ℃, hydrogen flow: 35mL/min, air flow: 350mL/min.
Unless otherwise specified, the catalyst is prepared at room temperature under normal pressure under a nitrogen atmosphere, and the raw materials and the solvent are distilled and purified in advance and then subjected to nitrogen substitution for use.
As the water-soluble phosphine ligand represented by the general formula (I), the hydroformylation reaction in examples was carried out using a compound represented by the following chemical formula. These compounds can be prepared synthetically according to known methods.
Example 1:
step S1 hydroformylation reaction:
to a 100mL glass flask under nitrogen was added a flask containing Rh (acac) (CO) 2 81.8mg (rhodium atom 0.317 mmol) and Pd (acac) 2 9.8mg (palladium atom 0.032 mmol) of a dimethyl sulfoxide solution 5g, followed by adding 20g of an aqueous solution containing 4.96g (6.34 mmol) of the ligand A and stirring at room temperature for 20 minutes, to prepare a catalyst A.
80g of desalted water, 125g of dimethyl sulfoxide, 80g (0.634 mol) of 2, 7-octadien-1-ol and 0.8g of triethylamine were charged into a 500mL autoclave, and after 3 times of substitution with nitrogen, the autoclave was purged and pressurized to 2MPa with a mixed gas of hydrogen and carbon monoxide (molar ratio of hydrogen to carbon monoxide: 1:1) while stirring at 500rpm and raising the temperature to 80 ℃. Subsequently, the catalyst a solution prepared in advance was rapidly fed under pressure into a high-pressure reaction vessel using a mixed gas of hydrogen and carbon monoxide (molar ratio of hydrogen to carbon monoxide: 1:1) and the total pressure was made 2.5MPa. The time after pressurized delivery of the catalyst a solution to the reaction vessel was defined as the start of the reaction. The ratio of phosphine ligand A to rhodium atom in the preparation of the catalyst A solution was 20:1, the ratio of palladium atom to rhodium atom was 0.1:1, the molar ratio of rhodium atom to raw material 2, 7-octadien-1-ol in the hydroformylation reaction was 0.0005:1, the mass ratio of triethylamine to raw material was 1wt%, and the water content in the aqueous solvent was 43.5wt%.
For the hydroformylation reaction liquid after a certain period of reaction, quantitative analysis of the product was performed by gas chromatography.
The conversion of the starting material 2, 7-octadien-1-ol is calculated according to the following formula 1, in which the units of the respective amounts are mol.
Examples of the reaction product include 1, 9-nonanal, 2-methyl-1, 8-octadienal, 9-hydroxy-7-nonen-1-al, 9-hydroxy-6-nonen-1-al, 8-hydroxy-2-methyl-6-octen-1-al, 2-methyl-1, 8-octadienal, 2, 6-octadien-1-ol, and n-octanol. Wherein each amount is in mol.
Selectivity for high boiling point product=100- (sum of selectivities of respective products calculated by expression 2) (expression 3)
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 98.2%, the selectivity of the product 1, 9-nonanal was 91.5%, the selectivity of 2-methyl-1, 8-octadienal was 6.8%, the normal/isomer ratio was 24:1, the selectivity of 9-hydroxy-7-nonen-1-aldehyde was 0.4%, and the selectivity of the other components and the high boiling products amounted to 1.3%.
Step S2, reaction liquid extraction:
the autoclave was cooled to 30℃and the reaction mixture was then pressure-fed into a pressure-resistant glass reaction vessel pressurized to 0.3MPa beforehand with a mixed gas of hydrogen and carbon monoxide (molar ratio 1:1) under the action of the internal pressure of the vessel. 200mL of cyclohexane was pumped into a glass reaction vessel, the temperature in the vessel was maintained at 30℃and stirred at a pressure of 0.3MPa for 20min. After stopping stirring, the reaction mixture was separated into oil-water phases, and after standing for 10min, the extraction layer (oil phase) was withdrawn through a pipe using internal pressure. The pressure-resistant glass reaction vessel containing the aqueous phase was kept at a pressure of 0.3MPa and a temperature of 30℃and 135mL of fresh cyclohexane was again added thereto, and the mixture was stirred under the same conditions for 10 minutes and then allowed to stand for 5 minutes. The upper extract layer was withdrawn from the autoclave and combined with the cyclohexane extract phase layer previously withdrawn, and finally 5mL of water was added to back-extract it, and the aqueous phase was incorporated into the pressure-resistant glass reaction vessel. The volume ratio of cyclohexane to the hydroformylation reaction liquid was 1.2:1.
The rhodium content, palladium content and phosphine ligand content contained in the aqueous phase are calculated by rhodium concentration, palladium concentration, phosphorus concentration and weight of the recovered aqueous phase, wherein the rhodium concentration, palladium concentration and phosphorus concentration are respectively quantitatively analyzed by an inductively coupled plasma mass spectrometer. The recovery rate of the three components is calculated by the following mathematical expression, wherein each unit of amount in the expression is mol.
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The recovery rate of rhodium atoms in the aqueous phase after extraction was 97.8%, the recovery rate of palladium atoms was 98.2%, and the recovery rate of water-soluble phosphine ligand A was 96.6%.
Example 2:
the same operation was conducted, except that 3.875g (4.755 mmol) of ligand B was used instead of the ligand A used in example 1, to prepare a catalyst B. The ratio of ligand B to rhodium atoms in the catalyst preparation was 15:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 95.5%, the selectivity of the product 1, 9-nonanal was 90.4%, the selectivity of 2-methyl-1, 8-octadienal was 5.3%, the normal/isomer ratio was 17:1, the selectivity of 9-hydroxy-7-nonen-1-aldehyde was 1.7%, and the selectivity of the other components and the high boiling products amounted to 2.6%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid is extracted is 98.5%, the recovery rate of palladium atoms is 98.9%, and the recovery rate of water-soluble phosphine ligand B is 95.8%.
Example 3:
the same operation was conducted, except that 10.44g (11.095 mmol) of ligand C was used instead of the ligand A used in example 1, to prepare a catalyst C. The ratio of ligand C to rhodium atoms in the catalyst preparation was 35:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 96.7%, the selectivity of the product 1, 9-nonanal was 89.3%, the selectivity of 2-methyl-1, 8-octadienal was 7.1%, the normal/isomer ratio was 12.5:1, the selectivity of 9-hydroxy-7-nonen-1-al was 2.2%, and the selectivity of the other components and the high boiling products amounted to 1.4%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted was 97.1%, the recovery rate of palladium atoms was 98.3%, and the recovery rate of the water-soluble phosphine ligand C was 96.9%.
Example 4:
the same operation was conducted, except that 2.88g (3.80 mmol) of ligand D was used instead of the ligand A used in example 1, to prepare a catalyst D. The ratio of ligand D to rhodium atoms in the catalyst preparation was 12:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 96.7%, the selectivity of the product 1, 9-nonanal was 89.3%, the selectivity of 2-methyl-1, 8-octadienal was 7.1%, the normal/isomer ratio was 12.5:1, the selectivity of 9-hydroxy-7-nonen-1-al was 2.2%, and the selectivity of the other components and the high boiling products amounted to 1.4%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted was 97.1%, the recovery rate of palladium atoms was 98.3%, and the recovery rate of the water-soluble phosphine ligand D was 96.9%.
Example 5:
the same operation was conducted, except that 3.13g (3.17 mmol) of ligand E was used instead of the ligand A used in example 1, to prepare a catalyst E. The ratio of ligand E to rhodium atoms in the catalyst preparation was 10:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 97.9%, the selectivity of the product 1, 9-nonanal was 89.9%, the selectivity of 2-methyl-1, 8-octadienal was 5.8%, the normal/isomer ratio was 15.5:1, the selectivity of 9-hydroxy-7-nonen-1-al was 1.1%, and the selectivity of the other components and the high boiling products amounted to 3.2%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted was 98.2%, the recovery rate of palladium atoms was 97.5%, and the recovery rate of the water-soluble phosphine ligand E was 98.6%.
Example 6:
the same operation was conducted, except that 6.32g (5.71 mmol) of ligand F was used instead of the ligand A used in example 1, to prepare a catalyst F. The ratio of ligand F to rhodium atoms in the catalyst preparation was 18:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 96.1%, the selectivity of the product 1, 9-nonanal was 90.8%, the selectivity of 2-methyl-1, 8-octadienal was 4.6%, the normal/isomer ratio was 19.7:1, the selectivity of 9-hydroxy-7-nonen-1-al was 1.2%, and the selectivity of the other components and the high boiling products amounted to 3.4%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid is extracted is 99.3%, the recovery rate of palladium atoms is 98.6%, and the recovery rate of the water-soluble phosphine ligand F is 96.1%.
Comparative example 1:
the same operation was conducted, except that 2.21G (6.34 mmol) of ligand G was used instead of the ligand A used in example 1, to prepare a catalyst G. The ratio of ligand G to rhodium atoms in the catalyst preparation was 20:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 92.7%, the selectivity of the product 1, 9-nonanal was 69.2%, the selectivity of 2-methyl-1, 8-octadienal was 10.9%, the normal/isomer ratio was 6.3:1, the selectivity of 9-hydroxy-7-nonen-1-al was 8.5%, and the selectivity of the other components and the high boiling products amounted to 11.4%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted was 65.5%, the recovery rate of palladium atoms was 68.2%, and the recovery rate of the water-soluble phosphine ligand G was 79.3%.
Comparative example 2:
the same operation was conducted, except that 2.16g (3.80 mmol) of ligand H was used instead of the ligand A used in example 1, to prepare a catalyst H. The ratio of ligand H to rhodium atoms in the catalyst preparation was 12:1.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 95.5%, the selectivity of the product 1, 9-nonanal was 78.3%, the selectivity of 2-methyl-1, 8-octadienal was 11.6%, the normal/isomer ratio was 6.8:1, the selectivity of 9-hydroxy-7-nonen-1-al was 6.4%, and the selectivity of the other components and the high boiling products amounted to 3.7%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted was 79.6%, the recovery rate of palladium atoms was 80.1%, and the recovery rate of water-soluble phosphine ligand H was 84.6%.
Table 1 summarizes the results of the hydroformylation reactions of examples 1-6 and comparative examples 1-2 and the recovery of rhodium, palladium, and phosphorus. As can be seen from Table 1, the water-soluble ligands of the general formula S1 according to the invention, compared with the water-soluble monophosphine ligands (comparative examples 1 and 2), are better able to carry out a one-step hydroformylation of 2, 7-octadien-1-ol to give a dialdehyde product based on 1, 9-nonanedial directly, while achieving a higher normal isomerism ratio than in the prior art, after formation of the catalyst with rhodium and palladium. More importantly, rhodium, palladium and phosphine ligands can be recovered in a high proportion through the extraction process of the step S2, so that the use cost of the catalyst is greatly reduced.
TABLE 1 application of different Water-soluble phosphine ligands to 2, 7-octadien-1-ol hydroformylation to 1, 9-nonanediol results
Example 7:
step S1 hydroformylation reaction:
rh containing (OAc) was added to a 100mL glass flask under nitrogen atmosphere 2 69.3mg (rhodium atom 0.428 mmol) and Pd (OAc) 2 14.4mg (palladium atom 0.064 mmol) of sulfolane solution 10g, followed by addition of an aqueous solution 20g containing 8.37g (10.7 mmol) of ligand A and stirring at room temperature for 20min, to prepare catalyst A.
80g of desalted water, 175g of sulfolane, 46.7g (0.253 mol) of 2, 5-hexadien-1-ol and 1.17g of triethylamine were charged into a 500mL autoclave, and after 3 times of substitution with nitrogen, the autoclave was purged and pressurized to 2MPa with a mixed gas of hydrogen and carbon monoxide (molar ratio of hydrogen to carbon monoxide: 1:1) while stirring at 500rpm and raising the temperature to 80 ℃. Subsequently, the catalyst a solution prepared in advance was rapidly fed under pressure into a high-pressure reaction vessel using a mixed gas of hydrogen and carbon monoxide (molar ratio of hydrogen to carbon monoxide: 1:1) and the total pressure was made 2.5MPa. The time after pressurized delivery of the catalyst a solution to the reaction vessel was defined as the start of the reaction. The ratio of phosphine ligand A to rhodium atom in the preparation of the catalyst A solution was 25:1, the ratio of palladium atom to rhodium atom was 0.15:1, the molar ratio of rhodium atom to raw material 2, 5-hexadiene-1-ol in the hydroformylation reaction was 0.0009:1, the mass ratio of triethylamine to raw material was 2.5wt%, and the water content in the aqueous solvent was 35wt%.
For the hydroformylation reaction liquid after a certain period of reaction, quantitative analysis of the product was performed by gas chromatography.
After 3h of reaction, the conversion of the starting 2, 5-hexadien-1-ol was 97.6%, the selectivity for the linear product 1, 9-heptanediol was 87.5%, the selectivity for the branched 2-methyl-1, 6-hexanediol was 10.3%, the normal/isomer ratio was 8.5:1, the selectivity for the product in which the terminal allylic groups did not form an aldehyde, namely 7-hydroxy-5-hepten-1-al, was 0.8%, and the selectivity for the other components and the high boiling products amounted to 1.4%.
Step S2, reaction liquid extraction:
the autoclave was cooled to 30℃and the reaction mixture was then pressure-fed into a pressure-resistant glass reaction vessel pressurized to 0.3MPa beforehand with a mixed gas of hydrogen and carbon monoxide (molar ratio 1:1) under the action of the internal pressure of the vessel. 300mL of cyclohexane was pumped into a glass reaction vessel, the temperature in the vessel was maintained at 40℃and stirred at a pressure of 0.2MPa for 20min. After stopping stirring, the reaction mixture was separated into oil-water phases, and after standing for 10min, the extraction layer (oil phase) was withdrawn through a pipe using internal pressure. The pressure-resistant glass reaction vessel containing the aqueous phase was kept at a pressure of 0.3MPa and a temperature of 40℃and 300mL of fresh cyclohexane was again added thereto, and the mixture was stirred under the same conditions for 10 minutes and then allowed to stand for 5 minutes. The upper extract layer was withdrawn from the autoclave and combined with the cyclohexane extract phase layer previously withdrawn, and finally 5mL of water was added to back-extract it, and the aqueous phase was incorporated into the pressure-resistant glass reaction vessel. The volume ratio of cyclohexane to the hydroformylation reaction liquid was 2:1.
The rhodium content, palladium content and phosphine ligand content contained in the aqueous phase are calculated by rhodium concentration, palladium concentration, phosphorus concentration and weight of the recovered aqueous phase, wherein the rhodium concentration, palladium concentration and phosphorus concentration are respectively quantitatively analyzed by an inductively coupled plasma mass spectrometer. The recovery rate of rhodium atoms in the aqueous phase after extraction was 98.0%, the recovery rate of palladium atoms was 97.9%, and the recovery rate of water-soluble phosphine ligand A was 95.3%.
Example 8:
as shown in table 2, except that the following reaction conditions were replaced in example 7, namely: the same procedure was carried out with a phosphine ligand A to rhodium atom ratio of 10:1, a palladium atom to rhodium atom ratio of 0.08:1, a tributylamine mass ratio to the starting material of 1.3wt%, and a water content of 58wt% in the sulfolane-water solvent.
After 3h of reaction, the conversion of the starting 2, 6-heptadien-1-ol was 98.9%, the selectivity of the linear product 1, 8-octanedioaldehyde was 89.4%, the selectivity of the branched 2-methyl-1, 7-heptanediol was 6.3%, the normal/isomer ratio was 14.2:1, the selectivity of the product having no terminal allylic group forming aldehyde, i.e., 8-hydroxy-6-octen-1-al, was 2.7%, and the selectivity of the other components and the high boiling products amounted to 1.6%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid is extracted by normal hexane is 97.5%, the recovery rate of palladium atoms is 98.4%, and the recovery rate of the water-soluble phosphine ligand A is 95.9%.
Example 9:
as shown in table 2, except that the following reaction conditions were replaced in example 7, namely: the same procedure was carried out with a phosphine ligand E to rhodium atom ratio of 18:1, a palladium atom to rhodium atom ratio of 0.25:1, a triethanolamine mass ratio to the starting material of 3wt%, and a water content of 55wt% in NMP-water solvent.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 97.1%, the selectivity for the linear product 1, 9-nonanal was 90.3%, the selectivity for the branched 2-methyl-1, 8-octadienal was 6.1%, the normal/isomer ratio was 14.8:1, the selectivity for the product having no terminal allylic aldehyde, i.e., 9-hydroxy-7-nonen-1-aldehyde, was 1.5%, and the selectivity for the other components and the high boiling products amounted to 2.1%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted with methylcyclohexane was 98.8%, the recovery rate of palladium atoms was 97.6%, and the recovery rate of the water-soluble phosphine ligand E was 97.1%.
Example 10:
as shown in table 2, except that the following reaction conditions were replaced in example 7, namely: the same procedure was carried out with a phosphine ligand E to rhodium atom ratio of 20:1, a palladium atom to rhodium atom ratio of 0.2:1, a starting material of 2, 8-nonadien-1-ol, trioctylamine to starting material mass ratio of 1.5wt%, and a PEG-200-hydrosolvent water content of 40 wt%.
After 3h of reaction, the conversion of the starting 2, 8-nonadien-1-ol was 99.1%, the selectivity for the linear product 1, 10-decanedialdehyde was 88.8%, the selectivity for the branched 2-methyl-1, 9-nonanedial was 7.1%, the normal/isomer ratio was 12.5:1, the selectivity for the product having no terminal allylic aldehyde, i.e., 10-hydroxy-8-decen-1-al, was 2.2%, and the selectivity for the other components and the high boiling products amounted to 1.9%.
The recovery rate of rhodium atoms in the aqueous phase after cyclohexane extraction of the hydroformylation reaction liquid was 95.9%, the recovery rate of palladium atoms was 96.2%, and the recovery rate of the water-soluble phosphine ligand E was 96.5%.
Example 11:
as shown in table 2, except that the following reaction conditions were replaced in example 7, namely: the same procedure was carried out with a phosphine ligand F to rhodium atom ratio of 15:1, a palladium atom to rhodium atom ratio of 0.11:1, a starting material of 2, 7-octadien-1-ol, tripropylamine in a mass ratio of 2% relative to the starting material, and a water content of 50% in DMF-water solvent.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 97.5%, the selectivity for the linear product 1, 9-nonanal was 89.9%, the selectivity for the branched 2-methyl-1, 8-octadienal was 7.8%, the normal/isomer ratio was 11.5:1, the selectivity for the product having no terminal allylic aldehyde, i.e., 9-hydroxy-7-nonen-1-aldehyde, was 1.0%, and the selectivity for the other components and the high boiling products amounted to 1.3%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted with methylcyclohexane was 97.2%, the recovery rate of palladium atoms was 96.5%, and the recovery rate of the water-soluble phosphine ligand F was 95.6%.
Example 12:
as shown in table 2, except that the following reaction conditions were replaced in example 7, namely: the same procedure was carried out with a phosphine ligand F to rhodium atom ratio of 30:1, a palladium atom to rhodium atom ratio of 0.1:1, a raw material 2, 9-decadien-1-ol, triethylamine to raw material mass ratio of 1.8wt%, and a water content of 58wt% in a polyethylene glycol dimethyl ether-water solvent.
After 3h of reaction, the conversion of the starting 2, 9-decadien-1-ol was 96.1%, the selectivity for the linear product 1, 11-undecadipaldehyde was 90.3%, the selectivity for the branched 2-methyl-1, 10-decandialdehyde was 5.6%, the normal/isomerism ratio was 16.1:1, the selectivity for the 11-hydroxy-9-decen-1-al, which is the product of the terminal allylic group not isomerised to aldehyde, was 2.3%, and the selectivity for the other components and the high boiling products amounted to 1.8%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid is extracted by normal hexane is 98.9 percent, the recovery rate of palladium atoms is 98.1 percent, and the recovery rate of the water-soluble phosphine ligand F is 96.7 percent.
Comparative example 3:
As shown in Table 2, the same operations were carried out except that triethanolamine was not added in place of the triethanolamine in example 9.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 97.8%, the selectivity for the linear product 1, 9-nonanal was 75.6%, the selectivity for the branched 2-methyl-1, 8-octadienal was 8.2%, the normal/isomer ratio was 9.2:1, the selectivity for the product having no terminal allylic aldehyde, i.e., 9-hydroxy-7-nonen-1-aldehyde, was 11.7%, and the selectivity for the other components and the high boiling products amounted to 4.5%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid was extracted with methylcyclohexane was 97.2%, the recovery rate of palladium atoms was 96.6%, and the recovery rate of the water-soluble phosphine ligand E was 95.3%.
Comparative example 4:
as shown in Table 2, the same operations were carried out except that the palladium compound was not added in place of example 9.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 96.2%, the selectivity for the linear product 1, 9-nonanal was 62.7%, the selectivity for the branched 2-methyl-1, 8-octadienal was 10.3%, the normal/isomer ratio was 6.1:1, the selectivity for the product of which the terminal allylic group did not form an aldehyde, i.e., 9-hydroxy-7-nonen-1-aldehyde, was 21.9%, and the selectivity for the other components and the high boiling products amounted to 5.1%.
The recovery rate of rhodium atoms in the aqueous phase after the hydroformylation reaction liquid is extracted by methylcyclohexane was 95.2%, and the recovery rate of the water-soluble phosphine ligand E was 93.8%.
Comparative example 5:
as shown in Table 2, the same operations were carried out except that the rhodium compound was not added instead of example 9.
After 3h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 36.5%, the selectivity for the linear product 1, 9-nonanal was 34.6%, the selectivity for the branched 2-methyl-1, 8-octadienal was 18.3%, the normal/isomer ratio was 1.9:1, the selectivity for the product in which the terminal allylic groups did not form an aldehyde, i.e., 9-hydroxy-7-nonen-1-al, was 13.7%, and the selectivity for the other components and high boiling products amounted to 33.4%.
The recovery rate of palladium atoms in the aqueous phase after the hydroformylation reaction liquid is extracted by methylcyclohexane was 92.2%, and the recovery rate of the water-soluble phosphine ligand E was 90.3%.
Table 2 summarizes the hydroformylation reaction results of examples 7-12 and comparative examples 3-5 and the recovery of rhodium, palladium and phosphorus. As can be seen from Table 2, the method of the present invention has good substrate applicability, can obtain long carbon chain dialdehyde products with high yields from C6 to C10, and can reuse Rh, pd and ligand with high recovery rate after extraction. Furthermore, as can be seen from example 9 and comparative examples 3 to 5, the addition of a small amount of palladium to the rhodium catalyst, the rh—pd bimetallic complex formed can exhibit a higher synergistic catalytic effect in catalyzing the hydroformylation reaction, can obtain a higher reaction selectivity and normal/heterogeneous ratio, and the above-mentioned advantageous synergistic effect cannot be obtained by adding only rhodium or palladium. Meanwhile, under the condition of adding a small amount of auxiliary agent organic tertiary amine, palladium can catalyze the terminal allyl in the raw material molecule to further isomerize into aldehyde, so that a long carbon chain dialdehyde product is obtained, and the beneficial effects can be achieved only by adding the palladium and the auxiliary agent of the organic tertiary amine at the same time.
Example 13
Step S1 hydroformylation reaction:
to a 100mL glass flask under nitrogen was added a flask containing Rh (acac) (CO) 2 135.4mg (rhodium atom 0.525 mmol) and Pd (OAc) 2 A catalyst F solution was prepared by adding 10g of a sulfolane solution of 11.8mg (palladium atom 0.053 mmol) and then adding 20g of an aqueous solution containing 8.72g (7.88 mmol) of ligand F and stirring at room temperature for 20 min.
80g of desalted water, 150g of sulfolane, 132.5g (1.05 mol) of 2, 7-octadien-1-ol and 2.65g of triethylamine were charged into a 500mL autoclave, and after 3 times of substitution with nitrogen, the autoclave was purged and pressurized to 2MPa with a mixed gas of hydrogen and carbon monoxide (molar ratio of hydrogen to carbon monoxide: 2:1) while stirring at 500rpm and raising the temperature to 80 ℃. Subsequently, the catalyst F solution prepared in advance was rapidly fed under pressure into the autoclave using a mixed gas of hydrogen and carbon monoxide (molar ratio of hydrogen to carbon monoxide: 2:1) and the total pressure was made 2.5MPa. The time after pressurized delivery of the catalyst a solution to the reaction vessel was defined as the start of the reaction. The ratio of phosphine ligand A to rhodium atom in the preparation of the catalyst A solution was 15:1, the ratio of palladium atom to rhodium atom was 0.1:1, the molar ratio of rhodium atom to raw material 2, 7-octadien-1-ol in the hydroformylation reaction was 0.0005:1, the mass ratio of triethylamine to raw material was 2wt%, and the water content in the aqueous solvent was 38.5wt%. For the hydroformylation reaction liquid after a certain period of reaction, quantitative analysis of the product was performed by gas chromatography. After 4h of reaction, the conversion of the starting 2, 7-octadien-1-ol was 98.7%, the selectivity of the product 1, 9-nonanal was 90.8%, the selectivity of 2-methyl-1, 8-octadienal was 5.8%, the normal/isomer ratio was 15.7:1, the selectivity of 9-hydroxy-7-nonen-1-al was 1.3%, and the selectivity of the other components and the high boiling products amounted to 2.1%.
TABLE 2 preparation of different dialdehydes telomerization and results
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Step S2, reaction liquid extraction:
the autoclave was cooled to 30℃and the reaction mixture was then pressure-fed under the action of the internal pressure of the autoclave into a pressure-resistant glass reaction vessel which was previously pressurized to 0.3MPa with a mixed gas of hydrogen and carbon monoxide (molar ratio 2:1). 400mL of cyclohexane was pumped into a glass reaction vessel, the temperature in the vessel was maintained at 30℃and stirred at a pressure of 0.3MPa for 20min. After stopping stirring, the reaction mixture was separated into oil-water phases, and after standing for 10min, the extraction layer (oil phase) was withdrawn through a pipe using internal pressure. The pressure-resistant glass reaction vessel containing the aqueous phase was kept at a pressure of 0.3MPa and a temperature of 30℃and 300mL of fresh cyclohexane was again added thereto, and the mixture was stirred under the same conditions for 10 minutes and then allowed to stand for 5 minutes. The upper extract layer was withdrawn from the autoclave and combined with the cyclohexane extract phase layer previously withdrawn, and finally 5mL of water was added to back-extract it, and the aqueous phase was incorporated into the pressure-resistant glass reaction vessel. The volume ratio of cyclohexane to the hydroformylation reaction liquid was 1.1:1.
The rhodium content, palladium content and phosphine ligand content contained in the aqueous phase are calculated by rhodium concentration, palladium concentration, phosphorus concentration and weight of the recovered aqueous phase, wherein the rhodium concentration, palladium concentration and phosphorus concentration are respectively quantitatively analyzed by an inductively coupled plasma mass spectrometer. The recovery rate of rhodium atoms in the aqueous phase after extraction was 98.9%, the recovery rate of palladium atoms was 98.4%, and the recovery rate of water-soluble phosphine ligand A was 97.6%.
Circulation of the aqueous phase containing the catalyst:
the catalyst-containing raffinate phase obtained in step S2 was recycled to the hydroformylation reaction step S1 for continuous hydroformylation and extraction for a total of 30 times. During this period, no catalyst and phosphine ligand were replenished and only 5g of sulfolane solvent was added to each raffinate layer. Table 3 shows the changes in conversion, selectivity and catalyst recovery for the reaction after every 5 catalyst cycles.
As can be seen from Table 3, the catalyst system of the present invention showed little significant change in the conversion of the reaction, the selectivity of each product, and the recovery rate of rhodium, palladium, and phosphine ligands in the aqueous phase, and the catalyst maintained high catalytic activity for a long period of time, in the course of 30 reactions and extraction operations. Meanwhile, the catalyst recovery is carried out by adopting the extraction separation process without adopting high-temperature rectification, so that the occurrence of metal precipitation and thermal degradation of the rhodium catalyst in the high-temperature rectification process is avoided, and the activity of the catalyst is further maintained for a long time. Therefore, the use cost of the catalyst is greatly reduced, the technical competitiveness is improved, and the method is very beneficial to the control of the industrialized cost.
Step S3, rectification and purification:
the 30 times extracted oil phase is rectified by using a packed rectifying tower with 20 theoretical plates at the normal pressure and the temperature of a tower kettle of 80-90 ℃, and light components including extractant cyclohexane, water, triethylamine and the like are mainly extracted. The oil phase in the tower bottom is distilled to obtain a small amount of material at 0.06KPaA and at the tower top temperature of 61-65 deg.c, most of 1, 9-nonanal is distilled to obtain a large amount of 1, 9-nonanal at the tower top temperature of 72-76 deg.c, the purity is 99.5% after gas chromatographic analysis, and the purity of 1, 9-nonanal is 86.2% after gas chromatographic analysis.
TABLE 3 catalyst set conditions
Industrial applicability
According to the method of the invention, dialdehydes can be produced industrially advantageously. For example, 1, 9-nonanediol and 2-methyl-1, 8-octanediol and 1, 9-azelaic acid are prepared by directly carrying out the hydroformylation reaction using 2, 7-octadien-1-ol as a raw material. The dialdehydes can be further used for producing 1, 9-nonanediol and 2-methyl-1, 8-octanediol, and are used for manufacturing long carbon polyester, polyurethane and the like; in addition, it can be converted into 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine by reaction with ammonia and hydrogen, and can be used for producing long carbon chain high temperature nylon, etc.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of dialdehyde is characterized in that: the method comprises the following steps:
s1: subjecting non-conjugated diolefin having alkenyl groups with carbon-carbon double bonds and allyl alcohol groups at each molecular end to hydroformylation with carbon monoxide and hydrogen in an aqueous phase under the action of a catalyst to generate a reaction mixture;
s2: extracting the reaction mixture obtained in the step S1, and recycling the raffinate water phase containing the catalyst obtained after the extraction to the hydroformylation reaction step S1;
s3: and (3) rectifying the extracted oil phase containing the dialdehyde obtained in the step (S2) at least twice to obtain a dialdehyde product.
2. A method of preparing a dialdehyde as claimed in claim 1, wherein: the catalyst in the step S1 consists of a ligand and at least one VIII transition metal compound, wherein the ligand comprises at least one compound selected from the general formula (I);
wherein:
R 1 、R 2 、R 3 、R 4 is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, COOR a 、COO - M + 、SO 3 R a 、SO 3 - M + 、NE 1 E 2 alkylene-NE 1 E 2 、NE 1 E 2 E 3+ X - Alkylene NE 1 E 2 E 3+ X - 、OR a 、SR a Any one of halogen, trifluoromethyl, nitro, acyl and cyano; r is R 1 、R 2 、R 3 、R 4 Are identical or different groups;
wherein R is a 、E 1 、E 2 And E is 3 R are identical or different radicals a 、E 1 、E 2 And E is 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl; m is M + Is a cation, X - Is an anion;
preferably M + Comprises Li + 、Na + 、K + Or a cation HN + F 1 F 2 F 3 Any one of, wherein F 1 、F 2 And F 3 Are identical or different radicals F 1 、F 2 And F 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl;
X - including any one of fluoride ion, chloride ion or bromide ion;
A 1 、A 2 o, S, siR of a shape of O, S, siR b R c 、NR d Or CR (CR) 5 R 6 Any one of A 1 、A 2 Are identical or different groups;
wherein R is b 、R c 、R d 、R 5 And R is 6 Each independently is any one of hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl;
R 7 、R 8 、R 9 、R 10 is any one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl or heteroaryl;
R 7 、R 8 、R 9 、R 10 the substituents on the two are the same or different;
preferably, R 7 、R 8 、R 9 、R 10 With one, two or three substituents, which are substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, COOR f 、COO - U + 、SO 3 - R f 、SO 3 U + 、NE 4 E 5 alkylene-NE 4 E 5 、NE 4 E 5 E 6+ V - Alkylene NE 4 E 5 E 6+ V - 、OR f 、SR f Any one of halogen, trifluoromethyl, nitro, acyl and cyano; u (U) + Is a cation, V - Is an anion;
preferably U + Comprises Li + 、Na + 、K + Or a cation HN + F 1 F 2 F 3 Any one of, wherein F 1 、F 2 And F 3 Are identical or different radicals F 1 、F 2 And F 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl;
V - including any one of fluoride ion, chloride ion or bromide ion;
wherein R is f 、E 4 、E 5 、E 6 Are identical or different radicals R f 、E 4 、E 5 、E 6 Is any one of hydrogen, alkyl, cycloalkyl or aryl.
3. A method of preparing a dialdehyde as claimed in claim 2, wherein: the VIII transition group metal element in the VIII transition group metal compound is selected from one or two of rhodium and palladium;
preferably, the VIII transition metal element in the VIII transition metal compound is rhodium or palladium, wherein the molar ratio of palladium atoms to rhodium atoms is (0.01-0.5): 1.
4. A method of preparing a dialdehyde as claimed in claim 2, wherein: the ligand is a compound of a general formula (I-1) or a general formula (I-2),
wherein:
R 1 、R 3 is hydrogen, C 1 -C 4 Alkyl, C 5 -C 8 Cycloalkyl, aryl, heteroaryl, OR a 、SR a Any one of halogen, trifluoromethyl, nitro, acyl and cyano, R 1 And R is 3 Are the same or different groups;
R a is hydrogenAny one of alkyl, cycloalkyl or aryl;
A 1 for O, S or CR 5 R 6 Any one of R 5 、R 6 Is hydrogen, C 1 -C 4 Any one of alkyl groups, R 5 、R 6 Are the same or different groups;
R 11 、R 12 、R 13 、R 14 is hydrogen, substituted or unsubstituted C 1 -C 4 Alkyl, substituted or unsubstituted C 5 -C 8 Any one of cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; r is R 11 、R 12 、R 13 、R 14 Are the same or different groups;
preferably, R 11 、R 12 、R 13 、R 14 With one, two or three substituents, including alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, COOR f 、COO - Y + 、SO 3 - R f 、SO 3 Y + 、NE 4 E 5 alkylene-NE 4 E 5 、NE 4 E 5 E 6+ Z - Alkylene NE 4 E 5 E 6+ Z - 、OR f 、SR f Any one of halogen, trifluoromethyl, nitro, acyl and cyano;
wherein R is f 、E 4 、E 5 And E is 6 Is the same or different and is selected from any one of hydrogen, alkyl, cycloalkyl or aryl respectively;
R 11 、R 12 、R 13 、R 14 the substituents on the two are the same or different;
Z - is an anion, Y + Is a cation, Y + Is Li + 、Na + 、K + Or a cation HN + F 1 F 2 F 3 Any one of, wherein F 1 、F 2 And F 3 Are the same or different groups and are used as the reactive groups,F 1 、F 2 and F 3 Is any one of hydrogen, alkyl, cycloalkyl or aryl;
preferably Z - Including any of fluoride, chloride, or bromide.
5. A method of preparing a dialdehyde as claimed in claim 1, wherein: the number of carbon atoms of the non-conjugated diene raw material with carbon-carbon double bond alkenyl and allyl alcohol groups at the tail end of each molecule in the step S1 is 6-12;
preferably, the non-conjugated diene comprises one of 2, 5-hexadien-1-ol, 2, 6-heptadien-1-ol, 2, 7-octadien-1-ol, 2, 8-nonadien-1-ol, 2, 9-decadien-1-ol.
6. A method of preparing a dialdehyde as claimed in claim 1, wherein: the hydroformylation reaction referred to in step S1 is carried out in an aqueous phase comprising a water-soluble solvent and water;
the water-soluble solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, acetone, tetrahydrofuran, dioxane, heptanone, sulfolane, polyethylene glycol and polyethylene glycol dimethyl ether; and/or
The water content of the aqueous phase is 25-60 wt%.
7. A process for the preparation of a dialdehyde as claimed in any one of claims 1 to 6, wherein: adding organic tertiary amine into the hydroformylation reaction in the step S1, wherein the added mass of the organic tertiary amine is 0.1-10wt% of the mass of the unconjugated diene;
Preferably, the organic tertiary amine comprises one or more of trialkylamine, trialkylalcohol amine, alicyclic tertiary amine, pyridine;
preferably, the reaction temperature of the hydroformylation reaction is 40 to 150 ℃, and the mixed gas H of hydrogen and carbon monoxide 2 The composition mole ratio of the catalyst to CO is 0.1-10, and the reaction pressure is 0.1-10 MPa。
8. The method for preparing dialdehyde as set forth in claim 7, wherein: said step S2 comprises extracting the reaction mixture obtained from step S1 with a saturated aliphatic hydrocarbon or a saturated alicyclic hydrocarbon and separating it into an extracted oil phase containing dialdehydes and a raffinate phase;
preferably, the saturated aliphatic hydrocarbon comprises at least one of n-pentane, n-hexane and n-octane;
preferably, the saturated alicyclic hydrocarbon comprises at least one of cyclopentane, cyclohexane, methylcyclohexane, decalin and ethers, wherein the ethers are selected from any one of dibutyl ether, diisopropyl ether, ethylphenyl ether and methyl tert-butyl ether;
preferably, the extraction separation in the step S2 is carried out in inert atmosphere, the extraction temperature is 20-80 ℃, and the extraction pressure is 0.1-5 MPa;
preferably, the inert atmosphere gas comprises one or more of helium, neon, argon, krypton, xenon or nitrogen.
9. A method of preparing a dialdehyde as claimed in claim 1, wherein: the product prepared by the method comprises one of straight-chain alkane dialdehyde and methyl alkane dialdehyde,
preferably, the straight chain alkanedialdehyde comprises one of 1, 7-heptanedioal, 1, 8-octanednal, 1, 9-nonanediol, 1, 10-decanedialdehyde, 1, 11-undecadipaldehyde;
preferably, the methylalkane dialdehyde comprises one of 2-methyl-1, 6-hexanedial, 2-methyl-1, 7-heptanedial, 2-methyl-1, 8-octanednal, 2-methyl-1, 9-nonanedial, 2-methyl-1, 10-decanedialdehyde.
10. Use of a process for the preparation of a dialdehyde as claimed in claims 1 to 9, characterized in that: the dialdehyde prepared by the preparation method can be applied to synthesis of dihydric alcohol, diamine and dibasic acid;
preferably, the dialdehyde prepared by the preparation method can be applied to preparing special nylon, long carbon chain polyester and essence and spice.
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