CN105523892A - Method for producing 1, 3-propanediol - Google Patents
Method for producing 1, 3-propanediol Download PDFInfo
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- CN105523892A CN105523892A CN201410573625.7A CN201410573625A CN105523892A CN 105523892 A CN105523892 A CN 105523892A CN 201410573625 A CN201410573625 A CN 201410573625A CN 105523892 A CN105523892 A CN 105523892A
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- hydroformylation
- acetoxyl group
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- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 title abstract 5
- 229940035437 1,3-propanediol Drugs 0.000 title abstract 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 title abstract 5
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010948 rhodium Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 18
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 15
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 15
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004480 active ingredient Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 92
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 88
- 229910052739 hydrogen Inorganic materials 0.000 claims description 63
- 239000001257 hydrogen Substances 0.000 claims description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 61
- 229920003023 plastic Polymers 0.000 claims description 42
- 239000004033 plastic Substances 0.000 claims description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 41
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 41
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 25
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010955 niobium Substances 0.000 claims description 15
- 229910052797 bismuth Inorganic materials 0.000 claims description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003284 rhodium compounds Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- DOUBAFNWVFAWEC-UHFFFAOYSA-N 3-hydroxypropyl acetate Chemical compound CC(=O)OCCCO DOUBAFNWVFAWEC-UHFFFAOYSA-N 0.000 abstract 2
- PRSPLAWXBFRHKV-UHFFFAOYSA-N 3-oxopropyl acetate Chemical compound CC(=O)OCCC=O PRSPLAWXBFRHKV-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 177
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 117
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 114
- 238000003756 stirring Methods 0.000 description 95
- 239000000463 material Substances 0.000 description 80
- 239000007789 gas Substances 0.000 description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 57
- 229910052786 argon Inorganic materials 0.000 description 57
- 239000010936 titanium Substances 0.000 description 57
- 229910052719 titanium Inorganic materials 0.000 description 57
- 238000010792 warming Methods 0.000 description 57
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 40
- 239000012530 fluid Substances 0.000 description 38
- 238000010438 heat treatment Methods 0.000 description 38
- 238000000746 purification Methods 0.000 description 38
- 230000002459 sustained effect Effects 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 229910000564 Raney nickel Inorganic materials 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 239000012071 phase Substances 0.000 description 20
- 239000011148 porous material Substances 0.000 description 20
- 206010013786 Dry skin Diseases 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 19
- 238000004090 dissolution Methods 0.000 description 19
- 238000005470 impregnation Methods 0.000 description 19
- 239000012535 impurity Substances 0.000 description 19
- 239000007791 liquid phase Substances 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- -1 sanitas Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZREIPSZUJIFJNP-UHFFFAOYSA-K bismuth subsalicylate Chemical compound C1=CC=C2O[Bi](O)OC(=O)C2=C1 ZREIPSZUJIFJNP-UHFFFAOYSA-K 0.000 description 2
- 229960000782 bismuth subsalicylate Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- MIJKIIBNAPRONL-UHFFFAOYSA-N acetic acid;neodymium Chemical compound [Nd].CC(O)=O MIJKIIBNAPRONL-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- LJFCDOMDEACIMM-UHFFFAOYSA-N zinc chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[Zn+2] LJFCDOMDEACIMM-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing 1, 3-propanediol. The method mainly solves the problem that the prior art for preparing 1, 3-propanediol through vinyl acetate hydroformylation, hydrogenation and hydrolysis has a low yield and low selectivity. The method provided through the invention comprises vinyl acetate hydroformylation for 3-acetoxypropanal preparation, 3-acetoxypropanal hydrogenation for 3-acetoxypropanol preparation and 3-acetoxypropanol alcoholysis for 1, 3-propanediol preparation. A hydroformylation catalyst utilizes SiO2, Al2O3 or their mixture as a carrier and active ingredients comprise rhodium and lanthanide metal elements and at least one of VA and VB metals. The method well solves the technical problem and can be used for 1, 3-propanediol industrial production.
Description
Technical field
The present invention relates to and produce 1,3-PD method used.
Background technology
1,3-PD (1.3-PDO) is a kind of important industrial chemicals, is mainly used in the synthesis of softening agent, washing composition, sanitas, emulsifying agent, also for industries such as food, makeup and pharmacy.Because it is a kind of important trevira monomer, its topmost purposes is as monomer and terephthalic acid synthesizing new polyester material one polytrimethylene terephthalate (PTT).
The preparation method of 1,3-PD has oxyethane single stage method, oxyethane two-step approach, acrolein hydration method, acetaldehyde stiasny method, vinylformic acid ester process, biological process, vinyl acetate between to for plastic hydroformylation etc.At present, the industrialized preparing process of 1.3-PDO is chemical synthesis, and world market is primarily of German Degussa company, shell Shell company of the U.S. and the monopolization of three, du pont company.Degussa company adopt be acrolein hydration hydrogenation method (AC method), Shell Co. Ltd adopt be oxirane carbonyl method (EO method), E.I.Du Pont Company adopt be oneself innovation thorugh biologic engineering method (MF method).Its ethylene oxide two-step process and acrolein hydration method technique are current prevailing technology.
Teaching in the patents such as patent US4072709 (ProductionofLacticAcid) utilizes vinyl-acetic ester for raw material; by adopting homogeneous phase rhodium compound to be catalyzer; by hydroformylation reaction, obtain 2 (or 3)-acetoxyl group propionic aldehyde.Be separated or be not separated, then 3-acetoxyl group propionic aldehyde obtains 1.3-PDO by hydrogenation and hydrolytic process.But all there is the problem that 1.3-PDO yield is low and selectivity is not high in aforesaid method in preparation 1.3-PDO process.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of 1,3-PD and selectivity are low, provides a kind of method that production 1,3-PD is newly used, and the method has the advantages that 1,3-PD yield is high and selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: produce 1, the method used of ammediol, comprise the following steps: (1) for raw material with vinyl acetate between to for plastic, carbon monoxide and hydrogen, is carried out hydroformylation reaction and obtained 3-acetoxyl group propionic aldehyde under hydroformylation catalyst and promotor exist; (2) in the presence of a hydrogenation catalyst, make hydrogen and 3-acetoxyl group propionic aldehyde react and obtain 3-acetoxyl group propyl alcohol; (3) alcoholysis of 3-acetoxyl group propyl alcohol obtains 1,3-PD; Wherein, described hydroformylation catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active ingredient comprises rhodium, lanthanide element and is selected from least one metallic element in VA and VB.Preferred described active ingredient comprises rhodium, lanthanide element, at least one metallic element that is selected from least one metallic element in VA and is selected from VB simultaneously.Now in the selectivity improving 1,3-PD and yield, there is synergy between the metallic element of VA and the metallic element of VB.
In technique scheme, at least one of described lanthanide element preferably in lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium.
In technique scheme, at least one of described VA metal preferably in antimony and bismuth.
In technique scheme, at least one of described VB metal preferably in vanadium, niobium and tantalum.
In technique scheme, as most preferred technical scheme, described active ingredient comprises rhodium metal element, lanthanide element, VA metallic element and VB metallic element simultaneously; Such as described active ingredient is made up of rhodium, cerium, antimony and vanadium, or is made up of rhodium, cerium, antimony, bismuth and vanadium, or is made up of rhodium, cerium, antimony, bismuth, vanadium and niobium, or is made up of rhodium, cerium, lanthanum, antimony, bismuth, vanadium and niobium.
In technique scheme, in described hydroformylation catalyst, the content of rhodium is preferably 3.00 ~ 15.00g/L, is more preferably 5.00 ~ 10.00g/L; In described hydroformylation catalyst, the content of lanthanide element is preferably 0.10 ~ 3.00g/L, is more preferably 0.50 ~ 3.00g/L; At least one content being selected from metal in VA and VB in described hydroformylation catalyst is preferably 0.10 ~ 5.00g/L, is more preferably 1.00 ~ 5.00g/L.Described hydroformylation catalyst carrier specific surface used is preferably 50 ~ 300m
2/ g, is more preferably 150 ~ 200m
2/ g, pore volume is preferably 0.80 ~ 1.20, is more preferably 0.90 ~ 1.00.. described promotor is preferably at least one in pyridine and triphenyl phosphorus.
Key of the present invention is the selection of hydroformylation catalyst, those skilled in the art will know that the proportioning determining suitable temperature of reaction, reaction times, reaction pressure and material how according to actual needs.But the temperature of hydroformylation reaction is preferably 50 ~ 180 DEG C in technique scheme; The pressure of reaction is preferably 1.0 ~ 15.0MPa; The time of reaction is preferably 1.0 ~ 15.0h.The mol ratio of carbon monoxide and hydrogen is preferably 0.10 ~ 10.0.
In technique scheme, described hydroformylation catalyst, the optional production method comprised the steps obtains:
The solution of metallic compound in rhodium compound, lanthanide element compound, VA and VB mixes with carrier by the composition 1. pressing catalyzer;
2. dry.
In technique scheme, step is at least one of described rhodium compound preferably in rhodium acetate, rhodium nitrate, rhodium chloride and rhodium sulfate 1.; Step is at least one of described lanthanide element compound preferably in lanthanum acetate, Lanthanum trichloride, lanthanum nitrate, cerous acetate, cerous nitrate, Cerium II Chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, Ytterbium trichloride, Europium trichloride and lutecium chloride 1.; At least one of step 1. in the preferred Bismuth Subcarbonate of described VA metallic compound, bismuth sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth subsalicylate, weisspiessglanz, antimony trisulfate and antimony chloride; Step is at least one of metallic compound preferably in vanadium trichloride, Vanadium Pentoxide in FLAKES, columbium pentachloride and tantalum pentachloride in described VB 1.; Step 2. described drying temperature is 80 ~ 120 DEG C, is more preferably 100 ~ 120 DEG C.
The preparation key of catalyzer of the present invention is the preparation of hydroformylation Primary Catalysts after obtaining Primary Catalysts, can obtain catalyzer of the present invention by making Primary Catalysts with described promotor contact.The mode that Primary Catalysts contacts with promotor is not particularly limited, and is also not particularly limited the opportunity of contact making both.Both such as can be made before catalyzer of the present invention is used for chemical reaction contact to form described catalyzer, and in the reaction system that both can also be made to apply at catalyzer of the present invention, contact makes catalyzer in-situ preparation.
The present invention synthesizes 1; in the method for ammediol; after step (1) terminates; separation can be carried out to the mixture of hydroformylation reaction to obtain target product 3-acetoxyl group propionic aldehyde and carry out step (2) again, also can step (1) generate 3-acetoxyl group propionic aldehyde after do not separate and directly carry out step (2).Those skilled in the art know the suitable hydrogenation catalyst of selection and determine suitable hydrogenation reaction temperature, time and material proportion.Conventional hydrogenation catalyst has the metal catalyst, metal oxide catalyst, metal sulfide catalyst, complex catalyst etc. of transition metal, such as platinum, palladium, nickel, ruthenium carried catalyst, cupric oxide-copper chromite, alumina-silica zinc-chromium oxide catalyst, nickel-molybdenum sulphide and RhCl [P (C
6h
5)
3].In the present invention, preferred Raney's nickel is as hydrogenation catalyst, and suitable hydrogenation temperature is preferably 30 ~ 100 DEG C; Hydrogenation reaction pressure preferably 0.5 ~ 8.0MPa; The hydrogenation reaction time is preferably 10 ~ 200min; The mol ratio of aldehyde and hydrogen preferably 0.10 ~ 2.0; Solvent preferably water, at least one in toluene.
After step (2) terminates, separation can be carried out to the mixture of hydrogenation reaction to obtain target product 3-acetoxyl group propyl alcohol and carry out step (3) again, also can step (2) generate 3-acetoxyl group propyl alcohol after do not separate and directly carry out step (3).Those skilled in the art know the suitable alcoholysis catalysts of selection and determine suitable alcoholysis reaction temperature, time and material proportion.But at least one in technique scheme in alcoholysis reaction in the preferred basic catalyst of alcoholysis catalysts and an acidic catalyst; At least one of the low-carbon (LC) saturated alcohol of the preferred C1 ~ C5 of the alcohol in alcoholysis reaction.Alcoholysis reaction catalyzer is more preferably dissolved in the sodium methylate of alcohol; Alcohol in alcoholysis reaction more preferably methyl alcohol.In technique scheme, alcoholysis reaction temperature is preferably 30 ~ 100 DEG C; Alcoholysis reaction pressure preferably 0 ~ 2.0MPa.
Final product of the present invention through cooling, decompression, be separated after adopt gas chromatograph-mass spectrometer (GC-MASS) to analyze, by the following transformation efficiency of formulae discovery vinyl acetate between to for plastic and the yield of 1,3-PD and selectivity:
Compared with prior art; key of the present invention is that the active ingredient of hydroformylation catalyst comprises rhodium, lanthanide element and is selected from least one metallic element in VA and VB; be conducive to the activity and the stability that improve hydroformylation catalyst; thus improve yield and the selectivity of 1,3-PD.
Experimental result shows; when adopting catalyzer of the present invention; 1; ammediol yield 75.42%, selectivity reaches 89.43%, achieves good technique effect; especially when in hydroformylation catalyst, active ingredient comprises rhodium, lanthanide element simultaneously, is selected from least one metallic element in VA and is selected from least one metallic element in VB; achieve more outstanding technique effect, can be used in the industrial production of 1,3-PD.Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLa with containing the RhCl of 3.10gSb
33H
2o, La (OAc)
35H
2o and Cl
3the abundant mixed dissolution of Sb is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L, Sb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.42%, and selectivity is 89.43%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 2]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLa with containing the RhCl of 3.10gNb
33H
2o, La (OAc)
35H
2o and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L, Nb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.38%, and selectivity is 89.47%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of hydroformylation Primary Catalysts: will 6.50gRh and the RhCl containing 2.40gLa be contained
33H
2o and La (OAc)
35H
2the abundant mixed dissolution of O, in pure water, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 65.33%, and selectivity is 81.67%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
By finding out compared with embodiment 1 ~ 2; the hydroformylation catalyst that the present invention adopts; use simultaneously more excellent than the performance only containing Rh and La active constituent catalyst containing Rh, La and Sb active ingredient, catalyst performance simultaneously containing Rh, La and Nb active ingredient; 1,3-PD selectivity and yield all want high.
[embodiment 3]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gCe with containing the Rh (OAc) of 3.10gSb
3, Ce (OAc)
36H
2o and Sb
2o
3abundant mixed dissolution is in 8wt% aqueous nitric acid in concentration, obtains steeping fluid 400ml, is 200m by 1.0L specific surface
2/ g, pore volume is 1.00, and diameter is the spherical Al of 5.6mm
2o
3carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 80 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Ce content 2.40g/L, Sb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.41%, and selectivity is 89.32%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 4]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gCe with containing the RhCl of 3.10gSb
33H
2o, CeCl
36H
2o and Sb
2(SO
4)
3abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 150m by 1.0L specific surface
2/ g, pore volume is 0.90, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 120 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Ce content 2.40g/L, Sb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.30%, and selectivity is 89.51%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 5]
The preparation of hydroformylation Primary Catalysts: by containing 5.00gRh, containing 0.50gCe with containing the Rh of 1.00gBi
2(SO
4)
315H
2o, Ce (NO
3)
36H
2o and (BiO)
2cO
30.5H
2the abundant mixed dissolution of O, in pure water, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 5.00g/L, Ce content 0.50g/L, Bi content 1.00g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 70.61%, and selectivity is 86.27%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 6]
The preparation of hydroformylation Primary Catalysts: by containing 10.00gRh, containing 3.00gPr with containing the RhCl of 5.00gBi
33H
2o, Pr (OAc)
35H
2o and BiCl
3abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 10.00g/L, Pr content 3.00g/L, Bi content 5.00g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 76.12%, and selectivity is 88.95%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 7]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gNd with containing the RhCl of 3.10gBi
33H
2o, Nd (OAc)
35H
2o and bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2o) fully mixed dissolution is in pure water, and obtaining steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Nd content 2.40g/L, Bi content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.34%, and selectivity is 89.40%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 8]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gYb with containing the RhCl of 3.10gBi
33H
2o, YbCl
36H
2o and bismuth subsalicylate (C
7h
5biO
4) fully mixed dissolution be in the aqueous hydrochloric acid of 8wt% in concentration, obtaining steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Yb content 2.40g/L, Bi content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.42%, and selectivity is 89.44%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 9]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gEu with containing the RhCl of 3.10gV
33H
2o, EuCl
36H
2o and VCl
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Eu content 2.40g/L, V content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.39%, and selectivity is 89.52%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 10]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLu with containing the RhCl of 3.10gV
33H
2o, LuCl
36H
2o and V
2o
5abundant mixed dissolution is in the aqueous nitric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Lu content 2.40g/L, V content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 0.2MPa after air; then carbon monoxide and hydrogen is passed into until pressure 1.0MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 50 DEG C; the mol ratio of hydrogen and carbon monoxide is 1:10; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 71.36%, and selectivity is 88.26%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 11]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gSm with containing the RhCl of 3.10gTa
33H
2o, SmCl
36H
2o and TaCl
5abundant mixed dissolution is in the aqueous sulfuric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Sm content 2.40g/L, Ta content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 15.0MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 180 DEG C; the mol ratio of hydrogen and carbon monoxide is 10:1; after sustained reaction 15.0h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.89%, and selectivity is 89.12%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 12]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLa, containing 1.70gSb with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, Cl
3sb and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L, Sb content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 76.60%, and selectivity is 90.58%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out, in the selectivity improving 1,3-PD and yield, in the catalyzer that the present invention uses, between VA metal Sb and VB metal Nb, to there is synergy on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2.
[embodiment 13]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gCe, containing 1.70gSb with containing the RhCl of 1.40gNb
33H
2o, CeCl
36H
2o, Cl
3sb and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Ce content 2.40g/L, Sb content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 76.72%, and selectivity is 90.67%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 14]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 1.70gSb with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 78.14%, and selectivity is 91.48%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out, in the selectivity improving 1,3-PD and yield, in the catalyzer that the present invention uses, in lanthanide series metal, between La and Ce, to there is synergy on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13.
[embodiment 15]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 1.70gBi with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2and NbCl O)
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Bi content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 78.05%, and selectivity is 91.54%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 16]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, containing 1.10gBi with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2and NbCl O)
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 79.27%, and selectivity is 92.46%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, in raising 1, the selectivity of ammediol and yield aspect, in the catalyzer that the present invention uses, between VA metal Sb, Bi, there is synergy, describe between Rh, La, Ce, Sb, Bi and Nb six kinds of active ingredients and there is well synergy.
[embodiment 17]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, containing 1.10gBi with containing the RhCl of 1.40gV
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2and VCl O)
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, V content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 79.23%, and selectivity is 92.53%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 18]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, containing 1.10gBi, containing 0.90gNb with containing the RhCl of 0.50gV
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2o), NbCl
5and VCl
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, Nb content 0.90g/L, V content 0.50g/L.。
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 80.40%, and selectivity is 93.31%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, in raising 1, the selectivity of ammediol and yield aspect, in the catalyzer that the present invention uses, between VB metal V, Nb, there is synergy, describe between Rh, La, Ce, Sb, Bi, Nb and V seven kinds of active ingredients and there is well synergy.
Table 1
Table 2 (continued)
Table 2 (Continued)
Claims (10)
1. produce ammediol method used, comprise the following steps: (1) for raw material with vinyl acetate between to for plastic, carbon monoxide and hydrogen, is carried out hydroformylation reaction and obtained 3-acetoxyl group propionic aldehyde under hydroformylation catalyst and promotor exist; (2) in the presence of a hydrogenation catalyst, make hydrogen and 3-acetoxyl group propionic aldehyde react and obtain 3-acetoxyl group propyl alcohol; (3) alcoholysis of 3-acetoxyl group propyl alcohol obtains 1.3-propylene glycol; Wherein, described hydroformylation catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active ingredient comprises rhodium, lanthanide element and is selected from least one metallic element in VA and VB.
2. method according to claim 1, is characterized in that described lanthanide element is selected from least one in lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium.
3. method according to claim 1, is characterized in that described VA metal is selected from least one in antimony and bismuth.
4. method according to claim 1, is characterized in that described VB metal is selected from least one in vanadium, niobium and tantalum.
5. method according to claim 1; it is characterized in that the content of rhodium in hydroformylation catalyst is: 3.00 ~ 15.00g/L; the content of lanthanide element is: 0.10 ~ 3.00g/L, and at least one content being selected from metal in VA and VB described in hydroformylation catalyst is 0.10 ~ 5.00g/L.
6. method according to claim 1, is characterized in that hydroformylation step (1) described promotor is selected from least one in pyridine and triphenyl phosphorus.
7. method according to claim 1, is characterized in that the temperature of step (1) hydroformylation reaction is 50 ~ 180 DEG C.
8. method according to claim 1, is characterized in that the preparation method of described hydroformylation catalyst, comprises the steps:
The solution of metallic compound in rhodium compound, lanthanide element compound, VA and VB mixes with carrier by the composition 1. pressing catalyzer;
2. dry.
9. method according to claim 1, is characterized in that step (3) alcoholysis catalysts is selected from least one in basic catalyst and an acidic catalyst.
10. method according to claim 1, is characterized in that the alcohol in step (3) alcoholysis reaction is selected from least one of the low-carbon (LC) saturated alcohol of C1 ~ C5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665939A (en) * | 2017-10-17 | 2019-04-23 | 中国科学院上海高等研究院 | A kind of method that propyl alcohol prepares 1,3-PD |
| CN111533767A (en) * | 2020-04-30 | 2020-08-14 | 卢海元 | Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol |
| CN114522739A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Method for preparing 1, 3-propylene glycol from vinyl acetate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
| CN101116816A (en) * | 2007-07-03 | 2008-02-06 | 中国石油大学(华东) | Preparation method of supported rhodium catalyst for high carbon olefin hydroformylation to produce high carbon aldehyde |
| WO2011075905A1 (en) * | 2009-12-25 | 2011-06-30 | Chen Xiaozhou | Methods for preparing ester of 1,3-propylene glycol and 1,3- propylene glycol |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
| CN102458651A (en) * | 2009-04-21 | 2012-05-16 | 陶氏技术投资有限公司 | Rhenium-promoted epoxidation catalysts and methods of making and using them |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
-
2014
- 2014-10-24 CN CN201410573625.7A patent/CN105523892B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
| CN101116816A (en) * | 2007-07-03 | 2008-02-06 | 中国石油大学(华东) | Preparation method of supported rhodium catalyst for high carbon olefin hydroformylation to produce high carbon aldehyde |
| CN102458651A (en) * | 2009-04-21 | 2012-05-16 | 陶氏技术投资有限公司 | Rhenium-promoted epoxidation catalysts and methods of making and using them |
| WO2011075905A1 (en) * | 2009-12-25 | 2011-06-30 | Chen Xiaozhou | Methods for preparing ester of 1,3-propylene glycol and 1,3- propylene glycol |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665939A (en) * | 2017-10-17 | 2019-04-23 | 中国科学院上海高等研究院 | A kind of method that propyl alcohol prepares 1,3-PD |
| CN111533767A (en) * | 2020-04-30 | 2020-08-14 | 卢海元 | Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol |
| CN114522739A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Method for preparing 1, 3-propylene glycol from vinyl acetate |
| CN114522739B (en) * | 2020-11-23 | 2023-10-20 | 中国科学院大连化学物理研究所 | Method for preparing 1, 3-propylene glycol from vinyl acetate |
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