CN105521780B - 3 acetoxyl group propionic aldehyde catalyst - Google Patents
3 acetoxyl group propionic aldehyde catalyst Download PDFInfo
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- CN105521780B CN105521780B CN201410575053.6A CN201410575053A CN105521780B CN 105521780 B CN105521780 B CN 105521780B CN 201410575053 A CN201410575053 A CN 201410575053A CN 105521780 B CN105521780 B CN 105521780B
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- Prior art keywords
- catalyst
- propionic aldehyde
- acetoxyl group
- group propionic
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- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- -1 acetoxyl group Chemical group 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 44
- 239000010948 rhodium Substances 0.000 claims description 42
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011572 manganese Substances 0.000 claims description 23
- 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 22
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052797 bismuth Inorganic materials 0.000 claims description 14
- 229910052792 caesium Inorganic materials 0.000 claims description 14
- 229910052702 rhenium Inorganic materials 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 111
- 238000002360 preparation method Methods 0.000 description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- 238000004458 analytical method Methods 0.000 description 42
- 238000002803 maceration Methods 0.000 description 40
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- 238000001816 cooling Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- 238000000926 separation method Methods 0.000 description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 21
- 230000006837 decompression Effects 0.000 description 21
- 238000001035 drying Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 21
- 239000007791 liquid phase Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 21
- 239000011148 porous material Substances 0.000 description 21
- 239000000376 reactant Substances 0.000 description 21
- 230000002459 sustained effect Effects 0.000 description 21
- 239000010936 titanium Substances 0.000 description 21
- 229910052719 titanium Inorganic materials 0.000 description 21
- 238000010792 warming Methods 0.000 description 21
- 206010013786 Dry skin Diseases 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 10
- 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 10
- 229910002785 ReO3 Inorganic materials 0.000 description 9
- ZREIPSZUJIFJNP-UHFFFAOYSA-K bismuth subsalicylate Chemical compound C1=CC=C2O[Bi](O)OC(=O)C2=C1 ZREIPSZUJIFJNP-UHFFFAOYSA-K 0.000 description 9
- 229960000782 bismuth subsalicylate Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007037 hydroformylation reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 150000002924 oxiranes Chemical class 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- SYBXSZMNKDOUCA-UHFFFAOYSA-J rhodium(2+);tetraacetate Chemical compound [Rh+2].[Rh+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O SYBXSZMNKDOUCA-UHFFFAOYSA-J 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- VTSCAPDXKUEDTQ-UHFFFAOYSA-N [Cl].[Rh].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl].[Rh].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 VTSCAPDXKUEDTQ-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 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
- 238000011953 bioanalysis Methods 0.000 description 1
- QSBNOZODKXUXSP-UHFFFAOYSA-K bismuth;azane;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound N.[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QSBNOZODKXUXSP-UHFFFAOYSA-K 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 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
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical group [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 1
- 150000003284 rhodium compounds Chemical class 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
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 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 1
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to 3 acetoxyl group propionic aldehyde catalyst, mainly solve the problems, such as that 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low in the prior art, by using 3 acetoxyl group propionic aldehyde catalyst, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes at least one, the technical scheme selected from least one of alkali metal and selected from least one of VIIB and VA metals metallic element selected from platinum cluster metallic element, the technical problem is preferably resolved, in the industrial production available for 1.3 propane diols.
Description
Technical field
The present invention relates to 3- acetoxyl group propionic aldehyde catalyst, the preparation method and 3- acetoxyl group propionic aldehyde of the catalyst
Synthetic method.
Background technology
1.3- propane diols (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, detergent, preservative,
The synthesis of emulsifying agent, it is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its
Most important purposes is as monomer and the polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material one.
The preparation method of 1.3- propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde
Stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc..At present, 1.3-PDO industrialized preparing process
For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and du pont company three
Family's monopolization.Degussa companies are using acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd using oxirane carbonyl
The thorugh biologic engineering method (MF methods) that change method (EO methods), E.I.Du Pont Company innovate using oneself.Its ethylene oxide two-step process
It is current prevailing technology with acrolein hydration method technique.
It is well known that there is a carbon-carbon double bond in vinyl acetate, hydroformylation reaction can occur for the key, the one of double bond
An aldehyde radical is added on individual carbon atom, generates the isomer of acetoxyl group propionic aldehyde.The aldehyde can become hydroxyl by hydrogenation
Base, ester group can be become hydroxyl by hydrolysis and form glycol, and such vinyl acetate is by hydroformylation, hydrogenation and hydrolysis can
Prepare 1.3- propane diols.
Taught in the patents such as patent US4072709 (Production of lactic acid) and utilize vinyl acetate
It is catalyst by using homogeneous rhodium compound or propionate is raw material, by hydroformylation reaction, obtains α-acetyl oxygen
Base propionic aldehyde or α-propionyloxy propionic aldehyde.Whether separation or not, then obtains 1.3-PDO by hydrogenation and hydrolytic process, or
Oxidation and hydrolysis obtain lactic acid.But there are 3- acetoxyl groups propionic aldehyde receipts in the above method during 3- acetoxyl group propionic aldehyde is prepared
The problem of rate is low and selective not high.
The content of the invention
The problem of one of technical problems to be solved by the invention are that 3- acetoxyl group propionic aldehyde yields are low and selectivity is low, carries
For a kind of catalyst for the synthesis of 3- acetoxyl groups propionic aldehyde, the catalyst has 3- acetoxyl group propionic aldehyde high incomes to 3- acetyl
The characteristics of epoxide propionic aldehyde is selectively high.
The two of the technical problems to be solved by the invention are the producers using one of the above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are the 3- acetyl using one of the above-mentioned technical problem catalyst
The synthetic method of epoxide propionic aldehyde.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：3- acetoxyl groups propionic aldehyde is catalyzed
Agent, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component is included selected from platinum cluster metallic element extremely
Lack one kind, selected from least one of alkali metal and selected from least one of VIIB and VA metallic element.It is preferred that institute
State active component while including platinum cluster metallic element, alkali metal, selected from least one of VIIB metallic elements and be selected from
At least one of VA metals metallic element.Now 3- acetyl is being improved between the metallic element in VIIB metallic element and VA
There is synergy in terms of epoxide propionic aldehyde selectivity and yield.
In above-mentioned technical proposal, the platinum cluster metallic element preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium.
In above-mentioned technical proposal, the alkali metal preferably is selected from least one of lithium, sodium, potassium, rubidium and caesium..
In above-mentioned technical proposal, the VIIB metals preferably are selected from least one of manganese and rhenium.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, as most preferred technical scheme, the active component simultaneously including platinum cluster metallic element,
Alkali metal, VIIB metallic elements and VA metallic elements；Such as the active component is made up of rhodium, caesium, rhenium and bismuth (or antimony),
Either it is made up of rhodium, caesium, rhenium (or manganese), bismuth and antimony or is made up of rhodium, caesium (or potassium), rhenium, manganese, bismuth and antimony, or by rhodium
(or ruthenium), caesium, potassium, rhenium, manganese, bismuth and antimony composition.The most the preferably active component is by rhodium, ruthenium, caesium, potassium, rhenium, manganese, bismuth and antimony
Composition.
In above-mentioned technical proposal, the content of platinum cluster metallic element is preferably 3.00~15.00g/L in the catalyst, more
Preferably 5.00~10.00g/L；The content of alkali metal is preferably 0.10~3.00g/L in the catalyst, more preferably
0.50~3.00g/L；In the catalyst selected from VIIB and VA at least one content of metal be preferably 0.10~
5.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the catalyst is preferably 50~300m2/ g, more
Preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The production method of catalyst described in case, comprises the following steps：
1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of alkali metal, VIIB and VA
The solution of the compound of metallic element mixes with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. platinum cluster metallic element preferably is selected from radium chloride, rhodium acetate two is matched somebody with somebody
Body, triphenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, the ammonia palladium of dichloro four, palladium, ammonium chloropalladite, ruthenic chloride, cross ruthenic acid four in
At least one of amine, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid；Step 1. institute
State alkali metal compound and preferably be selected from alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metal sulfates and alkali gold
Belong at least one of acetate；The compound of step 1. VIIB metallic elements has selected from manganese acetate, manganese chloride, sulfuric acid
At least one of manganese, methyl rhenium trioxide and ammonium perrhenate；The compound of step 1. VA metallic elements preferably is selected from chlorination
At least one of antimony, antimony sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth nitrate and bismuth sulfate.2. the drying temperature is 80 to step
~120 DEG C, more preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of 3- acetoxyl group propionic aldehyde,
Using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, appoint in the technical scheme of one of above-mentioned technical problem
Reaction generation 3- acetoxyl group propionic aldehyde in the presence of one catalyst and accelerator.The preferred pyridine of the accelerator and triphenyl
At least one of phosphorus.
The key of the present invention is the selection of catalyst, and skilled person will know how suitable according to determination is actually needed
Reaction temperature, the reaction time, the proportioning of reaction pressure and material.But the temperature reacted in above-mentioned technical proposal is preferably
50~180 DEG C；The pressure of reaction is preferably 1.0~15.0MPa；The time of reaction is preferably 1.0~15.0h.Carbon monoxide with
The mol ratio of hydrogen is preferably 0.10~10.0.
Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the conversion ratio of vinyl acetate and the yield and selectivity of 3- acetoxyl group propionic aldehyde：
Compared with prior art, key of the invention is that the active component of catalyst includes platinum cluster metallic element, alkali gold
Belong to element and selected from least one of VIIB and VA metallic element, be advantageous to improve the activity and stability of major catalyst, from
And improve the yield and selectivity of 3- acetoxyl group propionic aldehyde.
Test result indicates that during using catalyst of the present invention, 3- acetoxyl group propionic aldehyde yield 84.78%, selectively reach
94.69%, achieve active component in preferable technique effect, especially catalyst while include platinum cluster metallic element, alkali gold
Belong to element, selected from least one of VIIB metallic elements and selected from least one of VA metallic elements when, achieve more
Prominent technique effect, in the industrial production available for 1.3- propane diols.The present invention is further explained below by embodiment
State.
Embodiment
【Embodiment 1】
The preparation of catalyst：By the part (Rh of rhodium acetate two containing 6.20gRh, containing 2.00gCs and containing 2.80gRe2
(OAc)4), CsCl and methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3) be sufficiently mixed and be dissolved in pure water, impregnated
Liquid 400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned leaching
In stain liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs
Content 2.00g/L, Re content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.78%, and selectivity is 94.69%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 2】
The preparation of catalyst：By the part (Rh of rhodium acetate two containing 6.20gRh, containing 2.00gCs and containing 2.80gBi2
(OAc)4), CsCl and bismuth subsalicylate (C7H5BiO4) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, by 1.0L
It is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs content 2.00g/L,
Bi contents 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.71%, and selectivity is 94.57%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By the part (Rh of rhodium acetate two containing 6.20gRh and containing 2.00gCs2(OAc)4) and CsCl it is abundant
Mixed dissolution obtains maceration extract 400ml in pure water, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm
Spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Should through ICP measure
The Rh contents of catalyst are 6.20g/L, Cs contents 2.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 72.18%, and selectivity is 85.16%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, Cs and Re work
Property component and meanwhile performance of the catalyst performance ratio containing only Rh and Cs active constituent catalysts containing Rh, Cs and Bi active component will
More excellent, the selectivity and yield of 3- acetoxyl group propionic aldehyde will be high.
【Embodiment 3】
The preparation of catalyst：By the RhCl containing 5.00gRh, containing 0.50gLi and containing 1.00gRe3·6H2O, LiCl and excessively rhenium
Sour ammonium (H4NO4Re) it is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 200m by 1.0L2/ g, pore volume are
1.00, a diameter of 5.6mm spherical Al2O3Carrier impregnation stands 3h in 80 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Li contents 0.50g/L, Re content 1.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 79.62%, and selectivity is 92.79%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 4】
The preparation of catalyst：By the Rh containing 10.00gRh, containing 3.00gNa and containing 5.00gMn2(SO4)3·15H2O、Na2O and
MnSO4·H2O, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into surface
For 150m2/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 120 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 10.00g/L, Na contents 3.00g/L, Mn content
5.00g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.74%, and selectivity is 94.13%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 5】
The preparation of catalyst：By the Rh (NO containing 6.20gRh, containing 2.00gK and containing 2.80gMn3)3、K2SO4And MnCl2·
4H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume 0.94, diameter
For 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Rh contents that ICP determines the catalyst are 6.20g/L, K contents 2.00g/L, Mn content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.73%, and selectivity is 94.62%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 6】
The preparation of catalyst：By the ammonia palladium (Pd (NH of dichloro four containing 6.20gPd, containing 2.00gRb and containing 2.80gMn3)4Cl2·H2O)、RbNO3With Mn (OAc)2·4H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Pd contents that the catalyst is determined through ICP are 6.20g/L, Rb contents 2.00g/L, Mn content
2.80g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.30%, and selectivity is 94.34%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 7】
The preparation of catalyst：By the Pd (OAc) containing 6.20gPd, containing 2.00gCs and containing 2.80gBi2, CsCl and citric acid
Bismuth ammonium (Bi (NH3)2C6H7O7·H2O) it is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract 400ml, will
1.0L is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is quiet in above-mentioned maceration extract
3h is put in 100 DEG C of dryings, obtains the catalyst.The Pd contents that the catalyst is determined through ICP are 6.20g/L, Cs contents
2.00g/L, Bi content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.26%, and selectivity is 94.31%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 8】
The preparation of catalyst：By the RuCl containing 6.20gRu, containing 2.00gCs and containing 2.80gBi3·XH2O, CsCl and BiCl3
It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume
For 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract
Catalyst.The Ru contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Bi content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.10%, and selectivity is 94.72%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 9】
The preparation of catalyst：By the ammonium chloroplatinite ((NH containing 6.20gPt, containing 2.00gCs and containing 2.80gBi4)2PtCl4), CsCl and Bi2(SO4)3It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L
It is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The Pt contents that the catalyst is determined through ICP are 6.20g/L, Cs content 2.00g/L,
Bi contents 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.16%, and selectivity is 94.57%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 10】
The preparation of catalyst：By the OsCl containing 6.20gOs, containing 2.00gCs and containing 2.80gSb3·3H2O, CsCl and Sb2
(SO4)3It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g,
Pore volume is 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
The catalyst.The Os contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Sb content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 0.2MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 1.0MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:After 10, sustained response 1.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 78.58%, and selectivity is 93.33%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 11】
The preparation of catalyst：By the IrCl containing 6.20gIr, containing 2.00gCs and containing 2.80gSb3·XH2O, CsCl and Cl3Sb
It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtain maceration extract 400ml, than surface is 168m by 1.0L2/
G, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.The Ir contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Sb content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 15.0MPa
Degree, controlling reaction temperature are 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.90%, and selectivity is 94.36%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 12】
The preparation of catalyst：By the part of rhodium acetate two containing 6.20gRh, containing 2.00gCs, containing 1.30gRe and containing 1.50gBi
(Rh2(OAc)4), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3) and bismuth subsalicylate (C7H5BiO4) fully
Mixed dissolution obtains maceration extract 400ml in pure water, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm
Spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Should through ICP measure
The Rh contents of catalyst are 6.20g/L, Cs contents 2.00g/L, Re content 1.30g/L, Bi content 1.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 86.02%, and selectivity is 95.87%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 2, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, in the catalyst that the present invention uses, there is synergy between VIIB metal Re and VA metals Bi.【Embodiment 13】
The preparation of catalyst：By the part of rhodium acetate two containing 6.20gRh, containing 2.00gCs, containing 1.30gRe and containing 1.50gSb
(Rh2(OAc)4), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3) and Cl3Sb, which is sufficiently mixed, to be dissolved in concentration and is
In 8wt% aqueous hydrochloric acid solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Rh contents for determining the catalyst are 6.20g/L, Cs contents 2.00g/L, Re content 1.30g/L, Sb content 1.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.91%, and selectivity is 95.89%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 14】
The preparation of catalyst：By the vinegar containing 6.20gRh, containing 2.00gCs, containing 1.30gRe, containing 0.95gBi and containing 0.55gSb
Sour part (the Rh of rhodium two2(OAc)4), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3), bismuth subsalicylate
(C7H5BiO4) and Cl3Sb, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, will
1.0L is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is quiet in above-mentioned maceration extract
3h is put in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs contents
2.00g/L, Re content 1.30g/L, Bi content 0.95g/L, Sb content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 86.83%, and selectivity is 96.34%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that the present invention uses, there is synergy in VA metals between Bi and Sb.Illustrate Rh, Cs,
Synergy well between five kinds of active components of Re, Bi and Sb be present.
【Embodiment 15】
The preparation of catalyst：By the vinegar containing 6.20gRh, containing 2.00gCs, containing 1.30gMn, containing 0.95gBi and containing 0.55gSb
Sour part (the Rh of rhodium two2(OAc)4)、CsCl、Mn(OAc)2·4H2O, bismuth subsalicylate (C7H5BiO4) and Cl3Sb is sufficiently mixed molten
Solution obtains maceration extract 400ml in the aqueous hydrochloric acid solution that concentration is 8wt%, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Mn content 1.30g/L, Bi content
0.95g/L, Sb content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 86.92%, and selectivity is 96.29%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 16】
The preparation of catalyst：To contain 6.20gRh, containing 2.00gCs, containing 0.80gRe, containing 0.50gMn, containing 0.95gBi and contain
0.55gSb part (the Rh of rhodium acetate two2(OAc)4), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3)、Mn
(OAc)2·4H2O, bismuth subsalicylate (C7H5BiO4) and Cl3Sb is sufficiently mixed the aqueous hydrochloric acid solution for being dissolved in that concentration is 8wt%
In, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier
It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents of the catalyst are determined through ICP
For 6.20g/L, Cs contents 2.00g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content
0.55g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 87.74%, and selectivity is 97.41%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between VIIB metals Re, Mn, illustrate Rh, Cs, Re,
Synergy well between six kinds of active components of Mn, Bi and Sb be present.
【Embodiment 17】
The preparation of catalyst：To contain 6.20gRh, containing 2.00gK, containing 0.80gRe, containing 0.50gMn, containing 0.95gBi and contain
0.55gSb part (the Rh of rhodium acetate two2(OAc)4)、K2SO4, methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3)、Mn
(OAc)2·4H2O, bismuth subsalicylate (C7H5BiO4) and Cl3Sb is sufficiently mixed the aqueous hydrochloric acid solution for being dissolved in that concentration is 8wt%
In, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier
It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents of the catalyst are determined through ICP
For 6.20g/L, K contents 2.00g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content 0.55g/
L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 87.58%, and selectivity is 97.56%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 18】
The preparation of catalyst：To contain 6.20gRh, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, containing 0.50gMn, contain
The 0.95gBi and part (Rh of rhodium acetate two containing 0.55gSb2(OAc)4)、CsCl、K2SO4, methyl rhenium trioxide (abbreviation MTO, point
Minor CH3ReO3)、Mn(OAc)2·4H2O, bismuth subsalicylate (C7H5BiO4) and Cl3It is 8wt% that Sb, which is sufficiently mixed and is dissolved in concentration,
Aqueous hydrochloric acid solution in, obtain maceration extract 400ml, than surface be 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm's
Spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.This is determined through ICP to urge
The Rh contents of agent are 6.20g/L, Cs contents 1.55g/L, K content 0.45g/L, Re content 0.80g/L, Mn content 0.50g/L,
Bi contents 0.95g/L, Sb content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.49%, and selectivity is 98.65%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between alkali metal Cs, K, illustrate Rh, Cs, K, Re,
Synergy well between seven kinds of active components of Mn, Bi and Sb be present.
【Embodiment 19】
The preparation of catalyst：To contain 6.20gRu, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, containing 0.50gMn, contain
The 0.95gBi and RuCl containing 0.55gSb3·XH2O、CsCl、K2SO4, methyl rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3)、
Mn(OAc)2·4H2O, bismuth subsalicylate (C7H5BiO4) and Cl3Sb is sufficiently mixed the aqueous hydrochloric acid solution for being dissolved in that concentration is 8wt%
In, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier
It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Ru contents of the catalyst are determined through ICP
For 6.20g/L, Cs contents 1.55g/L, K content 0.45g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/
L, Sb content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.25%, and selectivity is 98.67%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 20】
The preparation of catalyst：To contain 5.00gRh, containing 1.20gRu, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, contain
0.50gMn, the part (Rh of rhodium acetate two containing 0.95gBi and containing 0.55gSb2(OAc)4)、RuCl3·XH2O、CsCl、K2SO4, first
Base rhenium trioxide (abbreviation MTO, molecular formula CH3ReO3)、Mn(OAc)2·4H2O, bismuth subsalicylate (C7H5BiO4) and Cl3Sb is abundant
Mixed dissolution obtains maceration extract 400ml in the aqueous hydrochloric acid solution that concentration is 8wt%, than surface is 168m by 1.0L2/ g, hole
Hold for 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Ru contents 1.20g/L, Cs content 1.55g/L, K content
0.45g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.96%, and selectivity is 99.14%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 20 and embodiment 18 and embodiment 19, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between platinum cluster metal Rh, Ru, illustrate Rh, Ru, Cs,
K, synergy well between eight kinds of active components of Re, Mn, Bi and Sb be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (8)
1.3- acetoxyl group propionic aldehyde catalyst, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component
At least one including at least one selected from platinum group, selected from least one of alkali metal, in VIIB
Kind of at least one of metallic element and VA metallic element, the content of platinum group is 3.00~15.00g/ in catalyst
L, the content of alkali metal is 0.10~3.00g/L, at least one and VA selected from metal in VIIB described in catalyst
At least one content of metal is 0.10~5.00g/L.
2. catalyst according to claim 1, it is characterised in that the platinum group metal is in platinum, palladium, osmium, iridium, ruthenium and rhodium
At least one.
3. catalyst according to claim 1, it is characterised in that the alkali metal is in lithium, sodium, potassium, rubidium and caesium
It is at least one.
4. catalyst according to claim 1, it is characterised in that the VIIB metals are selected from least one of manganese and rhenium.
5. catalyst according to claim 1, it is characterised in that the VA metals are selected from least one of antimony and bismuth.
6. as the production method of the catalyst described in claim 1, comprise the following steps：
1. by the composition of catalyst by the compound of platinum group, the compound of alkali metal, VIIB and VA metals
The solution of the compound of metallic element mixes with carrier；
2. dry.
The synthetic method of 7.3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent,
3- acetoxyl group propionic aldehyde is synthesized in the presence of catalyst any one of Claims 1 to 5 and accelerator.
8. synthetic method according to claim 7, it is characterised in that the accelerator is in pyridine and triphenyl phosphorus
It is at least one.
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