CN105498785A - Catalyst for synthesis of 3-acetoxy propionaldehyde - Google Patents
Catalyst for synthesis of 3-acetoxy propionaldehyde Download PDFInfo
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- CN105498785A CN105498785A CN201410498364.7A CN201410498364A CN105498785A CN 105498785 A CN105498785 A CN 105498785A CN 201410498364 A CN201410498364 A CN 201410498364A CN 105498785 A CN105498785 A CN 105498785A
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- China
- Prior art keywords
- catalyst
- acetoxyl group
- content
- propionic aldehyde
- group propionic
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 152
- 238000003786 synthesis reaction Methods 0.000 title abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 24
- PRSPLAWXBFRHKV-UHFFFAOYSA-N 3-oxopropyl acetate Chemical compound CC(=O)OCCC=O PRSPLAWXBFRHKV-UHFFFAOYSA-N 0.000 title abstract 5
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 150000002505 iron Chemical class 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 184
- 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
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 28
- 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 23
- 239000010931 gold Substances 0.000 claims description 19
- 229910052797 bismuth Inorganic materials 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 229910052701 rubidium Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 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
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 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 90
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 48
- 239000000463 material Substances 0.000 description 45
- -1 polytrimethylene terephthalate Polymers 0.000 description 45
- 238000002360 preparation method Methods 0.000 description 44
- 239000007789 gas Substances 0.000 description 43
- 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 42
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 32
- 238000000034 method Methods 0.000 description 27
- 239000011148 porous material Substances 0.000 description 22
- 206010013786 Dry skin Diseases 0.000 description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 21
- 238000004090 dissolution Methods 0.000 description 21
- 238000001035 drying Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 21
- 239000007791 liquid phase Substances 0.000 description 21
- 238000002156 mixing Methods 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
- ZREIPSZUJIFJNP-UHFFFAOYSA-K bismuth subsalicylate Chemical compound C1=CC=C2O[Bi](O)OC(=O)C2=C1 ZREIPSZUJIFJNP-UHFFFAOYSA-K 0.000 description 10
- 229960000782 bismuth subsalicylate Drugs 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 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
- 238000007037 hydroformylation reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 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
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 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 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 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
- 229910000410 antimony oxide Inorganic materials 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
- 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
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-ZVGUSBNCSA-L copper;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O RSJOBNMOMQFPKQ-ZVGUSBNCSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 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
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 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
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 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
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesis of 3-acetoxy propionaldehyde, and mainly solves the problems of low activity and selectivity of 3-acetoxy propionaldehyde catalyst in the prior art. According to a technical scheme, the 3-acetoxy propionaldehyde catalyst adopts SiO2, Al2O3 or a mixture thereof as the carrier, the active component includes at least one of iron series elements, an alkali metal element and at least one metal element selected from VA and IB, thus welling solving the problems. The 3-acetoxy propionaldehyde catalyst can be used for the industrial production of 1.3-propanediol.
Description
Technical field
The present invention relates to 3-acetoxyl group propionic aldehyde and synthesize catalyst used, the production method of described catalyst and the synthetic method of 3-acetoxyl group propionic aldehyde.
Background technology
1.3-propane diols (1.3-PDO) is a kind of important industrial chemicals, is mainly used in the synthesis of plasticizer, washing agent, anticorrisive agent, emulsifying agent, also for industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its topmost purposes is as monomer and terephthalic acid (TPA) synthesizing new polyester material one polytrimethylene terephthalate (PTT).
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, the industrialized preparing process of 1.3-PDO is chemical synthesis, and international 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.
As everyone knows, having a carbon-carbon double bond in vinyl acetate, can there is hydroformylation reaction in this key, a carbon atom of double bond adds an aldehyde radical, generates the isomer of acetoxyl group propionic aldehyde.This aldehyde can become hydroxyl by hydrogenation, and ester group can become hydroxyl by hydrolysis and form glycol, and such vinyl acetate just can prepare 1.3-propane diols through hydroformylation, hydrogenation and hydrolysis.
Teaching in the patents such as patent US4072709 (Productionoflacticacid) utilizes vinyl acetate or propionate to be raw material; by adopting homogeneous phase rhodium compound to be catalyst; by hydroformylation reaction, obtain α-acetoxyl group propionic aldehyde or α-propionyloxy propionic aldehyde.Be separated or be not separated, then obtain 1.3-PDO by hydrogenation and hydrolytic process, or oxidation and hydrolysis obtain lactic acid.But all there is the low and selective not high problem of 3-acetoxyl group propionic aldehyde yield in said method in preparation 3-acetoxyl group propionic aldehyde process.
Summary of the invention
One of technical problem to be solved by this invention is the low and selective low problem of 3-acetoxyl group propionic aldehyde yield, there is provided a kind of 3-acetoxyl group propionic aldehyde to synthesize catalyst used, it is high to the selective high feature of 3-acetoxyl group propionic aldehyde that this catalyst has 3-acetoxyl group propionic aldehyde yield.
Two of technical problem to be solved by this invention is the production methods adopting one of above-mentioned technical problem described catalyst.
Three of technical problem to be solved by this invention is the synthetic methods of the 3-acetoxyl group propionic aldehyde adopting one of above-mentioned technical problem described catalyst.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: 3-acetoxyl group propionic aldehyde synthesizes catalyst used, and described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, at least one metallic element that active component comprises at least one of chosen from Fe series elements, alkali metal and is selected from VA and IB.Preferred described active component comprises iron series element, alkali metal, at least one metallic element that is selected from least one metallic element in VA and is selected from IB simultaneously.Now there is synergy improving in the selective and yield of 3-acetoxyl group propionic aldehyde between the metallic element of VA and the metallic element of IB.
In technique scheme, at least one in the excellent chosen from Fe of described iron series element, cobalt and nickel.
In technique scheme, at least one of described alkali metal preferably in lithium, sodium, potassium, rubidium and caesium.
In technique scheme, at least one of described VA metal preferably in antimony and bismuth.
In technique scheme, at least one of described IB metal preferably in copper, silver and gold.
In technique scheme, as most preferred technical scheme, described active component comprises iron series element, alkali metal, VA metallic element and IB metallic element simultaneously; Such as described active component is made up of cobalt (or nickel), lithium, bismuth and gold, or be made up of cobalt, nickel, lithium (or rubidium), bismuth and gold, or be made up of cobalt, nickel, lithium, rubidium, bismuth and gold (or boron), or be made up of cobalt, nickel, lithium, rubidium, bismuth (or antimony), gold and silver.The most preferred described active component is made up of cobalt, nickel, lithium, rubidium, antimony, bismuth, gold and silver.
In technique scheme, in described catalyst, the content of iron series element is preferably 3.00 ~ 15.00g/L, is more preferably 7.00 ~ 12.00g/L; In described catalyst, the content of alkali metal 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 IB in described catalyst is preferably 0.10 ~ 5.00g/L, is more preferably 1.00 ~ 5.00g/L.Described 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.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the production method of catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
1. the solution pressing the compound of metallic element in the compound of composition by iron series element of catalyst, the compound of alkali metal, VA and IB mixes with carrier;
2. dry.
In technique scheme, at least one of compound preferably in ferrocene, carbonyl cobalt, cobalt acetate, cobalt chloride, carbonyl nickel and nickel chloride of step 1. described iron series element.Step is at least one of described alkali metal compound preferably in alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metal sulfates and alkali metal acetate 1..At least one of step 1. in the preferred basic bismuth carbonate of described VA metallic compound, bismuth sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth subsalicylate, antimony oxide, antimony sulfate and antimony chloride; Step is at least one of metallic compound preferably in copper citrate, copper chloride, Schweinfurt green, silver ammino solution, silver tetrafluoroborate, gold chloride and tetra chlorauric acid ammonium in described IB 1..Step 2. described baking temperature is 80 ~ 120 DEG C, is more preferably 100 ~ 120 DEG C.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the synthetic method of 3-acetoxyl group propionic aldehyde, with vinyl acetate, carbon monoxide and hydrogen for raw material, take toluene as solvent, under catalyst according to any one of the described technical scheme of one of above-mentioned technical problem and promoter exist, reaction generates 3-acetoxyl group propionic aldehyde.At least one in the preferred pyridine of described promoter and triphenyl phosphorus.
Key of the present invention is the selection of catalyst, those skilled in the art will know that the proportioning determining suitable reaction temperature, reaction time, reaction pressure and material how according to actual needs.But the temperature of reacting in technique scheme 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.The mol ratio of carbon monoxide and hydrogen is preferably 0.10 ~ 10.0.
Product of the present invention through cooling, decompression, be separated after adopt gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) to analyze, by the conversion ratio of following formulae discovery vinyl acetate and the yield of 3-acetoxyl group propionic aldehyde and selective:
Compared with prior art, key of the present invention is that the active component of catalyst comprises iron series element, alkali metal and is selected from least one metallic element in VA and IB, be conducive to improving the activity of major catalyst and stability, thus improve the yield of 3-acetoxyl group propionic aldehyde and selective.
Experimental result shows, when adopting of the present invention, 3-acetoxyl group propionic aldehyde yield 61.47%, selectively reach 95.26%, achieve good technique effect, especially, when active component comprises iron series element, alkali metal simultaneously, is selected from least one metallic element in VA and is selected from least one metallic element in IB in catalyst, achieve more outstanding technique effect, can be used in the industrial production of 1.3-propane diols.Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the Co of 2.80gBi
2(CO)
8, LiCl and bismuth subsalicylate (C
7h
5biO
4) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Bi content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.47% as calculated, and selective is 95.26%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 2]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the Co of 2.80gAu
2(CO)
8, LiCl and tetra chlorauric acid ammonium (NH
4auCl
42H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Au content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.73% as calculated, and selective is 95.11%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst: will 8.50gCo and the Co containing 2.10gLi be contained
2(CO)
8be that in the aqueous acetic acid of 10wt%, obtaining maceration extract 400ml, is 168m by 1.0L specific surface in concentration with the abundant mixed dissolution of LiCl
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 50.23% as calculated, and selective is 85.39%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
By finding out compared with embodiment 1 ~ 2, the catalyst that the present invention adopts, use simultaneously more excellent than the performance only containing Co and Li active constituent catalyst containing Co, Li and Bi active component, catalyst performance simultaneously containing Co, Li and Au active component, the selective and yield of 3-acetoxyl group propionic aldehyde all wants height.
[embodiment 3]
The preparation of catalyst: by containing 7.00gCo, containing 0.50gNa with containing the Co (OAc) of 1.00gBi
24H
2o, Na
2o and (BiO)
2cO
30.5H
2the abundant mixed dissolution of O is in 8wt% aqueous hydrochloric acid solution in concentration, obtains maceration extract 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 maceration extract, leaves standstill 3h in 80 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 7.00g/L, Na content 0.50g/L, Bi content 1.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 57.32% as calculated, and selective is 93.48%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 4]
The preparation of catalyst: by containing 12.00gFe, containing 3.00gK with containing the ferrocene (Fe (C of 5.00gBi
5h
5)
2), K
2sO
4and BiCl
3abundant mixed dissolution is in the aqueous solution of nitric acid of 8wt% in concentration, obtains maceration extract 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 maceration extract, leaves standstill 3h in 120 DEG C of dryings, obtains described catalyst.The Fe content measuring this catalyst through ICP is 12.00g/L, K content 3.00g/L, Bi content 5.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 62.93% as calculated, and selective is 94.82%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 5]
The preparation of catalyst: by containing 8.50gNi, containing 2.10gRb with containing the Ni (CO) of 2.80gBi
4, RbNO
3with bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2o) fully mixed dissolution is in 10wt% aqueous acetic acid in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Ni content measuring this catalyst through ICP is 8.50g/L, Rb content 2.10g/L, Bi content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.60% as calculated, and selective is 95.06%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 6]
The preparation of catalyst: by containing 8.50gNi, containing 2.10gCs with containing the Ni (NO of 2.80gSb
3)
26H
2o, CsOAc and Cl
3the abundant mixed dissolution of Sb is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Ni content measuring this catalyst through ICP is 8.50g/L, Cs content 2.10g/L, Sb content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.39% as calculated, and selective is 95.13%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 7]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the CoCl of 2.80gSb
26H
2o, LiCl and Sb
2o
3abundant mixed dissolution is in the aqueous solution of nitric acid of 8wt% in concentration, obtains maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Sb content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.23% as calculated, and selective is 95.34%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 8]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the Co (NO of 2.80gSb
3)
26H
2o, LiCl and Sb
2(SO
4)
3abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Sb content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.28% as calculated, and selective is 95.54%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 9]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the Co of 2.80gCu
2(CO)
8, LiCl and cupric tartrate (C
4h
4o
6cuXH
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Cu content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 61.43% as calculated, and selective is 95.17%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 10]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the Co of 2.80gAg
2(CO)
8, LiCl and silver ammino solution ([Ag (NH
3)
2] OH) and fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Ag content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:10, after sustained response 1.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 58.41% as calculated, and selective is 94.56%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 11]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi with containing the Co of 2.80gAg
2(CO)
8, LiCl and silver tetrafluoroborate (AgBF
4) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Ag content 2.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:1, after sustained response 15.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 62.07% as calculated, and selective is 94.14%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 12]
The preparation of catalyst: by containing 8.50gCo, containing 2.10gLi, containing 1.70gBi with containing the Co of 1.10gAu
2(CO)
8, LiCl, bismuth subsalicylate (C
7h
5biO
4) and tetra chlorauric acid ammonium (NH
4auCl
42H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Bi content 1.70g/L, Au content 1.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 64.06% as calculated, and selective is 96.37%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between VA metal Bi and IB metal A u, to there is synergy on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2.
[embodiment 13]
The preparation of catalyst: by containing 8.50gNi, containing 2.10gLi, containing 1.70gBi with containing the Ni (CO) of 1.10gAu
4, LiCl, bismuth subsalicylate (C
7h
5biO
4) and tetra chlorauric acid ammonium (NH
4auCl
42H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Ni content measuring this catalyst through ICP is 8.50g/L, Li content 2.10g/L, Bi content 1.70g/L, Au content 1.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 63.88% as calculated, and selective is 96.35%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 14]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 2.10gLi, containing 1.70gBi with containing the Co of 1.10gAu
2(CO)
8, Ni (CO)
4, LiCl, bismuth subsalicylate (C
7h
5biO
4) and tetra chlorauric acid ammonium (NH
4auCl
42H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Li content 2.10g/L, Bi content 1.70g/L, Au content 1.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 64.97% as calculated, and selective is 96.84%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, in Ferrious material, between Ni and Co, to there is synergy on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13.
[embodiment 15]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 2.10gRb, containing 1.70gBi with containing the Co of 1.10gAu
2(CO)
8, Ni (CO)
4, RbNO
3, bismuth subsalicylate (C
7h
5biO
4) and tetra chlorauric acid ammonium (NH
4auCl
42H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Rb content 2.10g/L, Bi content 1.70g/L, Au content 1.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 65.05% as calculated, and selective is 96.73%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 16]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gBi with containing the Co of 1.10gAu
2(CO)
8, Ni (CO)
4, LiCl, RbNO
3, bismuth subsalicylate (C
7h
5biO
4) and tetra chlorauric acid ammonium (NH
4auCl
42H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, and obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Li content 0.80g/L, Rb content 1.30g/L, Bi content 1.70g/L, Au content 1.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 66.41% as calculated, and selective is 97.39%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between alkali metal Li, Rb, there is synergy, describe between Co, Ni, Li, Rb, Bi and Au six kinds of active components and there is well synergy.
[embodiment 17]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gBi with containing the Co of 1.10gAg
2(CO)
8, Ni (CO)
4, LiCl, RbNO
3, bismuth subsalicylate (C
7h
5biO
4) and silver tetrafluoroborate (AgBF
4) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Li content 0.80g/L, Rb content 1.30g/L, Bi content 1.70g/L, Ag content 1.10g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 66.35% as calculated, and selective is 97.47%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 18]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gBi, containing 0.70gAu with containing the Co of 0.40gAg
2(CO)
8, Ni (CO)
4, LiCl, RbNO
3, bismuth subsalicylate (C
7h
5biO
4), tetra chlorauric acid ammonium (NH
4auCl
42H
2and silver tetrafluoroborate (AgBF O)
4) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Li content 0.80g/L, Rb content 1.30g/L, Bi content 1.70g/L, Au content 0.70g/L, Ag content 0.40g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 67.55% as calculated, and selective is 98.16%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between IB metal A u, Ag, there is synergy, describe between Co, Ni, Li, Rb, Bi, Au and Ag seven kinds of active components and there is well synergy.
[embodiment 19]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gSb, containing 0.70gAu with containing the Co of 0.40gAg
2(CO)
8, Ni (CO)
4, LiCl, RbNO
3, Cl
3sb, tetra chlorauric acid ammonium (NH
4auCl
42H
2and silver tetrafluoroborate (AgBF O)
4) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Li content 0.80g/L, Rb content 1.30g/L, Sb content 1.70g/L, Au content 0.70g/L, Ag content 0.40g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 67.21% as calculated, and selective is 98.29%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 20]
The preparation of catalyst: by containing 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 0.90gBi, containing 0.80gSb, containing 0.70gAu with containing the Co of 0.40gAg
2(CO)
8, Ni (CO)
4, LiCl, RbNO
3, bismuth subsalicylate (C
7h
5biO
4), Cl
3sb, tetra chlorauric acid ammonium (NH
4auCl
42H
2and silver tetrafluoroborate (AgBF O)
4) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, obtaining maceration extract 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 maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP is 5.65g/L, Ni content 2.85g/L, Li content 0.80g/L, Rb content 1.30g/L, Bi content 0.90g/L, Sb content 0.80g/L, Au content 0.70g/L, Ag content 0.40g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.4MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 69.03% as calculated, and selective is 98.82%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 20 and embodiment 18 and embodiment 19, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between VA metal Bi, Sb, there is synergy, describe between Co, Ni, Li, Rb, Bi, Sb, Au and Ag eight kinds of active components and there is well synergy.
Table 1
Table 2 (continued)
Table 2 (Continued)
Claims (10)
1.3-acetoxyl group propionic aldehyde synthesizes catalyst used, and described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, at least one metallic element that active component comprises at least one of chosen from Fe series elements, alkali metal and is selected from VA and IB.
2. catalyst according to claim 1, is characterized in that at least one in described iron series element chosen from Fe, cobalt and nickel.
3. catalyst according to claim 1, is characterized in that described alkali metal is selected from least one in lithium, sodium, potassium, rubidium and caesium.
4. catalyst according to claim 1, is characterized in that described VA metal is selected from least one in antimony and bismuth.
5. catalyst according to claim 1, is characterized in that described IB metal is selected from least one in copper, silver and gold.
6. catalyst according to claim 1, it is characterized in that the content of iron series element in catalyst is: 3.00 ~ 15.00g/L, the content of alkali metal is: 0.10 ~ 3.00g/L.
7. catalyst according to claim 1, at least one content that it is characterized in that being selected from described in catalyst metal in VA and IB is 0.10 ~ 5.00g/L.
8., by the production method of catalyst according to claim 1, comprise the steps:
1. the solution pressing the compound of metallic element in the compound of composition by iron series element of catalyst, the compound of alkali metal, VA and IB mixes with carrier;
2. dry.
The synthetic method of 9.3-acetoxyl group propionic aldehyde, with vinyl acetate, carbon monoxide and hydrogen for raw material, is solvent with toluene, and according to any one of claim 1 ~ 7, catalyst and promoter synthesize 3-acetoxyl group propionic aldehyde under existing.
10. synthetic method according to claim 9, is characterized in that described promoter is selected from least one in pyridine and triphenyl phosphorus.
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