CN105498769B - 3- acetoxyl group propionic aldehyde catalyst and preparation method - Google Patents
3- acetoxyl group propionic aldehyde catalyst and preparation method Download PDFInfo
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Abstract
The present invention relates to 3 acetoxyl group propionic aldehyde catalyst and preparation methods, mainly solve the problems, such as that 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low in the prior art, and by using the catalyst of 3 acetoxyl group propionic aldehyde, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes at least one, the technical solution selected from least one of alkali earth metal and selected from least one of VB and IVA metals metallic element selected from platinum cluster metallic element, the technical problem is preferably resolved, in the industrial production available for 1.3 propylene glycol.
Description
Technical field
The present invention relates to 3- acetoxyl group propionic aldehyde catalyst, the preparation method of the catalyst and 3- acetoxyl group propionic aldehyde
Synthetic method.
Background technology
1.3- propylene glycol (1.3-PDO) is a kind of important industrial chemicals, be mainly used for plasticizer, detergent, preservative,
The synthesis of emulsifier is also used for the industries such as food, cosmetics and pharmacy.Since it is a kind of important polyester fiber monomer,
Most important purposes is as monomer and one polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material.
The preparation method of 1.3- propylene glycol has ethylene oxide one-step method, ethylene oxide 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
For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and DuPont Corporation 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 are one carbon-carbon double bonds in vinyl acetate, which can occur hydroformylation reaction, the one of double bond
Plus an aldehyde radical on a carbon atom, the isomer of acetoxyl group propionic aldehyde is generated.The aldehyde can be by adding hydrogen to become hydroxyl
Base, ester group can be become hydroxyl by hydrolysis and form glycol, and such vinyl acetate is by hydroformylation plus hydrogen and hydrolysis
Prepare 1.3- propylene glycol.
It is taught in the patents such as patent US4072709 (Production of lactic acid) and utilizes vinyl acetate
Or vinyl propionate is raw material, is catalyst by using homogeneous rhodium compound, by hydroformylation reaction, obtains α-acetyl oxygen
Base propionic aldehyde or α-propionyloxy propionic aldehyde.Separation or not, then by add hydrogen and hydrolytic process obtain 1.3-PDO or
Oxidation and hydrolysis obtain lactic acid.But there are 3- acetoxyl groups propionic aldehyde receipts during 3- acetoxyl group propionic aldehyde is prepared for the above method
The problem of rate is low and selective not high.
Invention content
The problem of the first technical problem to be solved by the present invention is that 3- acetoxyl group propionic aldehyde yields are low and selectivity is low, carries
For a kind of 3- acetoxyl groups propionic aldehyde catalyst, which there is 3- acetoxyl group propionic aldehyde high incomes 3- acetoxyl groups propionic aldehyde is selected
The characteristics of selecting property is high.
The second technical problem to be solved by the present invention is the preparation side using one of the above-mentioned technical problem catalyst
Method.
The third technical problem to be solved by the present invention is the 3- acetyl using one of the above-mentioned technical problem catalyst
The synthetic method of oxygroup 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 earth metal and selected from least one of VB and IVA metallic element.It is preferred that
The active component is simultaneously including platinum cluster metallic element, alkali earth metal, selected from least one of VB metallic elements and choosing
From at least one of IVA metals metallic element.At this time 3- second is being improved between the metallic element in the metallic element and IVA of VB
There is synergistic effect in terms of acyloxy 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 earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium..
In above-mentioned technical proposal, the VB metals preferably are selected from least one of vanadium, niobium and tantalum.
In above-mentioned technical proposal, the IVA metals preferably are selected from least one of germanium, tin and lead.
In above-mentioned technical proposal, as most preferred technical solution, the active component simultaneously including platinum cluster metallic element,
Alkali earth metal, VB metallic elements and IVA metallic elements；Such as the active component is by rhodium, barium, vanadium and tin (or germanium) group
Into being either made of or be made of rhodium, barium (or beryllium), vanadium, niobium, tin and germanium, Huo Zheyou rhodium, barium, vanadium (or niobium), tin and germanium
Rhodium (or iridium), barium, beryllium, vanadium, niobium, tin and germanium composition.The most preferably the active component by rhodium, iridium, barium, beryllium, vanadium, niobium, tin and
Germanium forms.
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 earth metal is preferably 0.10~3.00g/L in the catalyst, more preferably
For 0.50~3.00g/L；In the catalyst selected from VB and IVA at least one content of metal be preferably 0.10~
5.00g/L, more preferably 1.00~5.00g/L.Carrier specific surface used in the catalyst is preferably 50~300m2/ g, more
Preferably 150~200m2/ g, hole hold preferably 0.80~1.20, more preferably 0.90~1.00.
To solve above-mentioned technical problem two, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case, includes the following steps：
It 1. will be in the compound of platinum cluster metallic element, the compound of alkali earth metal, VB and IVA by the composition of catalyst
The solution of the compound of metallic element is mixed with carrier；
2. it dries.
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
Body, rhodium nitrate, palladium bichloride, four ammonia palladium of dichloro, palladium, ammonium chloropalladite, ruthenic chloride, is crossed in ruthenic acid four triphenylphosphine chlorine rhodium
At least one of amine, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid；Step 1. institute
It states alkaline earth metal compound and preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkaline earth nitrate, alkaline-earth metal sulphur
At least one of hydrochlorate and Alkaline Earth Metal Acetate；The compound of step 1. VB metallic elements have selected from vanadium trichloride,
At least one of vanadic anhydride, columbium pentachloride and tantalic chloride；The compound of step 1. IVA metallic elements preferably is selected from
It is preferred that at least one of stannous oxalate, germanium tetrachloride, stannous chloride, nitric acid stannous, stannous oxide, lead acetate and plumbi nitras.Step
Rapid 2. described drying temperature is 80~120 DEG C, more preferably 100~120 DEG C.
To solve above-mentioned technical problem three, 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 solution of one of above-mentioned technical problem
Reaction generation 3- acetoxyl group propionic aldehyde in the presence of one catalyst and accelerating agent.The preferred pyridine of the accelerating agent and triphenyl
At least one of phosphorus.
The key of the present invention is the selection of catalyst, suitable skilled person will know how determining according to actual needs
Reaction temperature, the reaction time, reaction pressure and material proportioning.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 molar ratio of hydrogen is preferably 0.10~10.0.
Product of the present invention is analyzed after cooling down, depressurizing, detach 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, alkaline earth
Metallic element and selected from least one of VB and IVA metallic element, is conducive to improve the activity and stability of major catalyst, from
And improve the yield and selectivity of 3- acetoxyl group propionic aldehyde.
The experimental results showed that the 3- acetoxyl group propionic aldehyde yield 84.45% prepared by the present invention, selectively reaches
94.53%, it achieves active component in preferable technique effect, especially catalyst and includes platinum cluster metallic element, alkaline earth simultaneously
Metallic element, selected from least one of VB metallic elements and selected from least one of IVA metallic elements when, achieve more
Prominent technique effect, in the industrial production available for 1.3- propylene glycol.The present invention is further explained below by embodiment
It states.
Specific embodiment
【Embodiment 1】
The preparation of catalyst：By the two ligand (Rh of rhodium acetate containing 6.20gRh, containing 2.40gBa and containing 2.90gV2(OAc)4)、
Ba(NO3)2With ammonium metavanadate (NH4VO3) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, is by 1.0L specific surfaces
168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents of the catalyst are measured as 6.20g/L through ICP, Ba content 2.40g/L, V content
2.90g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.45%, and selectivity is 94.53%, 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 two ligand (Rh of rhodium acetate containing 6.20gRh, containing 2.40gBa and containing 2.90gSn2
(OAc)4)、Ba(NO3)2With stannous oxalate (SnC2O4) be sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, it obtains
1.0L specific surfaces are 168m by maceration extract 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is upper
It states in maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is measured through ICP are 6.20g/
L, Ba content 2.40g/L, Sn content 2.90g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.51%, and selectivity is 94.37%, 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 two ligand (Rh of rhodium acetate containing 6.20gRh and containing 2.40gBa2(OAc)4) and Ba (NO3)2
It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, be 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, it is a diameter of
The spherical SiO of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Rh contents for measuring the catalyst are 6.20g/L, Ba contents 2.40g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 72.54%, and selectivity is 85.09%, 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 Examples 1 to 2, using simultaneously containing Rh, Ba and V work
Property component while catalyst performance containing Rh, Ba and Sn active component is than containing only the performance of Rh and Ba active constituent catalysts
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 0.50gBe and containing 1.00gV3·6H2O、BeCl2And VCl3
It is sufficiently mixed and is dissolved in a concentration of 10wt% aqueous acetic acids, obtain maceration extract 400ml, be 200m by 1.0L specific surfaces2/ g,
The spherical Al of Kong Rongwei 1.00, a diameter of 5.6mm2O3Carrier impregnation stands 3h in 80 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Rh contents that the catalyst is measured through ICP are 5.00g/L, Be content 0.50g/L, V 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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 78.44%, and selectivity is 92.68%, 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 3.00gCa and containing 5.00gNb2(SO4)3·15H2O, CaO and
NbCl5It is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, obtains maceration extract 400ml, be by 1.0L specific surfaces
150m2/ g, Kong Rongwei 0.90, the spherical SiO of a diameter of 5.6mm2It is dry in 120 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents of the catalyst are measured as 10.00g/L through ICP, Ca contents 3.00g/L, Nb 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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.25%, and selectivity is 94.28%, 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 2.40gMg and containing 2.90gTa3)3、MgSO4And TaCl5It fills
Mixed dissolution is divided to obtain maceration extract 400ml in a concentration of 8wt% aqueous sulfuric acids, is 168m by 1.0L specific surfaces2/ g, hole
It is 0.94 to hold, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP are 6.20g/L, Mg contents 2.40g/L, Ta 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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.37%, and selectivity is 94.51%, 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 four ammonia palladium (Pd (NH of dichloro containing 6.20gPd, containing 2.40gSr and containing 2.90gGe3)4Cl2·H2O)、Sr(OAC)2·0.5H2O and GeCl4It is sufficiently mixed and is dissolved in a concentration of 8wt% aqueous hydrochloric acid solutions, soaked
1.0L specific surfaces are 168m by stain liquid 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is above-mentioned
In maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Pd contents that the catalyst is measured through ICP are 6.20g/L,
Sr contents 2.40g/L, Ge content 2.90g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.34%, and selectivity is 94.21%, 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 2.40gBa and containing 2.90gSn2、Ba(NO3)2With
SnCl2·2H2O is sufficiently mixed in the acetic acid for being dissolved in a concentration of 10wt%, obtains maceration extract 400ml, is by 1.0L specific surfaces
168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Pd contents of the catalyst are measured as 6.20g/L through ICP, Ba contents 2.40g/L, Sn 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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.31%, and selectivity is 94.26%, 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 2.40gBa and containing 2.90gSn3·XH2O、Ba(NO3)2With
Sn(NO3)2It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, be 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94,
The spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.
The Ru contents that the catalyst is measured through ICP are 6.20g/L, Ba contents 2.40g/L, Sn content 2.90g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.27%, 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 9】
The preparation of catalyst：By the ammonium chloroplatinite ((NH containing 6.20gPt, containing 2.40gBa and containing 2.90gSn4)2PtCl4)、Ba(NO3)2And SnSO4It is sufficiently mixed in the hydrochloric acid for being dissolved in a concentration of 8wt%, obtains maceration extract 400ml, by 1.0L
Specific surface is 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The Pt contents of the catalyst are measured as 6.20g/L, Ba content 2.40g/L through ICP,
Sn contents 2.90g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.52%, 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 10】
The preparation of catalyst：By the OsCl containing 6.20gOs, containing 2.40gBa and containing 2.90gPb3·3H2O、Ba(NO3)2With
Pb(OAC)2·3H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surfaces2/ g, Kong Rong
It is 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described in above-mentioned maceration extract
Catalyst.The Os contents that the catalyst is measured through ICP are 6.20g/L, Ba contents 2.40g/L, Pb content 2.90g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 1.0MPa,
Controlling reaction temperature is 50 DEG C, and the molar ratio of hydrogen and carbon monoxide is 1:After 10, sustained response 1.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 78.32%, and selectivity is 93.52%, 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 2.40gBa and containing 2.90gPb3·XH2O、Ba(NO3)2With
Basic lead acetate (Pb (OAC)2·2Pb(OH)2) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, 1.0L is compared into table
Face is 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Ir contents of the catalyst are measured as 6.20g/L through ICP, Ba contents 2.40g/L, Pb content
2.90g/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 reaction kettles, 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 molar ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 84.85%, and selectivity is 94.11%, 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 two ligand of rhodium acetate containing 6.20gRh, containing 2.40gBa, containing 0.90gV and containing 2.00gSn
(Rh2(OAc)4)、Ba(NO3)2, ammonium metavanadate (NH4VO3) and stannous oxalate (SnC2O4) be sufficiently mixed and be dissolved in a concentration of 8wt%
Aqueous hydrochloric acid solution in, obtain maceration extract 400ml, by 1.0L specific surfaces be 168m2/ g, Kong Rongwei 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 measured through ICP to urge
The Rh contents of agent are 6.20g/L, Ba content 2.40g/L, V content 0.90g/L, Sn content 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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.83%, and selectivity is 95.65%, 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 12 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 synergistic effect between VB metal V and IVA metals Sn.
【Embodiment 13】
The preparation of catalyst：By two ligand of rhodium acetate containing 6.20gRh, containing 2.40gBa, containing 0.90gV and containing 2.00gGe
(Rh2(OAc)4)、Ba(NO3)2, ammonium metavanadate (NH4VO3) and GeCl4Be sufficiently mixed be dissolved in a concentration of 8wt% hydrochloric acid it is water-soluble
In liquid, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2It carries
Body is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The Rh that the catalyst is measured through ICP contains
It measures as 6.20g/L, Ba content 2.40g/L, V content 0.90g/L, Ge content 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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.71%, and selectivity is 95.69%, 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 14】
The preparation of catalyst：By the vinegar containing 6.20gRh, containing 2.40gBa, containing 0.90gV, containing 1.25gSn and containing 0.75gGe
Sour two ligand (Rh of rhodium2(OAc)4)、Ba(NO3)2, ammonium metavanadate (NH4VO3), stannous oxalate (SnC2O4) and GeCl4It is sufficiently mixed
It is dissolved in the aqueous hydrochloric acid solution of a concentration of 8wt%, obtains maceration extract 400ml, be 168m by 1.0L specific surfaces2/ g, Kong Rongwei
0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Rh contents of the catalyst are measured as 6.20g/L through ICP, Ba content 2.40g/L, V content 0.90g/L, Sn content
1.25g/L, Ge content 0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 86.59%, and selectivity is 96.47%, 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, in the selectivity for improving 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that the present invention uses, there is synergistic effect in IVA metals between Sn and Ge.Illustrate Rh, Ba,
V, there is synergistic effect well between five kinds of active components of Sn and Ge.
【Embodiment 15】
The preparation of catalyst：By the vinegar containing 6.20gRh, containing 2.40gBa, containing 0.90gNb, containing 1.25gSn and containing 0.75gGe
Sour two ligand (Rh of rhodium2(OAc)4)、Ba(NO3)2、NbCl5, stannous oxalate (SnC2O4) and GeCl4Be sufficiently mixed be dissolved in it is a concentration of
In the aqueous hydrochloric acid solution of 8wt%, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, it is a diameter of
The spherical SiO of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Rh contents of the catalyst are measured as 6.20g/L, Ba contents 2.40g/L, Nb content 0.90g/L, Sn content 1.25g/L, Ge contain
Measure 0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 86.61%, and selectivity is 96.33%, 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 16】
The preparation of catalyst：To contain 6.20gRh, containing 2.40gBa, containing 0.30gV, containing 0.60gNb, containing 1.25gSn and contain
Two ligand (the Rh of rhodium acetate of 0.75gGe2(OAc)4)、Ba(NO3)2, ammonium metavanadate (NH4VO3)、NbCl5, stannous oxalate
(SnC2O4) and GeCl4It is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, obtains maceration extract 400ml, by 1.0L
Specific surface is 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP are 6.20g/L, Ba contents 2.40g/L, V
Content 0.30g/L, Nb content 0.60g/L, Sn content 1.25g/L, Ge content 0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 87.55%, and selectivity is 97.27%, 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, in the selectivity for improving 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergistic effect between VB metals V, Nb, illustrate Rh, Ba, V, Nb,
There is synergistic effect well between six kinds of active components of Sn and Ge.
【Embodiment 17】
The preparation of catalyst：To contain 6.20gRh, containing 2.40gBe, containing 0.30gV, containing 0.60gNb, containing 1.25gSn and contain
Two ligand (the Rh of rhodium acetate of 0.75gGe2(OAc)4)、BeCl2, ammonium metavanadate (NH4VO3)、NbCl5, stannous oxalate (SnC2O4) and
GeCl4It is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, obtains maceration extract 400ml, be by 1.0L specific surfaces
168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents of the catalyst are measured as 6.20g/L through ICP, Be content 2.40g/L, V content
0.30g/L, Nb content 0.60g/L, Sn content 1.25g/L, Ge content 0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 87.38%, 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.
【Embodiment 18】
The preparation of catalyst：To contain 6.20gRh, containing 1.60gBa, containing 0.80gBe, containing 0.30gV, containing 0.60gNb, contain
The 1.25gSn and two ligand (Rh of rhodium acetate containing 0.75gGe2(OAc)4)、Ba(NO3)2、BeCl2, ammonium metavanadate (NH4VO3)、
NbCl5, stannous oxalate (SnC2O4) and GeCl4It is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, is impregnated
1.0L specific surfaces are 168m by liquid 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP are 6.20g/L, Ba
Content 1.60g/L, Be content 0.80g/L, V content 0.30g/L, Nb content 0.60g/L, Sn content 1.25g/L, Ge content
0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.26%, and selectivity is 98.31%, 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.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, in the selectivity for improving 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergistic effect between alkaline-earth metal Ba, Be, illustrate Rh, Ba, Be,
V, there is synergistic effect well between seven kinds of active components of Nb, Sn and Ge.
【Embodiment 19】
The preparation of catalyst：To contain 6.20gIr, containing 1.60gBa, containing 0.80gBe, containing 0.30gV, containing 0.60gNb, contain
The 1.25gSn and IrCl containing 0.75gGe3·XH2O、Ba(NO3)2、BeCl2, ammonium metavanadate (NH4VO3)、NbCl5, stannous oxalate
(SnC2O4) and GeCl4It is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, obtains maceration extract 400ml, by 1.0L
Specific surface is 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The Ir contents of the catalyst are measured as 6.20g/L, Ba content 1.60g/L through ICP,
Be content 0.80g/L, V content 0.30g/L, Nb content 0.60g/L, Sn content 1.25g/L, Ge content 0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.04%, and selectivity is 98.43%, 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 4.80gRh, containing 1.40gIr, containing 1.60gBa, containing 0.80gBe, containing 0.30gV, contain
0.60gNb, the two ligand (Rh of rhodium acetate containing 1.25gSn and containing 0.75gGe2(OAc)4)、IrCl3·XH2O、Ba(NO3)2、
BeCl2, ammonium metavanadate (NH4VO3)、NbCl5, stannous oxalate (SnC2O4) and GeCl4It is sufficiently mixed and is dissolved in a concentration of 8wt%'s
In aqueous hydrochloric acid solution, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, the ball of a diameter of 5.6mm
Shape SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is measured through ICP
The Rh contents of agent are 4.80g/L, Ir contents 1.40g/L, Ba content 1.60g/L, Be content 0.80g/L, V content 0.30g/L, Nb
Content 0.60g/L, Sn content 1.25g/L, Ge content 0.75g/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 reaction kettles, 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, while agitating and heating is warming up to reaction temperature until pressure 5.8MPa,
Controlling reaction temperature is 95 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：Above-mentioned reaction mixture obtained by the reaction is cooled down, decompression, is detached, liquid phase uses gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.76%, and selectivity is 99.17%, 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, in the selectivity for improving 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergistic effect between platinum cluster metal Rh, Ir, illustrate Rh, Ir, Ba,
There is synergistic effect well between eight kinds of active components of Be, V, Nb, Sn and Ge.
Table 1
Table 2
Claims (8)
1.3- acetoxyl group propionic aldehyde catalyst, the catalyst use SiO2、Al2O3Or its mixture be carrier, active component
Including at least one selected from platinum group, selected from least one of alkali earth metal and in VB extremely
Lack a kind of metallic element and selected from least one of IVA metallic elements；Wherein, the content of the platinum group is：
3.00-15.00g/l, the content of the alkali earth metal are：0.10-3.00g/l；It is described to be selected from least one of VB gold
Belong to element and the content selected from least one of IVA metallic elements is：0.10-5.00g/l.
2. catalyst according to claim 1, which is characterized in that the platinum group metal is in platinum, palladium, osmium, iridium, ruthenium and rhodium
At least one.
3. catalyst according to claim 1, which is characterized in that the alkali earth metal is selected from beryllium, magnesium, calcium, strontium and barium
At least one of.
4. catalyst according to claim 1, which is characterized in that the VB metals are selected from least one of vanadium, niobium and tantalum.
5. catalyst according to claim 1, which is characterized in that the IVA metals in germanium, tin and lead at least one
Kind.
6. by the preparation method of catalyst described in claim 1, include the following steps：
It 1. will be in the compound of platinum group, the compound of alkali earth metal, VB and IVA metals by the composition of catalyst
The solution of the compound of metallic element is mixed with carrier；
2. it dries.
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 any one of Claims 1 to 5 catalyst and accelerating agent.
8. synthetic method according to claim 7, which is characterized in that the accelerating agent is in pyridine and triphenyl phosphorus
It is at least one.
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| EP0949000A1 (en) * | 1994-02-22 | 1999-10-13 | The Standard Oil Company | Process for the preparation of fluid bed vinyl acetate catalyst |
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