CN105498785B - 3- acetoxyl group propionic aldehyde synthesis catalyst used - Google Patents
3- acetoxyl group propionic aldehyde synthesis catalyst used Download PDFInfo
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Abstract
The present invention relates to 3- acetoxyl group propionic aldehyde synthesis catalyst used, mainly solve the problems, such as that 3- acetoxyl groups propionic aldehyde catalyst activity and selectivity is relatively low in the prior art, and by using 3- acetoxyl group propionic aldehyde synthesis catalyst used, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes at least one, alkali metal element and the technical solution selected from least one of VA and IB metallic element selected from iron series element, preferably resolves the technical problem, can be used in the industrial production of 1.3- propylene glycol.
Description
Technical field
The present invention relates to 3- acetoxyl group propionic aldehyde synthesis catalyst used, the production methods and 3- second of the catalyst
The synthetic method of acyloxy propionic aldehyde.
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..Currently, 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
An aldehyde radical is added on a carbon atom, generates the isomer of acetoxyl group propionic aldehyde.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 that catalyst obtains α-acetyl oxygen by hydroformylation reaction by using homogeneous rhodium compound
Base propionic aldehyde or α-propionyloxy propionic aldehyde.Separation or not, then by adding hydrogen and hydrolytic process to obtain 1.3-PDO, or
Oxidation and hydrolysis obtain lactic acid.But there are 3- acetoxyl group propionic aldehyde receipts in the above method during preparing 3- acetoxyl group propionic aldehyde
The problem that rate is low and selectivity is not high.
Invention content
The first technical problem to be solved by the present invention is the problem that 3- acetoxyl group propionic aldehyde yields are low and selectivity is low, is carried
For a kind of 3- acetoxyl groups propionic aldehyde synthesis catalyst used, which has 3- acetoxyl group propionic aldehyde high incomes to 3- acetyl
The characteristics of oxygroup propionic aldehyde high selectivity.
The second technical problem to be solved by the present invention is the producer 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 group propionic aldehyde synthesizes
Catalyst used, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes selected from iron system member
Element at least one, alkali metal element and be selected from least one of VA and IB metallic element.It is preferred that the active component is simultaneously
Including iron series element, alkali metal element, selected from least one of VA metallic elements and selected from least one of IB metal members
Element.Have in terms of improving 3- acetoxyl groups propionic aldehyde selectivity and yield between the metallic element of VA and the metallic element of IB at this time
Synergistic effect.
In above-mentioned technical proposal, the iron series element preferably is selected from least one of iron, cobalt and nickel.
In above-mentioned technical proposal, the alkali metal preferably is selected from least one of lithium, sodium, potassium, rubidium and caesium.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, the IB metals preferably are selected from least one of copper, silver and gold.
In above-mentioned technical proposal, as most preferred technical solution, the active component is simultaneously including iron series element, alkali gold
Belong to element, VA metallic elements and IB metallic elements；Such as the active component is made of cobalt (or nickel), lithium, bismuth and gold, Huo Zheyou
Cobalt, nickel, lithium (or rubidium), bismuth and gold composition, be either made of cobalt, nickel, lithium, rubidium, bismuth and gold (or boron) or by cobalt, nickel, lithium,
Rubidium, bismuth (or antimony), gold and silver composition.The most the preferably active component is made of cobalt, nickel, lithium, rubidium, antimony, bismuth, gold and silver.
In above-mentioned technical proposal, the content of iron series element is preferably 3.00~15.00g/L in the catalyst, more preferably
For 7.00~12.00g/L；The content of alkali metal element is preferably 0.10~3.00g/L in the catalyst, and more preferably 0.50
~3.00g/L；In the catalyst selected from VA and IB 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 production method of catalyst described in case, includes the following steps：
1. by the composition of catalyst that metal in the compound of iron series element, the compound of alkali metal element, VA and IB is first
The solution of the compound of element is mixed with carrier；
2. drying.
In above-mentioned technical proposal, the compound of the step 1. iron series element preferably be selected from ferrocene, carbonyl cobalt, cobalt acetate,
At least one of cobalt chloride, carbonyl nickel and nickel chloride.1. the alkali metal compound preferably is selected from alkali metal oxide, alkali to step
At least one of metal chloride, alkali nitrates, alkali metal sulfates and alkali metal acetate.1. the VA is golden for step
Belong to the preferred basic bismuth carbonate of compound, bismuth sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth subsalicylate, antimony oxide, antimony sulfate and chlorine
Change at least one of antimony；1. preferably to be selected from copper citrate, copper chloride, copper acetate, silver-colored ammonia molten for metallic compound in the IB for step
At least one of liquid, silver tetrafluoroborate, gold chloride and tetra chlorauric acid ammonium.2. the drying temperature is 80~120 DEG C to step, 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, in one of above-mentioned technical problem technical solution
Reaction generates 3- acetoxyl group propionic aldehyde in the presence of any one catalyst and accelerating agent.The preferred pyridine of the accelerating agent and triphen
At least one of base 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, decompression, separation using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the yield and selectivity of the conversion ratio and 3- acetoxyl group propionic aldehyde of vinyl acetate：
Compared with prior art, it includes iron series element, alkali metal member that key of the invention, which is the active component of catalyst,
Element and be selected from least one of VA and IB metallic element, be conducive to improve major catalyst activity and stability, to improve
The yield and selectivity of 3- acetoxyl group propionic aldehyde.
The experimental results showed that when using the present invention, 3- acetoxyl group propionic aldehyde yield 61.47% selectively reaches
95.26%, it is first including iron series element, alkali metal simultaneously to achieve active component in preferable technique effect, especially catalyst
Element selected from least one of VA metallic elements and when being selected from least one of IB metallic elements, achieves more outstanding
Technique effect can be used in the industrial production of 1.3- propylene glycol.Below by embodiment, the present invention is further elaborated.
Specific implementation mode
【Embodiment 1】
The preparation of catalyst：By the Co containing 8.50gCo, containing 2.10gLi and containing 2.80gBi2(CO)8, LiCl and secondary salicylic acid
Bismuth (C7H5BiO4) be sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Co contents that the catalyst is measured through ICP are 8.50g/L, Li contents 2.10g/L, Bi
Content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.47%, and selectivity is 95.26%, 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 2】
The preparation of catalyst：By the Co containing 8.50gCo, containing 2.10gLi and containing 2.80gAu2(CO)8, LiCl and tetra chlorauric acid
Ammonium (NH4AuCl4·2H2O it) is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, obtains maceration extract 400ml, it will
1.0L specific surfaces are 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is quiet in above-mentioned maceration extract
3h is set in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is measured through ICP are 8.50g/L, Li contents
2.10g/L, Au 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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.73%, and selectivity is 95.11%, 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.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By the Co containing 8.50gCo and containing 2.10gLi2(CO)8It is sufficiently mixed with LiCl and is dissolved in concentration
It is 168m by 1.0L specific surfaces in the aqueous acetic acid of 10wt%, to obtain maceration extract 400ml2/ g, Kong Rongwei 0.94, diameter
For the spherical SiO of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Co contents that ICP measures the catalyst are 8.50g/L, Li contents 2.10g/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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 50.23%, and selectivity is 85.39%, 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 Co, Li and Bi work
Property component while catalyst performance containing Co, Li and Au active component is than containing only the performance of Co and Li 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 Co (OAc) containing 7.00gCo, containing 0.50gNa and containing 1.00gBi2·4H2O、Na2O and
(BiO)2CO3·0.5H2O, which is sufficiently mixed, to be dissolved in a concentration of 8wt% aqueous hydrochloric acid solutions, maceration extract 400ml is obtained, by 1.0L
Specific surface is 200m2The spherical Al of/g, Kong Rongwei 1.00, a diameter of 5.6mm2O3Carrier impregnation stands 3h in above-mentioned maceration extract
In 80 DEG C of dryings, the catalyst is obtained.The Co contents that the catalyst is measured through ICP are 7.00g/L, Na contents 0.50g/L, Bi
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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 57.32%, and selectivity is 93.48%, 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 ferrocene (Fe (C containing 12.00gFe, containing 3.00gK and containing 5.00gBi5H5)2)、K2SO4
And BiCl3It is sufficiently mixed in the aqueous solution of nitric acid 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 Fe contents that the catalyst is measured through ICP are 12.00g/L, K contents 3.00g/L, Bi 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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 62.93%, and selectivity is 94.82%, 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 Ni (CO) containing 8.50gNi, containing 2.10gRb and containing 2.80gBi4、RbNO3And bismuth citrate
Ammonium (Bi (NH3)2C6H7O7·H2O it) is sufficiently mixed and is dissolved in a concentration of 10wt% aqueous acetic acids, obtain maceration extract 400ml,
It is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation in above-mentioned maceration extract,
3h is stood in 100 DEG C of dryings, obtains the catalyst.The Ni contents that the catalyst is measured through ICP are 8.50g/L, Rb contents
2.10g/L, Bi content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.60%, and selectivity is 95.06%, 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 Ni (NO containing 8.50gNi, containing 2.10gCs and containing 2.80gSb3)2·6H2O, CsOAc and
Cl3Sb is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, 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 Ni contents that the catalyst is measured through ICP are 8.50g/L, Cs contents 2.10g/L, Sb content
2.80g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.39%, and selectivity is 95.13%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 7】
The preparation of catalyst：By the CoCl containing 8.50gCo, containing 2.10gLi and containing 2.80gSb2·6H2O, LiCl and Sb2O3
It is sufficiently mixed in the aqueous solution of nitric acid for being dissolved in 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 in above-mentioned maceration extract
To the catalyst.The Co contents that the catalyst is measured through ICP are 8.50g/L, Li contents 2.10g/L, Sb content 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.23%, and selectivity is 95.34%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 8】
The preparation of catalyst：By the Co (NO containing 8.50gCo, containing 2.10gLi and containing 2.80gSb3)2·6H2O, LiCl and
Sb2(SO4)3It 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 surfaces
For 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract
It is dry, obtain the catalyst.The Co contents that the catalyst is measured through ICP are 8.50g/L, Li contents 2.10g/L, Sb content
2.80g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.28%, and selectivity is 95.54%, 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 Co containing 8.50gCo, containing 2.10gLi and containing 2.80gCu2(CO)8, LiCl and cupric tartrate
(C4H4O6Cu·XH2O it) is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, obtains maceration extract 400ml, it will
1.0L specific surfaces are 168m2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is quiet in above-mentioned maceration extract
3h is set in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is measured through ICP are 8.50g/L, Li contents
2.10g/L, Cu 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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.43%, and selectivity is 95.17%, 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.
【Embodiment 10】
The preparation of catalyst：By the Co containing 8.50gCo, containing 2.10gLi and containing 2.80gAg2(CO)8, LiCl and silver ammino solution
([Ag(NH3)2]OH it) is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, 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.Through ICP measure the catalyst Co contents be 8.50g/L, Li content 2.10g/L,
Ag contents 2.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 0.2MPa is pressurized to after air in argon gas discharge kettle, then pass 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：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 58.41%, and selectivity is 94.56%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 11】
The preparation of catalyst：By the Co containing 8.50gCo, containing 2.10gLi and containing 2.80gAg2(CO)8, LiCl and tetrafluoro boric acid
Silver (AgBF4) be sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, 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 Co contents that the catalyst is measured through ICP are 8.50g/L, Li contents 2.10g/L, Ag 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 1.0MPa is pressurized to after air in argon gas discharge kettle, then pass 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：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 62.07%, and selectivity is 94.14%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 12】
The preparation of catalyst：By the Co containing 8.50gCo, containing 2.10gLi, containing 1.70gBi and containing 1.10gAu2(CO)8、
LiCl, bismuth subsalicylate (C7H5BiO4) and tetra chlorauric acid ammonium (NH4AuCl4·2H2O it) is sufficiently mixed and is dissolved in a concentration of 10wt%
Aqueous acetic acid 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 Co contents of agent are 8.50g/L, Li contents 2.10g/L, Bi content 1.70g/L, Au content 1.10g/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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 64.06%, and selectivity is 96.37%, 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.
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 VA metal Bi and IB metals Au.
【Embodiment 13】
The preparation of catalyst：By the Ni (CO) containing 8.50gNi, containing 2.10gLi, containing 1.70gBi and containing 1.10gAu4、
LiCl, bismuth subsalicylate (C7H5BiO4) and tetra chlorauric acid ammonium (NH4AuCl4·2H2O it) is sufficiently mixed and is dissolved in a concentration of 10wt%
Aqueous acetic acid 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 Ni contents of agent are 8.50g/L, Li contents 2.10g/L, Bi content 1.70g/L, Au content 1.10g/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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 63.88%, and selectivity is 96.35%, 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 containing 5.65gCo, containing 2.85gNi, containing 2.10gLi, containing 1.70gBi and containing 1.10gAu's
Co2(CO)8、Ni(CO)4, LiCl, bismuth subsalicylate (C7H5BiO4) and tetra chlorauric acid ammonium (NH4AuCl4·2H2O it) is sufficiently mixed molten
In the aqueous acetic acid of a concentration of 10wt% of Xie Yu, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei
0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described urge
Agent.The Co contents that the catalyst is measured through ICP are 5.65g/L, Ni contents 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：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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 64.97%, and selectivity is 96.84%, 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 Ferrious material between Ni and Co.
【Embodiment 15】
The preparation of catalyst：By containing 5.65gCo, containing 2.85gNi, containing 2.10gRb, containing 1.70gBi and containing 1.10gAu's
Co2(CO)8、Ni(CO)4、RbNO3, bismuth subsalicylate (C7H5BiO4) and tetra chlorauric acid ammonium (NH4AuCl4·2H2O it) is sufficiently mixed
It is dissolved in the aqueous acetic acid of a concentration of 10wt%, 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 in above-mentioned maceration extract, obtains described urge
Agent.The Co contents that the catalyst is measured through ICP are 5.65g/L, Ni contents 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：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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 65.05%, and selectivity is 96.73%, 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 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gBi and contain
1.10gAu Co2(CO)8、Ni(CO)4、LiCl、RbNO3, bismuth subsalicylate (C7H5BiO4) and tetra chlorauric acid ammonium (NH4AuCl4·
2H2O it) is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, 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 Co contents that the catalyst is measured through ICP are 5.65g/L, Ni contents 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：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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 66.41%, and selectivity is 97.39%, 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 the present invention uses, there is synergistic effect between alkali metal Li, Rb, illustrate Co, Ni, Li,
There is synergistic effect well between six kinds of active components of Rb, Bi and Au.
【Embodiment 17】
The preparation of catalyst：To contain 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gBi and contain
1.10gAg Co2(CO)8、Ni(CO)4、LiCl、RbNO3, bismuth subsalicylate (C7H5BiO4) and silver tetrafluoroborate (AgBF4) fully
Mixed dissolution obtains maceration extract 400ml in the aqueous acetic acid of a concentration of 10wt%, 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 Co contents that the catalyst is measured through ICP are 5.65g/L, and Ni contents 2.85g/L, Li content 0.80g/L, Rb contain
Measure 1.30g/L, Bi contents 1.70g/L, Ag content 1.10g/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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 66.35%, and selectivity is 97.47%, 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.
【Embodiment 18】
The preparation of catalyst：To contain 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gBi, contain
0.70gAu and Co containing 0.40gAg2(CO)8、Ni(CO)4、LiCl、RbNO3, bismuth subsalicylate (C7H5BiO4), tetra chlorauric acid ammonium
(NH4AuCl4·2H2) and silver tetrafluoroborate (AgBF O4) be sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, it obtains
It is 168m by 1.0L specific surfaces to maceration extract 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation exists
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is measured through ICP are
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：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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 67.55%, and selectivity is 98.16%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
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 the present invention uses, there is synergistic effect between IB metals Au, Ag, illustrate Co, Ni, Li,
There is synergistic effect well between seven kinds of active components of Rb, Bi, Au and Ag.
【Embodiment 19】
The preparation of catalyst：To contain 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 1.70gSb, contain
0.70gAu and Co containing 0.40gAg2(CO)8、Ni(CO)4、LiCl、RbNO3、Cl3Sb, tetra chlorauric acid ammonium (NH4AuCl4·2H2O)
With silver tetrafluoroborate (AgBF4) be sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, maceration extract 400ml is obtained,
It is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation in above-mentioned maceration extract,
3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is measured through ICP are 5.65g/L, Ni contents
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：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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 67.21%, and selectivity is 98.29%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 20】
The preparation of catalyst：To contain 5.65gCo, containing 2.85gNi, containing 0.80gLi, containing 1.30gRb, containing 0.90gBi, contain
0.80gSb, the Co containing 0.70gAu and containing 0.40gAg2(CO)8、Ni(CO)4、LiCl、RbNO3, bismuth subsalicylate (C7H5BiO4)、
Cl3Sb, tetra chlorauric acid ammonium (NH4AuCl4·2H2) and silver tetrafluoroborate (AgBF O4) be sufficiently mixed and be dissolved in a concentration of 10wt%'s
In aqueous acetic acid, 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 Co contents of agent be 5.65g/L, Ni contents 2.85g/L, Li content 0.80g/L, Rb content 1.30g/L, Bi content 0.90g/L,
Sb contents 0.80g/L, Au content 0.70g/L, Ag content 0.40g/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, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.4MPa
Degree, controlling reaction temperature are 120 DEG C, and the molar ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：By above-mentioned reaction mixture obtained by the reaction, cooling, decompression, separation, liquid phase use gas-chromatography-matter
Combined instrument (GC-MASS) is composed to analyze.
The yield for being computed 3- acetoxyl group propionic aldehyde is 69.03%, and selectivity is 98.82%, 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 the present invention uses, there is synergistic effect between VA metals Bi, Sb, illustrate Co, Ni, Li,
There is synergistic effect well between eight kinds of active components of Rb, Bi, Sb, Au and Ag.
Table 1
Table 2 (continued)
2 (Continued) of table
Claims (7)
- The synthetic method of 1.3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, 3- acetoxyl group propionic aldehyde is synthesized in the presence of catalyst and accelerating agent；The catalyst uses SiO2、Al2O3Or its mixture For carrier, active component includes at least one selected from iron series element, alkali metal element and is selected from least one of VA and IB Metallic element, the VA metals are selected from least one of antimony and bismuth；The accelerating agent in pyridine and triphenylphosphine extremely Few one kind.
- 2. synthetic method according to claim 1, it is characterised in that the iron series element in iron, cobalt and nickel at least one Kind.
- 3. synthetic method according to claim 1, it is characterised in that the alkali metal in lithium, sodium, potassium, rubidium and caesium extremely Few one kind.
- 4. synthetic method according to claim 1, it is characterised in that the IB metals in copper, silver and gold at least one Kind.
- 5. synthetic method according to claim 1, it is characterised in that the content of iron series element is in catalyst：3.00~ The content of 15.00g/L, alkali metal element is：0.10~3.00g/L.
- 6. synthetic method according to claim 1, it is characterised in that metal is at least in VA and IB described in catalyst A kind of content is 0.10~5.00g/L.
- 7. synthetic method according to claim 1, it is characterised in that the catalyst is using the production included the following steps Method obtains：1. by the composition of catalyst by metallic element in the compound of iron series element, the compound of alkali metal element, VA and IB The solution of compound is mixed with carrier；2. drying.
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| WO2011075905A1 (en) * | 2009-12-25 | 2011-06-30 | Chen Xiaozhou | Methods for preparing ester of 1,3-propylene glycol and 1,3- propylene glycol |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
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| WO2011075905A1 (en) * | 2009-12-25 | 2011-06-30 | Chen Xiaozhou | Methods for preparing ester of 1,3-propylene glycol and 1,3- propylene glycol |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
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| Title |
|---|
| 均相烯烃氢甲酰化铑催化剂的最新研究进展;夏娅娜等;《分子催化》;20071031;第21卷(第05期);472-482 * |
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