CN105498810B - Prepare the catalyst used in 3 acetoxyl group propionic aldehyde - Google Patents
Prepare the catalyst used in 3 acetoxyl group propionic aldehyde Download PDFInfo
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Abstract
The present invention relates to the catalyst prepared used in 3 acetoxyl group propionic aldehyde, mainly solve the problems, such as that 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low in the prior art, by using 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 scheme selected from least one of metalloid element and selected from least one of VIB and alkaline-earth metal metallic element selected from iron series element, the technical problem is preferably resolved, in the industrial production available for 1.3 propane diols.
Description
Technical field
The present invention relates to the catalyst prepared used in 3- acetoxyl group propionic aldehyde, the preparation method and 3- second of the catalyst
The synthetic method of acyloxy propionic aldehyde.
Background technology
1.3- propane diols (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, detergent, preservative,
The synthesis of emulsifying agent, it is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its
Most important purposes is as monomer and the polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material one.
The preparation method of 1.3- propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde
Stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc..At present, 1.3-PDO industrialized preparing process
For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and du pont company three
Family's monopolization.Degussa companies are using acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd using oxirane carbonyl
The thorugh biologic engineering method (MF methods) that change method (EO methods), E.I.Du Pont Company innovate using oneself.Its ethylene oxide two-step process
It is current prevailing technology with acrolein hydration method technique.
It is well known that there is a carbon-carbon double bond in vinyl acetate, hydroformylation reaction can occur for the key, the one of double bond
An aldehyde radical is added on individual carbon atom, generates the isomer of acetoxyl group propionic aldehyde.The aldehyde can become hydroxyl by hydrogenation
Base, ester group can be become hydroxyl by hydrolysis and form glycol, and such vinyl acetate is by hydroformylation, hydrogenation and hydrolysis can
Prepare 1.3- propane diols.
Taught in the patents such as patent US4072709 (Production of lactic acid) and utilize vinyl acetate
It is catalyst by using homogeneous rhodium compound or propionate is raw material, by hydroformylation reaction, obtains α-acetyl oxygen
Base propionic aldehyde or α-propionyloxy propionic aldehyde.Whether separation or not, then obtains 1.3-PDO by hydrogenation and hydrolytic process, or
Oxidation and hydrolysis obtain lactic acid.But there are 3- acetoxyl groups propionic aldehyde receipts in the above method during 3- acetoxyl group propionic aldehyde is prepared
The problem of rate is low and selective not high.
The content of the invention
The problem of one of technical problems to be solved by the invention are that 3- acetoxyl group propionic aldehyde yields are low and selectivity is low, carries
For a kind of catalyst prepared used in 3- acetoxyl group propionic aldehyde, the catalyst has 3- acetoxyl group propionic aldehyde high incomes to 3- acetyl
The characteristics of epoxide propionic aldehyde is selectively high.
The two of the technical problems to be solved by the invention are the producers using one of the above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are the 3- acetyl using one of the above-mentioned technical problem catalyst
The synthetic method of epoxide propionic aldehyde.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Prepare 3- acetoxyl group propionic aldehyde
Catalyst used, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component is included selected from iron system member
Element at least one, selected from least one of metalloid element and selected from least one of VIB and alkaline-earth metal metal
Element.It is preferred that the active component is simultaneously including iron series element, metalloid element, selected from least one of VIB metallic elements
With selected from least one of alkaline-earth metal metallic element.Now the metallic element in VIB metallic element and alkaline-earth metal it
Between improve 3- acetoxyl groups propionic aldehyde selectivity and yield in terms of have synergy.
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 metalloid element preferably is selected from least one of boron, arsenic and tellurium.
In above-mentioned technical proposal, the vib metal preferably is selected from least one of chromium, molybdenum and tungsten.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including iron series element, quasi- gold
Belong to element, vib metal element and alkali earth metal；Such as the active component is made up of cobalt, tellurium, chromium and strontium (or magnesium), or
Person is made up of cobalt, tellurium, chromium (or tungsten), strontium and magnesium, be either made up of cobalt, tellurium (or boron), chromium, tungsten, strontium and magnesium or by cobalt (or
Nickel), tellurium, boron, chromium, tungsten, strontium and magnesium composition.The most the preferably active component is by cobalt, nickel, tellurium, boron, chromium, tungsten, strontium and magnesium group
Into.
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 metalloid element is preferably 0.10~3.00g/L in the catalyst, and more preferably 0.50
~3.00g/L；At least one content selected from the metal in VIB and alkali gold penus in the catalyst is preferably 0.10~
5.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the catalyst is preferably 50~300m2/ g, more
Preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The production method of catalyst described in case, comprises the following steps：
1. by the composition of catalyst by the compound of iron series element, the compound of metalloid element, VIB and alkaline-earth metal
The solution of the compound of metallic element mixes with carrier；
2. dry.
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.The compound of the step 1. metalloid element preferably is selected from boric acid, five boron
At least one of sour ammonium, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, tellurium dioxide and telluric acid；Step 1. institute
State metallic compound in VIB preferably is selected from chromic acetate, chromic nitrate, chromium chloride, ammonium molybdate, molybdenum pentachloride and ammonium tungstate at least one
Kind；1. the alkaline earth metal compound preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkaline-earth metal nitric acid to step
At least one of salt, alkali earth metal sulfate and Alkaline Earth Metal Acetate.2. the drying temperature is 80~120 DEG C to step,
More preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of 3- acetoxyl group propionic aldehyde,
Using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, appoint in the technical scheme of one of above-mentioned technical problem
Reaction generation 3- acetoxyl group propionic aldehyde in the presence of one catalyst and accelerator.The preferred pyridine of the accelerator and triphenyl
At least one of phosphorus.
The key of the present invention is the selection of catalyst, and skilled person will know how suitable according to determination is actually needed
Reaction temperature, the reaction time, the proportioning of reaction pressure and material.But the temperature reacted in above-mentioned technical proposal is preferably
50~180 DEG C；The pressure of reaction is preferably 1.0~15.0MPa；The time of reaction is preferably 1.0~15.0h.Carbon monoxide with
The mol ratio of hydrogen is preferably 0.10~10.0.
Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the conversion ratio of vinyl acetate and the yield and selectivity of 3- acetoxyl group propionic aldehyde：
Compared with prior art, key of the invention is that the active component of catalyst includes iron series element, metalloid member
Element and selected from least one of VIB and alkaline-earth metal metallic element, is advantageous to improve the activity and stability of catalyst, so as to
Improve the yield and selectivity of 3- acetoxyl group propionic aldehyde.
Test result indicates that the 3- acetoxyl group propionic aldehyde yield 59.78% prepared by the present invention, selectively reaches
93.87%, achieve active component in preferable technique effect, especially catalyst while include iron series element, metalloid member
Element, selected from least one of VIB metallic elements and selected from least one of alkaline-earth metal metallic element when, achieve more
Prominent technique effect, in the industrial production available for 1.3- propane diols.The present invention is further explained below by embodiment
State.
Embodiment
【Embodiment 1】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.70gTe and containing 3.10gCr2(CO)8, ammonium tellurate ((NH4)2TeO4) and Cr (OAc)3·6H2O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract
400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, and Te contains
Measure 1.70g/L, Cr contents 3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 59.78%, and selectivity is 93.87%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 2】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.70gTe and containing 3.10gSr2(CO)8, ammonium tellurate ((NH4)2TeO4) and Sr (OAC)2·0.5H2O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract
400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, and Te contains
Measure 1.70g/L, Sr contents 3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 59.81%, and selectivity is 93.89%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By the Co containing 8.40gCo and containing 1.70gTe2(CO)8With ammonium tellurate ((NH4)2TeO4) fully mixed
Close and be dissolved in the aqueous acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface be 168m by 1.0L2/ g, pore volume
For 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract
Catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, Te contents 1.70g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 50.18%, and selectivity is 85.56%, 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.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Co, Te and Cr work
Property component and meanwhile performance of the catalyst performance ratio containing only Co and Te active constituent catalysts containing Co, Te and Sr active component will
More excellent, the selectivity and yield of 3- acetoxyl group propionic aldehyde will be high.
【Embodiment 3】
The preparation of catalyst：By the Co (OAc) containing 7.00gCo, containing 0.50gB and containing 1.00gCr2·4H2O, ammonium pentaborate
((NH4)B5O8·8H2) and CrCl O3·6H2O, which is sufficiently mixed, is dissolved in concentration in 10wt% aqueous acetic acids, to obtain maceration extract
400ml, than surface it is 200m by 1.0L2/ g, pore volume 1.00, a diameter of 5.6mm spherical Al2O3Carrier impregnation is in above-mentioned leaching
In stain liquid, 3h is stood in 80 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP and ICP-MS are
7.00g/L, B content 0.50g/L, Cr content 1.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 54.76%, and selectivity is 92.62%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 4】
The preparation of catalyst：By the ferrocene (Fe (C containing 12.00gFe, containing 3.00gB and containing 5.00gMo5H5)2), diformazan
Amido monoborane (C2H6) and ammonium molybdate ((NH BN4)6Mo7O24·4H2O) it is sufficiently mixed the nitric acid aqueous solution for being dissolved in that concentration is 8wt%
In solution, maceration extract 400ml is obtained, than surface is 150m by 1.0L2/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO2
Carrier impregnation stands 3h in 120 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.This is determined through ICP and ICP-MS to urge
The Fe contents of agent are 12.00g/L, B content 3.00g/L, Mo content 5.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 60.47%, 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 5】
The preparation of catalyst：By the Ni (CO) containing 8.40gNi, containing 1.70gAs and containing 3.10gMo4, arsenic acid (H3AsO4·
0.5H2) and Mo (CO) O6It is sufficiently mixed and is dissolved in ethanol, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, hole
Hold for 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Ni contents that the catalyst is determined through ICP are 8.40g/L, As contents 1.70g/L, Mo content 3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 59.93%, 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 6】
The preparation of catalyst：By the Ni (NO containing 8.40gNi, containing 1.70gTe and containing 3.10gW3)2·6H2O、TeCl4And tungsten
Sour ammonium ((NH4)10W12O41·4H2O) it is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract
400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Ni contents that the catalyst is determined through ICP are 8.40g/L, and Te contains
Measure 1.70g/L, W content 3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 60.17%, and selectivity is 93.80%, 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 8.40gCo, containing 1.70gTe and containing 3.10gW2·6H2O, telluric acid (H6TeO6)
With ammonium paratungstate ((NH4)10H2(W2O7)6) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, is than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It 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 determined through ICP are 8.40g/L, Te content 1.70g/L, W content
3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 59.86%, and selectivity is 94.01%, 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 8.40gCo, containing 1.70gTe and containing 3.10gBe3)2·6H2O, ammonium tellurate
((NH4)2TeO4) and BeCl2It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g,
Pore volume is 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
The catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, Te contents 1.70g/L, Be content 3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 60.10%, and selectivity is 93.93%, 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 8.40gCo, containing 1.70gTe and containing 3.10gMg2(CO)8, ammonium tellurate ((NH4)2TeO4) and MgSO4It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, Te contents 1.70g/L, Mg
Content 3.10g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 60.15%, and selectivity is 93.75%, 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 8.40gCo, containing 1.70gTe and containing 3.10gCa2(CO)8, ammonium tellurate ((NH4)2TeO4) and Ca (NO3)2It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract 400ml, will
1.0L is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is quiet in above-mentioned maceration extract
3h is put in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, Te contents
1.70g/L, Ca content 3.10g/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 reactors, first with 0.2MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 1.0MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:After 10, sustained response 1.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 54.84%, and selectivity is 93.33%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 11】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.70gTe and containing 3.10gBa2(CO)8, ammonium tellurate ((NH4)2TeO4) and BaO be sufficiently mixed be dissolved in concentration be 10wt% aqueous acetic acid in, obtain maceration extract 400ml, 1.0L compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, Te contents 1.70g/L, Ba content
3.10g/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 reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 15.0MPa
Degree, controlling reaction temperature are 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 60.88%, and selectivity is 93.63%, 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 8.40gCo, containing 1.70gTe, containing 1.70gCr and containing 1.40gSr2(CO)8, telluric acid
Ammonium ((NH4)2TeO4)、Cr(OAc)3·6H2O and Sr (OAC)2·0.5H2O is sufficiently mixed the acetic acid for being dissolved in that concentration is 10wt%
In the aqueous solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm's is spherical
SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalyst is determined through ICP
Co contents be 8.40g/L, Te contents 1.70g/L, Cr content 1.70g/L, Sr content 1.40g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.75%, and selectivity is 95.57%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 2, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, in the catalyst that the present invention uses, there is synergy between vib metal Cr and alkaline-earth metal Sr.
【Embodiment 13】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.70gTe, containing 1.70gCr and containing 1.40gMg2(CO)8, telluric acid
Ammonium ((NH4)2TeO4)、Cr(OAc)3·6H2O and MgSO4It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains
Than surface it is 168m by 1.0L to maceration extract 400ml2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier 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 determined through ICP are
8.40g/L, Te content 1.70g/L, Cr content 1.70g/L, Mg content 1.40g/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 reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 61.81%, and selectivity is 95.41%, 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 14】
The preparation of catalyst：By containing 8.40gCo, containing 1.70gTe, containing 1.70gCr, containing 1.10gSr and containing 0.30gMg's
Co2(CO)8, ammonium tellurate ((NH4)2TeO4)、Cr(OAc)3·6H2O、Sr(OAC)2·0.5H2O and MgSO4It is sufficiently mixed and is dissolved in
Concentration is in 10wt% aqueous acetic acid, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume 0.94,
A diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.
The Co contents that the catalyst is determined through ICP are 8.40g/L, Te contents 1.70g/L, Cr content 1.70g/L, Sr content 1.10g/L,
Mg contents 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 62.77%, and selectivity is 96.52%, 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.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that the present invention uses, there is synergy in alkaline-earth metal between Sr and Mg.Illustrate Co, Te,
Synergy well between five kinds of active components of Cr, Sr and Mg be present.
【Embodiment 15】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.70gTe, containing 1.70gW, containing 1.10gSr and containing 0.30gMg2
(CO)8, ammonium tellurate ((NH4)2TeO4), ammonium paratungstate ((NH4)10H2(W2O7)6)、Sr(OAC)2·0.5H2O and MgSO4It is fully mixed
Close and be dissolved in the aqueous acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface be 168m by 1.0L2/ g, pore volume
For 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract
Catalyst.The Co contents that the catalyst is determined through ICP are 8.40g/L, Te content 1.70g/L, W content 1.70g/L, Sr content
1.10g/L, Mg content 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 62.64%, and selectivity is 96.86%, 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 8.40gCo, containing 1.70gTe, containing 0.90gCr, containing 0.80gW, containing 1.10gSr and contain
0.30gMg Co2(CO)8, ammonium tellurate ((NH4)2TeO4)、Cr(OAc)3·6H2O, ammonium paratungstate ((NH4)10H2(W2O7)6)、Sr
(OAC)2·0.5H2O and MgSO4It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract 400ml,
Than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier 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 determined through ICP are 8.40g/L, Te contents
1.70g/L, Cr content 0.90g/L, W content 0.80g/L, Sr content 1.10g/L, Mg content 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 63.70%, and selectivity is 97.63%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between vib metal Cr, W, illustrate Co, Te, Cr, W,
Synergy well between six kinds of active components of Sr and Mg be present.
【Embodiment 17】
The preparation of catalyst：To contain 8.40gCo, containing 1.70gB, containing 0.90gCr, containing 0.80gW, containing 1.10gSr and contain
0.30gMg Co2(CO)8, dimethylamino monoborane (C2H6BN)、Cr(OAc)3·6H2O, ammonium paratungstate ((NH4)10H2
(W2O7)6)、Sr(OAC)2·0.5H2O and MgSO4It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, is soaked
Stain liquid 400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is above-mentioned
In maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP and ICP-MS are
8.40g/L, B content 1.70g/L, Cr content 0.90g/L, W content 0.80g/L, Sr content 1.10g/L, Mg content 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 63.58%, and selectivity is 97.72%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 18】
The preparation of catalyst：To contain 8.40gCo, containing 1.20gTe, containing 0.50gB, containing 0.90gCr, containing 0.80gW, contain
The 1.10gSr and Co containing 0.30gMg2(CO)8, ammonium tellurate ((NH4)2TeO4), dimethylamino monoborane (C2H6BN)、Cr
(OAc)3·6H2O, ammonium paratungstate ((NH4)10H2(W2O7)6)、Sr(OAC)2·0.5H2O and MgSO4It is sufficiently mixed and is dissolved in concentration
Than surface it is 168m by 1.0L in 10wt% aqueous acetic acid, to obtain maceration extract 400ml2/ g, pore volume 0.94, diameter
For 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Co contents that ICP and ICP-MS determines the catalyst are 8.40g/L, Te content 1.20g/L, B content 0.50g/L, Cr content
0.90g/L, W content 0.80g/L, Sr content 1.10g/L, Mg content 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 64.79%, and selectivity is 98.61%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between metalloid B, Te, illustrate Co, Te, B, Cr,
W, synergy well between seven kinds of active components of Sr and Mg be present.
【Embodiment 19】
The preparation of catalyst：To contain 8.40gNi, containing 1.20gTe, containing 0.50gB, containing 0.90gCr, containing 0.80gW, contain
The 1.10gSr and Ni (NO containing 0.30gMg3)2·6H2O, ammonium tellurate ((NH4)2TeO4), dimethylamino monoborane (C2H6BN)、Cr
(OAc)3·6H2O, ammonium paratungstate ((NH4)10H2(W2O7)6)、Sr(OAC)2·0.5H2O and MgSO4It is sufficiently mixed and is dissolved in concentration
Than surface it is 168m by 1.0L in 10wt% aqueous acetic acid, to obtain maceration extract 400ml2/ g, pore volume 0.94, diameter
For 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Ni contents that ICP and ICP-MS determines the catalyst are 8.40g/L, Te content 1.20g/L, B content 0.50g/L, Cr content
0.90g/L, W content 0.80g/L, Sr content 1.10g/L, Mg content 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 64.67%, and selectivity is 98.66%, 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 6.90gCo, containing 1.50gNi, containing 1.20gTe, containing 0.50gB, containing 0.90gCr, contain
0.80gW, the Ni (NO containing 1.10gSr and containing 0.30gMg3)2·6H2O, ammonium tellurate ((NH4)2TeO4), dimethylamino monoborane
(C2H6BN)、Cr(OAc)3·6H2O, ammonium paratungstate ((NH4)10H2(W2O7)6)、Sr(OAC)2·0.5H2O and MgSO4It is sufficiently mixed
It is dissolved in the aqueous acetic acid that concentration is 10wt%, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Co contents that the catalyst is determined through ICP and ICP-MS are 6.90g/L, Ni contents 1.50g/L, Te content 1.20g/L, B
Content 0.50g/L, Cr content 0.90g/L, W content 0.80g/L, Sr content 1.10g/L, Mg content 0.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.0MPa
Degree, controlling reaction temperature are 123 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 65.91%, and selectivity is 99.37%, 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 20 and embodiment 18 and embodiment 19, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between Ferrious material Ni, Co, illustrate Co, Ni, Te,
B, synergy well between eight kinds of active components of Cr, W, Sr and Mg be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (8)
1. preparing the catalyst used in 3- acetoxyl group propionic aldehyde, the catalyst uses SiO2、Al2O3Or its mixture is load
Body, active component include at least one selected from iron series element, selected from least one of metalloid element and selected from VIB
With at least one of alkaline-earth metal metallic element；The content of iron series element is 3.00~15.00g/L in catalyst, metalloid
The content of element is 0.10~3.00g/L；At least one content of metal is in VIB and alkaline-earth metal described in catalyst
0.10~5.00g/L.
2. catalyst according to claim 1, it is characterised in that the iron series element in iron, cobalt and nickel at least one
Kind.
3. catalyst according to claim 1, it is characterised in that the metalloid element in boron, arsenic and tellurium at least one
Kind.
4. catalyst according to claim 1, it is characterised in that the vib metal is selected from least one of chromium, molybdenum and tungsten.
5. catalyst according to claim 1, it is characterised in that the alkaline-earth metal in beryllium, magnesium, calcium, strontium and barium extremely
Few one kind.
6. as the production method of the catalyst described in claim 1, comprise the following steps：
1. by the composition of catalyst by metal in the compound of iron series element, the compound of metalloid element, VIB and alkaline-earth metal
The solution of the compound of element mixes with carrier；
2. dry.
The synthetic method of 7.3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent,
3- acetoxyl group propionic aldehyde is synthesized in the presence of catalyst any one of Claims 1 to 5 and accelerator.
8. synthetic method according to claim 7, it is characterised in that the accelerator is in pyridine and triphenyl phosphorus
It is at least one.
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| CN101121130A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile catalyst |
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