CN105498786B - Synthesize the catalyst used in 3- acetoxyl group propionic aldehyde - Google Patents
Synthesize the catalyst used in 3- acetoxyl group propionic aldehyde Download PDFInfo
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Abstract
The present invention relates to the catalyst used in 3 acetoxyl group propionic aldehyde of synthesis, mainly solve the problems, such as that 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low in the prior art, and by using the catalyst used in 3 acetoxyl group propionic aldehyde of synthesis, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes at least one, the technical solution selected from least one of metalloid element and selected from least one of VB and alkali metal metallic element selected from iron series element, the technical problem is preferably resolved, can be used in the industrial production of 1.3 propylene glycol.
Description
Technical field
The present invention relates to the catalyst used in synthesis 3- acetoxyl group propionic aldehyde, the preparation 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 the catalyst used in a kind of synthesis 3- acetoxyl group propionic aldehyde, 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：Synthesize 3- acetoxyl group propionic aldehyde
Catalyst used, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes selected from iron system member
At least one of element, selected from least one of metalloid element and selected from least one of VB and alkali metal metal member
Element.It is preferred that the active component is simultaneously including iron series element, metalloid element, selected from least one of VB metallic element and choosing
From at least one of alkali metal metallic element.At this time 3- is being improved between the metallic element in the metallic element and alkali metal of VB
There is synergistic effect in terms of acetoxyl group propionic aldehyde selectivity and yield.
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 VB metals preferably are selected from least one of vanadium, niobium and tantalum.
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, as most preferred technical solution, the active component is simultaneously including iron series element, quasi- gold
Belong to element, VB metallic elements and alkali metal element；Such as the active component is made of cobalt, boron, vanadium and rubidium (or potassium), Huo Zheyou
Cobalt, boron, vanadium (or tantalum), rubidium and potassium composition, be either made of cobalt, boron (or tellurium), vanadium, tantalum, rubidium and potassium or by cobalt (or nickel),
Boron, tellurium, vanadium, tantalum, rubidium and potassium composition.The most the preferably active component is made of cobalt, nickel, boron, tellurium, vanadium, tantalum, rubidium and potassium.
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；In the catalyst selected from VB and alkali metal 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. will be golden in the compound of iron series element, the compound of metalloid element, VB and alkali metal by the composition of catalyst
The solution for belonging to 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.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
It states metallic compound in VB and preferably is selected from least one of vanadium trichloride, vanadic anhydride, columbium pentachloride and tantalic chloride；Step
1. the alkali metal compound preferably be selected from alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metal sulfates and
At least one of alkali metal acetate.2. the drying temperature is 80~120 DEG C, more preferably 100~120 DEG C to step.
To solve above-mentioned technical problem three, technical scheme is as follows：The synthetic method of 3- acetoxyl group propionic aldehyde,
Using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, appoint in the technical solution of one of above-mentioned technical problem
Reaction generates 3- acetoxyl group propionic aldehyde in the presence of one catalyst and accelerating agent.The preferred pyridine of the accelerating agent and triphenyl
At least one of phosphorus.
The key of the present invention is the selection of catalyst, suitable skilled person will know how determining according to actual needs
Reaction temperature, the reaction time, reaction pressure and material proportioning.But the temperature reacted in above-mentioned technical proposal is preferably
50~180 DEG C；The pressure of reaction is preferably 1.0~15.0MPa；The time of reaction is preferably 1.0~15.0h.Carbon monoxide with
The molar ratio of hydrogen is preferably 0.10~10.0.
Product of the present invention is analyzed after cooling, 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, metalloid member that key of the invention, which is the active component of catalyst,
Element and be selected from least one of VB and alkali metal 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 the 3- acetoxyl group propionic aldehyde yield 59.86% prepared by the present invention, selectively reaches
93.84%, it is first including iron series element, metalloid simultaneously to achieve active component in preferable technique effect, especially catalyst
Element selected from least one of VB metallic elements and when being selected from least one of alkali metal metallic element, achieves more prominent
The technique effect gone out 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 8.40gCo, containing 1.50gB and containing 2.90gV2(CO)8, ammonium metaborate
(NH4HB4O7·3H2) and ammonium metavanadate (NH O4VO3) be sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, it obtains
1.0L specific surfaces are 168m by maceration extract 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is upper
It states in maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Co contents of the catalyst are measured through ICP and ICP-MS
For 8.40g/L, B content 1.50g/L, V content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 59.86%, and selectivity is 93.84%, 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.
【Embodiment 2】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.50gB and containing 2.90gRb2(CO)8, ammonium metaborate
(NH4HB4O7·3H2) and RbNO O3It is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, obtains maceration extract
1.0L specific surfaces are 168m by 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP and ICP-MS are
8.40g/L, B content 1.50g/L, Rb content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 59.91%, and selectivity is 93.77%, 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 1.50gB2(CO)8With ammonium metaborate (NH4HB4O7·3H2O)
It is sufficiently mixed in the aqueous acetic acid for being dissolved in 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, obtains in above-mentioned maceration extract
To the catalyst.The Co contents that the catalyst is measured through ICP and ICP-MS are 8.40g/L, B content 1.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 50.04%, and selectivity is 85.68%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
The catalyst used by can be seen that the present invention compared with Examples 1 to 2, using simultaneously containing Co, B and V activity
Component while catalyst performance containing Co, B and Rb active component is more excellent than containing only the performance of Co and B activity component catalyst,
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 1.00gV2·4H2O, ammonium pentaborate
((NH4)B5O8·8H2) and Cl O3V, which is sufficiently mixed, to be dissolved in a concentration of 10wt% aqueous acetic acids, and maceration extract 400ml is obtained,
It is 200m by 1.0L specific surfaces2The spherical Al of/g, Kong Rongwei 1.00, a diameter of 5.6mm2O3Carrier impregnation in above-mentioned maceration extract,
3h is stood in 80 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is measured through ICP and ICP-MS are 7.00g/L, B
Content 0.50g/L, V content 1.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 55.33%, and selectivity is 92.14%, 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 4】
The preparation of catalyst：By the ferrocene (Fe (C containing 12.00gFe, containing 3.00gB and containing 5.00gV5H5)2), dimethylamine
Base monoborane (C2H6) and V BN2O5It is sufficiently mixed in the aqueous solution of nitric acid for being dissolved in a concentration of 8wt%, obtains maceration extract 400ml,
It is 150m by 1.0L specific surfaces2/ g, Kong Rongwei 0.90, the spherical SiO of a diameter of 5.6mm2Carrier impregnation in above-mentioned maceration extract,
3h is stood in 120 DEG C of dryings, obtains the catalyst.The Fe contents that the catalyst is measured through ICP and ICP-MS are 12.00g/L,
B content 3.00g/L, V 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 12.5MPa
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 60.25%, and selectivity is 93.78%, 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 1.50gAs and containing 2.90gNb4, arsenic acid (H3AsO4·
0.5H2) and NbCl O5It is sufficiently mixed and is dissolved in ethyl alcohol, obtain maceration extract 400ml, be 168m by 1.0L specific surfaces2/ g, Kong Rong
It is 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described
Catalyst.The Ni contents that the catalyst is measured through ICP are 8.40g/L, As contents 1.50g/L, Nb content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 60.03%, and selectivity is 93.73%, 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 6】
The preparation of catalyst：By the Ni (NO containing 8.40gNi, containing 1.50gTe and containing 2.90gTa3)2·6H2O, ammonium tellurate
((NH4)2TeO4) and TaCl5It is sufficiently mixed in the aqueous sulfuric acid for being dissolved in a concentration of 8wt%, 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 Ni contents that the catalyst is measured through ICP are 8.40g/L, Te contents
1.50g/L, Ta content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 59.83%, and selectivity is 94.04%, 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 1.50gTe and containing 2.90gLi2·6H2O, telluric acid
(H6TeO6) and LiCl be sufficiently mixed and be dissolved in pure water, obtain maceration extract 400ml, by 1.0L specific surfaces be 168m2/ g, Kong Rong
It is 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described
Catalyst.The Co contents that the catalyst is measured through ICP are 8.40g/L, Te contents 1.50g/L, Li content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 59.93%, and selectivity is 93.83%, 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 1.50gB and containing 2.90gNa3)2·6H2O, ammonium metaborate
(NH4HB4O7·3H2) and Na O2O is sufficiently mixed in the aqueous hydrochloric acid solution for being dissolved in a concentration of 8wt%, obtains 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 Co contents that the catalyst is measured through ICP and ICP-MS are 8.40g/L, B
Content 1.50g/L, Na content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 12.5MPa
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 59.90%, and selectivity is 94.10%, 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 1.50gB and containing 2.90gK2(CO)8, ammonium metaborate
(NH4HB4O7·3H2) and K O2SO4It is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, obtains maceration extract
1.0L specific surfaces are 168m by 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP and ICP-MS are
8.40g/L, B content 1.50g/L, K content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 0.2MPa is pressurized to after air in argon gas discharge kettle, 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 55.78%, and selectivity is 93.49%, 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 1.50gB and containing 2.90gCs2(CO)8, ammonium metaborate
(NH4HB4O7·3H2O it) is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt% with CsOAc, obtains maceration extract
1.0L specific surfaces are 168m by 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP and ICP-MS are
8.40g/L, B content 1.50g/L, Cs content 2.90g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reaction kettles, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, 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 60.92%, and selectivity is 93.59%, 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 1.50gB, containing 1.10gV and containing 1.80gRb2(CO)8, metaboric acid
Ammonium (NH4HB4O7·3H2O), ammonium metavanadate (NH4VO3) and RbNO3Be sufficiently mixed be dissolved in a concentration of 10wt% acetic acid it is water-soluble
In liquid, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2It carries
Body is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The catalysis is measured through ICP and ICP-MS
The Co contents of agent are 8.40g/L, B content 1.50g/L, V content 1.10g/L, Rb content 1.80g/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 12.5MPa
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 61.94%, and selectivity is 95.63%, 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 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 synergistic effect between VB metals V and alkali metal Rb.
【Embodiment 12】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.50gB, containing 1.10gV and containing 1.80gK2(CO)8, metaboric acid
Ammonium (NH4HB4O7·3H2O), ammonium metavanadate (NH4VO3) and K2SO4It is sufficiently mixed the aqueous acetic acid for being dissolved in a concentration of 10wt%
In, 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
It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The catalyst is measured through ICP and ICP-MS
Co contents be 8.40g/L, B content 1.50g/L, V content 1.10g/L, K content 1.80g/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 12.5MPa
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 61.88%, and selectivity is 95.72%, 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 13】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.50gB, containing 1.10gV, containing 1.25gRb and containing 0.55gK2
(CO)8, ammonium metaborate (NH4HB4O7·3H2O), ammonium metavanadate (NH4VO3)、RbNO3And K2SO4Be sufficiently mixed be dissolved in it is a concentration of
In the aqueous acetic acid of 10wt%, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, it is a diameter of
The spherical SiO of 5.6mm2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Co contents that the catalyst is measured with ICP-MS are 8.40g/L, B content 1.50g/L, V content 1.10g/L, Rb content 1.25g/
L, K content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 63.02%, and selectivity is 96.97%, 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 13 and embodiment 11 and embodiment 12, 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 alkali metal between Rb and K.Illustrate Co, B, V, Rb
There is synergistic effect well between five kinds of active components of K.
【Embodiment 14】
The preparation of catalyst：By the Co containing 8.40gCo, containing 1.50gB, containing 1.10gTa, containing 1.25gRb and containing 0.55gK2
(CO)8, ammonium metaborate (NH4HB4O7·3H2O)、TaCl5、RbNO3And K2SO4It is sufficiently mixed the vinegar for being dissolved in a concentration of 10wt%
In aqueous acid, maceration extract 400ml is obtained, is 168m by 1.0L specific surfaces2/ g, Kong Rongwei 0.94, the spherical shape of a diameter of 5.6mm
SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.It is measured through ICP and ICP-MS
The Co contents of the catalyst are 8.40g/L, B content 1.50g/L, Ta content 1.10g/L, Rb content 1.25g/L, K content
0.55g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 62.91%, and selectivity is 97.05%, 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 15】
The preparation of catalyst：To contain 8.40gCo, containing 1.50gB, containing 0.40gV, containing 0.70gTa, containing 1.25gRb and contain
The Co of 0.55gK2(CO)8, ammonium metaborate (NH4HB4O7·3H2O), ammonium metavanadate (NH4VO3)、TaCl5、RbNO3And K2SO4Fully
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 and ICP-MS are 8.40g/L, B content 1.50g/L, V content 0.40g/
L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 63.78%, and selectivity is 97.85%, 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 15 and embodiment 13 and embodiment 14, 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 VB metals V, Ta, illustrate Co, B, V, Ta, Rb
There is synergistic effect well between six kinds of active components of K.
【Embodiment 16】
The preparation of catalyst：To contain 8.40gCo, containing 1.50gTe, containing 0.40gV, containing 0.70gTa, containing 1.25gRb and contain
The Co of 0.55gK2(CO)8, ammonium tellurate ((NH4)2TeO4), ammonium metavanadate (NH4VO3)、TaCl5、RbNO3And K2SO4It 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 8.40g/L, Te content 1.50g/L, V content 0.40g/L, Ta content
0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 63.66%, and selectivity is 97.86%, 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 17】
The preparation of catalyst：To contain 8.40gCo, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa, contain
1.25gRb and Co containing 0.55gK2(CO)8, ammonium metaborate (NH4HB4O7·3H2O), ammonium tellurate ((NH4)2TeO4), ammonium metavanadate
(NH4VO3)、TaCl5、RbNO3And K2SO4It is sufficiently mixed in the aqueous acetic acid for being dissolved in a concentration of 10wt%, obtains maceration extract
1.0L specific surfaces are 168m by 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier 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 measured through ICP and ICP-MS are
8.40g/L, B content 0.60g/L, Te content 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K
Content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 64.82%, and selectivity is 98.55%, 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 17 and embodiment 15 and embodiment 16, 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 metalloid B, Te, illustrate Co, B, Te, V,
There is synergistic effect well between seven kinds of active components of Ta, Rb and K.
【Embodiment 18】
The preparation of catalyst：To contain 8.40gNi, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa, contain
1.25gRb and Ni (NO containing 0.55gK3)2·6H2O, ammonium metaborate (NH4HB4O7·3H2O), ammonium tellurate ((NH4)2TeO4), partially
Ammonium vanadate (NH4VO3)、TaCl5、RbNO3And K2SO4It is sufficiently mixed in the aqueous sulfuric acid for being dissolved in a concentration of 8wt%, is soaked
1.0L specific surfaces are 168m by stain liquid 400ml2/ g, Kong Rongwei 0.94, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is above-mentioned
In maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Ni contents that the catalyst is measured through ICP and ICP-MS are
8.40g/L, B content 0.60g/L, Te content 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K
Content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 64.76%, and selectivity is 98.62%, 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 19】
The preparation of catalyst：To contain 6.30gCo, containing 2.10gNi, containing 0.60gB, containing 0.90gTe, containing 0.40gV, contain
0.70gTa, the Co containing 1.25gRb and containing 0.55gK2(CO)8、Ni(NO3)2·6H2O, ammonium metaborate (NH4HB4O7·3H2O), tellurium
Sour ammonium ((NH4)2TeO4), ammonium metavanadate (NH4VO3)、TaCl5、RbNO3And K2SO4It is sufficiently mixed and is 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.It is surveyed through ICP and ICP-MS
The Co contents of the fixed catalyst are 6.30g/L, Ni content 2.10g/L, B content 0.60g/L, Te content 0.90g/L, V content
0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.15mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium 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 12.5MPa
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 66.04%, and selectivity is 99.17%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 19 and embodiment 17 and embodiment 18, 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 Ferrious material Ni, Co, illustrate Co, Ni, B,
There is synergistic effect well between eight kinds of active components of Te, V, Ta, Rb and K.
Table 1
Table 2 (continued)
2 (Continued) of table
Claims (9)
1. synthesizing the catalyst used in 3- acetoxyl group propionic aldehyde, the catalyst uses SiO2、Al2O3Or its mixture is to carry
Body, active component by selected from iron series element at least one, selected from least one of metalloid element and in VB
At least one metallic element composition；The content of iron series element is in the catalyst：3.00 ~ 15.00g/L, metalloid element
Content is：At least one content of metal is 0.10 ~ 5.00g/L in 0.10 ~ 3.00g/L, VB.
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 VB metals are selected from least one of vanadium, niobium and tantalum.
5. catalyst according to claim 1, it is characterised in that the content of iron series element is in catalyst：7.00~12.00g/
The content of L, metalloid element is：0.50 ~3.00g/L.
6. catalyst according to claim 1, it is characterised in that at least one of metal contains in VB described in catalyst
Amount is 1.00 ~ 5.00g/L.
7. by the production method of catalyst described in claim 1, include the following steps：
1. by the composition of catalyst by the chemical combination of metallic element in the compound of iron series element, the compound of metalloid element, VB
The solution of object is mixed with carrier；
2. drying.
The synthetic method of 8.3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent,
3- acetoxyl group propionic aldehyde is synthesized in the presence of any one of claim 1 ~ 6 catalyst and accelerating agent.
9. synthetic method according to claim 8, it is characterised in that the accelerating agent is in pyridine and triphenyl phosphorus
It is at least one.
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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
| 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 |
| 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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