CN105498764B - 3 acetoxyl group propionic aldehyde catalyst and its production method - Google Patents
3 acetoxyl group propionic aldehyde catalyst and its production method Download PDFInfo
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Abstract
The present invention relates to 3 acetoxyl group propionic aldehyde catalyst and its production method, mainly solves the problems, such as that 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low in the prior art, by using 3 acetoxyl group propionic aldehyde catalyst, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkali metal and the technical scheme selected from least one of IVA and IVB metallic 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 3- acetoxyl group propionic aldehyde catalyst, 3- acetoxyl group propionic aldehyde catalyst manufacturing process and 3- acetyl
The synthetic method of epoxide 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 new 3- acetoxyl group propionic aldehyde catalyst, the catalyst has 3- acetoxyl group propionic aldehyde high incomes to 3- acetoxyl groups third
The characteristics of 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：3- acetoxyl groups propionic aldehyde is catalyzed
Agent, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component include rhodium, alkali metal and selected from IVA and
At least one of IVB metallic elements.It is preferred that the active component is simultaneously including rhodium, alkali metal, selected from least one of IVA
Metallic element and selected from least one of IVB metallic elements.Now between IVA metallic element and IVB metallic element
There is synergy in terms of improving 3- acetoxyl groups propionic aldehyde selectivity and yield.
In above-mentioned technical proposal, the alkali metal preferably is selected from least one of lithium, sodium, potassium, rubidium and caesium.
In above-mentioned technical proposal, the IVA metals preferably are selected from least one of germanium, tin and lead.
In above-mentioned technical proposal, the IVB metals preferably are selected from least one of titanium, zirconium and hafnium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium metal element, alkali
Metal, IVA metallic elements and IVB metallic elements；Such as the active component is made up of rhodium, lithium, rubidium, tin and hafnium, or by rhodium,
Lithium, rubidium, tin and zirconium composition, or be made up of rhodium, lithium, rubidium, tin, zirconium and hafnium.
In above-mentioned technical proposal, the content of rhodium is preferably 3.00~15.00g/L in the catalyst, and more preferably 5.00
~10.00g/L；The content of alkali metal is preferably 0.10~3.00g/L in the catalyst, more preferably 0.50~3.00g/L；
In the catalyst selected from IVA and IVB at least one content of metal be 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 catalyst composition by the solution of metallic compound in rhodium compound, alkali metal compound, IVA and IVB with
Carrier mixes；
2. dry.
In above-mentioned technical proposal, 1. the rhodium compound preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate step
At least one；1. the alkali metal compound preferably is selected from alkali metal oxide, alkali metal chloride, alkali metal nitric acid to step
At least one of salt, alkali metal sulfates and alkali metal acetate；The step 1. IVA metallic compounds preferably four chlorinations
At least one of germanium, stannous chloride, nitric acid stannous, stannous oxide, lead acetate and plumbi nitras；1. step metallizes in the IVB
Compound preferably is selected from least one of titanium tetrachloride, ammonium titanium fluoride, hexafluorotitanic acid, zirconium chloride, acetic acid zirconium and oxychloride hafnium；Step
2. the drying temperature is 80~120 DEG C, 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, the reaction generation 3- in the presence of catalyst and accelerator
Acetoxyl group propionic aldehyde.At least one of the preferred pyridine of the accelerator and triphenyl 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 rhodium, alkali metal and selected from IVA
With at least one of IVB metallic element, be advantageous to improve the activity and stability of major catalyst, so as to improve 3- acetyl oxygen
The yield and selectivity of base propionic aldehyde.
Test result indicates that during using catalyst of the present invention, 3- acetoxyl group propionic aldehyde yield 85.26%, selectively reach
94.87%, achieve active component in preferable technique effect, especially catalyst while include rhodium, alkali metal, selected from IVA
At least one of metallic element and during selected from least one of IVB metallic elements, achieve more prominent technique effect,
In industrial production available for 1.3- propane diols.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gSn3·3H2O, LiCl and
SnCl2·2H2O, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.50g/L, Sn content
3.50g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.26%, and selectivity is 94.87%, 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 RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gTi3·3H2O, LiCl and TiCl4
It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtain 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, obtained in above-mentioned maceration extract
To the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.50g/L, Ti content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.34%, and selectivity is 94.59%, 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.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By the RhCl containing 6.50Rh and containing 1.50gLi3·3H2O and LiCl be sufficiently mixed be dissolved in it is pure
In water, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carry
Body is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The Rh that the catalyst is determined through ICP contains
Measure as 6.50g/L, Li contents 1.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 73.86%, and selectivity is 84.45%, 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 Rh, Li and Sn work
Property component and meanwhile performance of the catalyst performance ratio containing only Rh and Li active constituent catalysts containing Rh, Li and Ti 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 Rh (OAc) containing 6.50gRh, containing 1.50gK and containing 3.50gGe3、K2SO4And GeCl4Fill
Point mixed dissolution is in 10wt% aqueous acetic acids in concentration, obtains maceration extract 400ml, than surface is 200m by 1.0L2/ g, hole
Hold for 1.00, a diameter of 5.6mm spherical Al2O3Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, K contents 1.50g/L, Ge content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.19%, and selectivity is 95.04%, 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 4】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.50gRb and containing 3.50gSn3·3H2O、RbNO3With
SnCl2·2H2O, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 150m2/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Rb contents 1.50g/L, Sn content
3.50g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.21%, and selectivity is 95.17%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 5】
The preparation of catalyst：By the Rh containing 5.00gRh, containing 0.50gCs and containing 1.00gPb2(SO4)3·15H2O、CsOAc
With Pb (OAc)2·3H2O, which is sufficiently mixed, to be dissolved in pure water, obtains 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 80 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Cs contents 0.50g/L, Pb content 1.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 80.15%, and selectivity is 89.63%, 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 6】
The preparation of catalyst：By the RhCl containing 10.00gRh, containing 3.00gNa and containing 5.00gPb3·3H2O、Na2O and Pb
(NO3)2It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 120 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 10.00g/L, Na contents 3.00g/L, Pb content
5.00g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.84%, and selectivity is 94.37%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 7】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gTi3·3H2O, LiCl and fluorine titanium
Sour ammonium ((NH4)2TiF6) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.50g/L, Ti content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 76.27%, and selectivity is 94.46%, 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 RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gTi3·3H2O, LiCl and hexafluoro
Metatitanic acid (H2TiF6) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.50g/L, Ti content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 85.71%, and selectivity is 93.64%, 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 RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gZr3·3H2O, LiCl and ZrCl4
It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume 0.94 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Rh contents for determining the catalyst are 6.50g/L, Li contents 1.50g/L, Zr content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.22%, and selectivity is 94.59%, 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 10】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gZr3·3H2O, LiCl and Zr
(OAC)4It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume 0.94, directly
Footpath is 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Rh contents that ICP determines the catalyst are 6.50g/L, Li contents 1.50g/L, Zr content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.31%, and selectivity is 94.97%, 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.
【Embodiment 11】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.50gLi and containing 3.50gHf3·3H2O, LiCl and chlorine oxygen
Change hafnium (HfOCl2·8H2O) it 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.50g/L, Hf content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 85.17%, and selectivity is 95.14%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 12】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.00gLi, containing 0.50gRb and containing 3.50gSn3·3H2O、
LiCl、RbNO3And SnCl2·2H2O, which is sufficiently mixed, to be 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, and Li contains
Measure 1.00g/L, Rb contents 0.50g/L, Sn content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 86.45%, and selectivity is 95.87%, 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.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 4, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, there is synergy between alkali metal Li, Rb and IVA metal Sn.
【Embodiment 13】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 1.00gLi, containing 0.50gRb and containing 3.50gZr3·3H2O、
LiCl、RbNO3With Zr (OAC)4It is sufficiently mixed and is dissolved in the 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.00g/L, Rb content 0.50g/L, Zr
Content 3.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 86.39%, and selectivity is 95.91%, 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 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn and containing 1.50gZr's
RhCl3·3H2O、LiCl、RbNO3、SnCl2·2H2O and Zr (OAC)4Be sufficiently mixed be dissolved in concentration be 8wt% hydrochloric acid it is water-soluble
In liquid, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carry
Body is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The Rh that the catalyst is determined through ICP contains
Measure as 6.50g/L, Li contents 1.00g/L, Rb content 0.50g/L, Sn content 2.00g/L, Zr content 1.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 87.33%, and selectivity is 96.41%, 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.
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, there is synergy between IVA metal Sn and IVB metals Zr.
【Embodiment 15】
The preparation of catalyst：By containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn and containing 1.50gHf's
RhCl3·3H2O、LiCl、RbNO3、SnCl2·2H2O and oxychloride hafnium (HfOCl2·8H2O) it is sufficiently mixed and is dissolved in concentration and is
In 8wt% aqueous hydrochloric acid solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Rh contents for determining the catalyst are 6.50g/L, Li contents 1.00g/L, Rb content 0.50g/L, Sn content 2.00g/L, and Hf contains
Measure 1.50g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 87.48%, and selectivity is 96.23%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 16】
The preparation of catalyst：To contain 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn, containing 0.50gZr and contain
1.00gHf RhCl3·3H2O、LiCl、RbNO3、SnCl2·2H2O、Zr(OAC)4With oxychloride hafnium (HfOCl2·8H2O) fully
Mixed dissolution obtains maceration extract 400ml in the aqueous hydrochloric acid solution that concentration is 8wt%, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Li contents 1.00g/L, Rb content 0.50g/L, and Sn contains
Measure 2.00g/L, Zr contents 0.50g/L, Hf content 1.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol 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 until pressure 5.2MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.0h, 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 88.17%, and selectivity is 97.09%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
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 the present invention uses, there is synergy, explanation between IVA metal Sn and IVB metals Zr, Hf
Synergy well between Rh, Li, Rb, Sn, Zr and Hf six kinds of active components be present.
Table 1
Table 2
Claims (8)
1.3- acetoxyl group propionic aldehyde catalyst, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component
Including rhodium, alkali metal and selected from least one of IVA and IVB metallic element；In catalyst the content of rhodium be 3.00~
15.00g/L, the content of alkali metal is 0.10~3.00g/L, and at least one content of the metal in IVA and IVB is
0.10~5.00g/L.
2. catalyst according to claim 1, it is characterised in that the alkali metal in lithium, sodium, potassium, rubidium and caesium at least
It is a kind of.
3. catalyst according to claim 1, it is characterised in that the IVA metals are selected from least one of germanium, tin and lead.
4. catalyst according to claim 1, it is characterised in that the IVB metals are selected from least one of titanium, zirconium and hafnium.
5. as the production method of the catalyst described in claim 1, comprise the following steps：
1. by the composition of catalyst by the solution and carrier of metallic compound in rhodium compound, alkali metal compound, IVA and IVB
Mixing；
2. dry.
6. the production method of catalyst according to claim 5, it is characterized in that step 1. the rhodium compound be selected from rhodium acetate,
At least one of rhodium nitrate, radium chloride and rhodium sulfate.
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 4 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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