CN105435784B - For preparing the catalyst of 3 acetoxyl group propionic aldehyde - Google Patents
For preparing the catalyst of 3 acetoxyl group propionic aldehyde Download PDFInfo
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Abstract
The present invention relates to the catalyst for preparing 3 acetoxyl group propionic aldehyde, mainly solve the problems, such as that 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low in the prior art, by using the catalyst for preparing 3 acetoxyl group propionic aldehyde, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, lanthanide element and the technical scheme selected from least one of IVA and VIB 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 the catalyst for preparing 3- acetoxyl group propionic aldehyde, 3- acetoxyl group propionic aldehyde catalyst manufacturing process
And the synthetic method of 3- acetoxyl group propionic aldehyde.
Background technology
1.3- propane diols (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, detergent, preservative,
The synthesis of emulsifying agent, it is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its
Most important purposes is as monomer and the polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material one.
The preparation method of 1.3- propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde
Stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc..At present, 1.3-PDO industrialized preparing process
For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and du pont company three
Family's monopolization.Degussa companies are using acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd using oxirane carbonyl
The thorugh biologic engineering method (MF methods) that change method (EO methods), E.I.Du Pont Company innovate using oneself.Its ethylene oxide two-step process
It is current prevailing technology with acrolein hydration method technique.
It is well known that there is a carbon-carbon double bond in vinyl acetate, hydroformylation reaction can occur for the key, the one of double bond
An aldehyde radical is added on individual carbon atom, generates the isomer of acetoxyl group propionic aldehyde.The aldehyde can become hydroxyl by hydrogenation
Base, ester group can be become hydroxyl by hydrolysis and form glycol, and such vinyl acetate is by hydroformylation, hydrogenation and hydrolysis can
Prepare 1.3- propane diols.
Taught in the patents such as patent US4072709 (Production of lactic acid) and utilize vinyl acetate
It is catalyst by using homogeneous rhodium compound or propionate is raw material, by hydroformylation reaction, obtains α-acetyl oxygen
Base propionic aldehyde or α-propionyloxy propionic aldehyde.Whether separation or not, then obtains 1.3-PDO by hydrogenation and hydrolytic process, or
Oxidation and hydrolysis obtain lactic acid.But there are 3- acetoxyl groups propionic aldehyde receipts in the above method during 3- acetoxyl group propionic aldehyde is prepared
The problem of rate is low and selective not high.
The content of the invention
The problem of one of technical problems to be solved by the invention are that 3- acetoxyl group propionic aldehyde yields are low and selectivity is low, carries
For a kind of catalyst for being used to prepare 3- acetoxyl group propionic aldehyde, the catalyst has 3- acetoxyl group propionic aldehyde high incomes to 3- acetyl
The characteristics of epoxide propionic aldehyde is selectively high.
The two of the technical problems to be solved by the invention are the producers using one of the above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are the 3- acetyl using one of the above-mentioned technical problem catalyst
The synthetic method of epoxide propionic aldehyde.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：For preparing 3- acetoxyl groups
The catalyst of propionic aldehyde, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, group of the lanthanides gold
Belong to element and selected from least one of IVA and VIB metallic element.It is preferred that the active component is simultaneously including rhodium, lanthanide series metal
Element, selected from least one of IVA metallic elements and selected from least one of VIB metallic elements.Now IVA metal member
There is synergy in terms of 3- acetoxyl groups propionic aldehyde selectivity and yield is improved between element and VIB metallic element.
In above-mentioned technical proposal, the lanthanide element preferably is selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium at least
It is a kind of.
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 vib metal preferably is selected from least one of chromium, molybdenum and tungsten.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium metal element, lanthanum
It is metallic element, IVA metallic elements and vib metal element；Such as the active component is made up of rhodium, samarium (or cerium), tin and chromium,
Either be made up of rhodium, samarium, cerium, tin and chromium (or molybdenum) or be made up of rhodium, cerium, samarium, tin, chromium and molybdenum, or by rhodium, cerium, samarium,
Tin, germanium, chromium and molybdenum composition.
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 lanthanide element is preferably 0.10~3.00g/L in the catalyst, more preferably 0.50~
3.00g/L；In the catalyst selected from IVA and VIB 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 the composition of catalyst by the change of metal in the compound of rhodium, the compound of lanthanide element, IVA and VIB
The solution of compound mixes with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. rhodium preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate
At least one of；The compound of the step 1. lanthanide element preferably be selected from lanthanum acetate, lanthanum chloride, lanthanum nitrate, cerous acetate,
At least one of cerous nitrate, cerium chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, ytterbium chloride, Europium chloride and lutecium chloride；
The step 1. preferred stannous oxalate of compound of the IVA metals, germanium tetrachloride, stannous chloride, nitric acid stannous, oxidation
At least one of stannous, lead acetate and plumbi nitras；Step 1. in the VIB compound of metal preferably be selected from chromic acetate, chromic nitrate,
At least one of chromium chloride, ammonium molybdate, molybdenum pentachloride and ammonium tungstate；2. the drying temperature is 80~120 DEG C to step, more excellent
Elect 100~120 DEG C as.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of 3- acetoxyl group propionic aldehyde,
Using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, appoint in the technical scheme of one of above-mentioned technical problem
Reaction generation 3- acetoxyl group propionic aldehyde in the presence of catalyst described in one and accelerator.The preferred pyridine of the accelerator and/or
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 be catalyst active component include rhodium, lanthanide element and
Selected from least one of IVA and VIB metallic element, be advantageous to improve the activity and stability of major catalyst, so as to improve
The yield and selectivity of 3- acetoxyl group propionic aldehyde.
Test result indicates that during using catalyst of the present invention, 3- acetoxyl group propionic aldehyde yield 85.22%, selectively reach
94.51%, achieve active component in preferable technique effect, especially catalyst while include rhodium, lanthanide element, choosing
During from least one of IVA metallic elements and selected from least one of VIB metallic elements, more prominent technology is achieved
Effect, in the 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 2.20gSm and containing 3.20gSn3·3H2O、SmCl3·6H2O
With stannous oxalate (SnC2O4) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, obtain maceration extract 400ml, will
1.0L is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is quiet in above-mentioned maceration extract
3h is put in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sm contents
2.20g/L, Sn content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 94.51%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 2】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.20gSm and containing 3.20gCr3·3H2O、SmCl3·6H2O
And CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sm contents 2.20g/L, Cr content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 94.58%, 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 6.50gRh and containing 2.20gSm3·3H2O and SmCl3·6H2O is sufficiently mixed
It is dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm ball
Shape SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is determined through ICP
The Rh contents of agent are 6.50g/L, Sm contents 2.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 73.54%, and selectivity is 83.66%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, Sm and Sn work
Property component and meanwhile performance of the catalyst performance ratio containing only Rh and Sm active constituent catalysts containing Rh, Sm and Cr 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 2.20gCe and containing 3.20gGe3、Ce(OAc)3·6H2O
And GeCl4It is sufficiently mixed and is dissolved in concentration in 8wt% aqueous hydrochloric acid solutions, to obtain maceration extract 400ml, being than surface by 1.0L
200m2/ g, pore volume 1.00, a diameter of 5.6mm spherical Al2O3It is dry in 80 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 6.50g/L, Ce contents 2.20g/L, Ge content
3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 85.23%, and selectivity is 94.57%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 4】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.20gCe and containing 3.20gSn3·3H2O、CeCl3·6H2O
And SnCl2·2H2O, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 150m2/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
120 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Ce contents 2.20g/L, Sn
Content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 85.27%, and selectivity is 94.62%, 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 5】
The preparation of catalyst：By the Rh containing 5.00gRh, containing 0.50gCe and containing 1.00gPb2(SO4)3·15H2O、Ce
(NO3)3·6H2O and Pb (OAc)2It 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, 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 5.00g/L, Ce 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 78.96%, and selectivity is 89.44%, 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 3.00gPr and containing 5.00gPb3·3H2O、Pr(OAc)3·
5H2O and Pb (NO3)2·3H2O, which is sufficiently mixed, to be dissolved in pure water, obtains 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 10.00g/L, Pr 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 85.75%, and selectivity is 94.12%, 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 2.20gNd and containing 3.20gPb3·3H2O、Nd(OAc)3·
5H2O and basic lead carbonate (2PbCO3-Pb(OH)2) be sufficiently mixed be dissolved in concentration be 8wt% nitric acid in, obtain 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 Nd contains
Measure 2.20g/L, Pb contents 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 94.28%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 8】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.20gYb and containing 3.20gCr3·3H2O、YbCl3·6H2O
With Cr (NO3)3·9H2O, 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 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, Yb contents 2.20g/L, Cr content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 85.48%, and selectivity is 94.24%, 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 2.20gEu and containing 3.20gMo3·3H2O、EuCl3·6H2O
And MoCl5It 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 100 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 6.50g/L, Eu contents 2.20g/L, Mo content
3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 94.57%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 10】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.20gLu and containing 3.20gMo3·3H2O、LuCl3·6H2O
With ammonium molybdate ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, is than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Lu contents 2.20g/L, Mo content
3.20g/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 78.15%, and selectivity is 93.98%, 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 2.20gLa and containing 3.20gW3·3H2O、La(OAc)3·
5H2O and ammonium tungstate ((NH4)10W12O41·4H2O) it is sufficiently mixed and is dissolved in pure water, obtain 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, La content 2.20g/L, W content
3.20g/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 85.84%, and selectivity is 93.89%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 12】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.20gSm, containing 2.20gSn and containing 1.00gCr3·3H2O、
SmCl3·6H2O, stannous oxalate (SnC2O4) and CrCl3·6H2O is sufficiently mixed the aqueous hydrochloric acid solution for being dissolved in that concentration is 8wt%
In, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier
It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents of the catalyst are determined through ICP
For 6.50g/L, Sm contents 2.20g/L, Sn content 2.20g/L, Cr 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 87.06%, and selectivity is 95.69%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, in the catalyst that the present invention uses, there is synergy between IVA metals Sn and vib metal Cr.
【Embodiment 13】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.20gCe, containing 2.20gSn and containing 1.00gCr3·3H2O、
CeCl3·6H2O, stannous oxalate (SnC2O4) and CrCl3·6H2O is sufficiently mixed the aqueous hydrochloric acid solution for being dissolved in that concentration is 8wt%
In, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier
It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents of the catalyst are determined through ICP
For 6.50g/L, Ce contents 2.20g/L, Sn content 2.20g/L, Cr 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 86.97%, and selectivity is 95.70%, 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 1.15gSm, containing 1.05gCe, containing 2.20gSn and containing 1.00gCr's
RhCl3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4) and CrCl3·6H2O, which is sufficiently mixed, to be dissolved in
Concentration is in 8wt% aqueous hydrochloric acid solution, obtains 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, Sm contents 1.15g/L, Ce content 1.05g/L, Sn content 2.20g/L, Cr
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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 87.92%, and selectivity is 97.01%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that the present invention uses, there is synergy in lanthanide series metal between Sm and Ce.
【Embodiment 15】
The preparation of catalyst：By containing 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 2.20gSn and containing 1.00gMo's
RhCl3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4) and ammonium molybdate ((NH4)6Mo7O24·4H2O) fill
Point mixed dissolution obtains maceration extract 400ml in the aqueous hydrochloric acid solution that concentration is 8wt%, 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, Sm contents 1.15g/L, Ce content 1.05g/L, Sn
Content 2.20g/L, Mo 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 87.95%, and selectivity is 96.88%, 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 1.15gSm, containing 1.05gCe, containing 2.20gSn, containing 0.60gCr and contain
0.40gMo RhCl3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4)、CrCl3·6H2O and molybdic acid
Ammonium ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml,
Than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract,
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, Sm contents
1.15g/L, Ce content 1.05g/L, Sn content 2.20g/L, Cr content 0.60g/L, Mo content 0.40g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 89.02%, and selectivity is 97.75%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between vib metal Cr, Mo, illustrate Rh, Sm, Ce,
Synergy well between six kinds of active components of Sn, Cr and Mo be present.
【Embodiment 17】
The preparation of catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 2.20gGe, containing 0.60gCr and contain
0.40gMo RhCl3·3H2O、SmCl3·6H2O、CeCl3·6H2O、GeCl4、CrCl3·6H2O and ammonium molybdate ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sm contents 1.15g/L, Ce
Content 1.05g/L, Ge content 2.20g/L, Cr content 0.60g/L, Mo content 0.40g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 88.94%, 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 18】
The preparation of catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 1.35gSn, containing 0.85gGe, contain
The 0.60gCr and RhCl containing 0.40gMo3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4)、GeCl4、
CrCl3·6H2O and ammonium molybdate ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%,
Maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are
6.50g/L, Sm content 1.15g/L, Ce content 1.05g/L, Sn content 1.35g/L, Ge content 0.85g/L, Cr content 0.60g/
L, Mo content 0.40g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 90.39%, and selectivity is 98.17%, 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 18 and embodiment 16 and embodiment 17, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between IVA metals Sn, Ge, illustrate Rh, Sm, Ce,
Synergy well between seven kinds of active components of Sn, Ge, Cr and Mo be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (8)
1. the catalyst for preparing 3- acetoxyl group propionic aldehyde, the catalyst use SiO2、Al2O3Or its mixture is load
Body, active component include rhodium, lanthanide element and selected from least one of IVA and VIB metallic elements；Rhodium in catalyst
Content is 3.00~15.00g/L, and the content of lanthanide element is 0.10~3.00g/L, the metal in IVA and VIB
At least one content be 0.10~5.00g/L.
2. catalyst according to claim 1, it is characterised in that the lanthanide element be selected from lanthanum, cerium, praseodymium, neodymium, samarium,
At least one of europium, ytterbium and lutetium.
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 vib metal is selected from least one of chromium, molybdenum and tungsten.
5. as the production method of the catalyst described in claim 1, comprise the following steps：
1. by the composition of catalyst by the compound of metal in the compound of rhodium, the compound of lanthanide element, IVA and VIB
Solution mixed with carrier；
2. dry.
6. the production method of catalyst according to claim 5, it is characterized in that the compound of the step 1. rhodium is selected from acetic acid
At least one of rhodium, 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 selected from pyridine and/or triphenyl phosphorus.
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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
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| CN102458651A (en) * | 2009-04-21 | 2012-05-16 | 陶氏技术投资有限公司 | Rhenium-promoted epoxidation catalysts and methods of making and using them |
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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
| CN102458651A (en) * | 2009-04-21 | 2012-05-16 | 陶氏技术投资有限公司 | Rhenium-promoted epoxidation catalysts and methods of making and using them |
| 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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