CN105498846B - 3 acetoxyl group propionic aldehyde catalyst and preparation method thereof - Google Patents
3 acetoxyl group propionic aldehyde catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to 3 acetoxyl group propionic aldehyde catalyst and preparation method thereof, 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 3 acetoxyl group propionic aldehyde catalyst, the catalyst includes major catalyst and accelerator, and the major catalyst includes carrier, active component；The activearm uses the compound of rhodium；The accelerator is selected from least one of organic amine and organophosphor；The carrier is that aluminized coating is contained and with the element modified silica of modified metal in its surface；The aluminium content is 1.00~10.00g/L；Modified metal constituent content is 0.010~1.00g/L；The modified metal element is selected from the technical scheme of at least one of IIB metallic elements, preferably solves the problem, in the industrial production available for 1.3 propane diols.
Description
Technical field
The present invention relates to 3- acetoxyl group propionic aldehyde catalyst, preparation method and application.
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 relatively low,
A kind of new 3- acetoxyl group propionic aldehyde catalyst is provided, the catalyst has 3- acetoxyl group propionic aldehyde high incomes to 3- acetoxyl groups
The characteristics of propionic aldehyde is selectively high.
The two of the technical problems to be solved by the invention are the preparation sides 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 include major catalyst and accelerator, and the major catalyst includes carrier, active component；The activearm is adopted
With the compound of rhodium；The accelerator is selected from least one of organic amine and organophosphor；The carrier is that aluminium is contained on its surface
Coating and with the element modified silica of modified metal；The aluminium content is 1.00~10.00g/L；Modified metal element contains
Measure as 0.010~1.00g/L；The modified metal element is selected from least one of IIB metallic elements.It is preferred that the organophosphor
Structure with such as following formula (I), more preferably R1、R2And R3For alkyl, C is further independently selected from1~C20Alkyl, further
Independently it preferably is selected from C6~C20Aryl or alkyl substituting aromatic base, such as phenyl, tolyl, naphthyl etc..
The compound of rhodium described in above-mentioned technical proposal is preferably RhCl3.The accelerator is preferably pyridine and triphenyl
At least one of phosphorus.The aluminized coating raw material in aluminium hydroxide, boehmite, boehmite and aluminum phosphate at least one
Kind.The IIB metallic elements preferably are selected from least one of Zn, Cd and Hg.More preferably described IIB metallic elements include Zn simultaneously
And Cd.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
Major catalyst preparation method described in case, comprises the following steps：
1. the aluminized coating raw material and Ludox are mixed to get coating liquid；
2. above-mentioned coating liquid is coated into silica surface, dry, roasting obtains the catalyst carrier precursor I；
3. the compound of the metallic element containing IIB is configured into the aqueous solution to be immersed on catalyst carrier precursor I, it is dried to obtain
The catalyst carrier II；
4. by the composition of catalyst by RhCl3Mixed with catalyst carrier II；
5. standing, drying, roasting, the major catalyst is obtained.
3. described drying temperature is preferably 80~120 DEG C to step in above-mentioned technical proposal.More preferably 100~120 DEG C.
It was found by the inventors of the present invention that in above-mentioned technical proposal, by activity component impregnation at the same time using aluminum phosphate, hydrogen-oxygen
Change aluminium and do aluminized coating raw material and with the catalyst obtained on Zn and Cd compound modified carrier either selectivity or 3-
Acetoxyl group propionic aldehyde yield has reached best.
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, toluene is solvent, in the presence of a catalyst reaction generation 3- acetoxyl groups third
Aldehyde.
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.Hydrogen and an oxygen
The mol ratio for changing carbon 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 methyl acetate and the yield and selectivity of ethylidene diacetate：
Compared with prior art, key of the invention is that catalyst carrier is used containing aluminized coating and entered with IIB metallic elements
Row is modified, is advantageous to improve the activity and stability of major catalyst, so as to improve the yield of 3- acetoxyl group propionic aldehyde and choosing
Selecting property.
Test result indicates that selected using the 3- acetoxyl group propionic aldehyde yields prepared by the catalyst of the present invention up to 84.93%
Selecting property reaches 95.48%, achieves preferable technique effect.Especially done in catalyst carrier using aluminum phosphate and aluminium hydroxide
Aluminized coating raw material and during with being modified collaboration containing Zn and metallic element containing Cd, achieves more prominent technique effect.Below by
The present invention is further elaborated for embodiment.
Embodiment
【Embodiment 1】
Catalyst carrier II preparation：It is 35wt% Ludox by the aluminium-hydroxide powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursors I
On, 100 DEG C are dried to obtain the catalyst carrier II.Carrier is 0.59g/ through icp analysis, Al content 5.15g/L, Zn content
L。
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 84.93%, and selectivity is 95.48%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】Comparative example.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
The a diameter of 5.6mm of 1.0L spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, in N in above-mentioned maceration extract2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 70.41%, and selectivity is 81.85%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 2】
For【Embodiment 1】Comparative example.
Catalyst carrier II preparation：It is 35wt% Ludox by the aluminium-hydroxide powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, obtains the catalyst carrier precursor
II.Carrier is through icp analysis, Al content 5.15g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 71.28%, and selectivity is 83.77%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 3】
For【Embodiment 1】Comparative example.
Catalyst carrier II preparation：By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L
It is immersed in a diameter of 5.6mm of 1.0L spherical SiO2On carrier, 100 DEG C of dryings, the catalyst carrier II is obtained.Carrier passes through
Icp analysis, Zn contents are 0.59g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 71.69%, and selectivity is 84.82%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
The catalyst carrier used by can be seen that the present invention compared with Example 1, while use and contain aluminized coating and use
IIB metallic elements be modified the performance of rear catalyst than the carrier without any modification, than only using the compound modified of aluminium
Carrier, the selection of 3- acetoxyl group propionic aldehyde more excellent than the only performance of catalyst made of the carrier of IIB metallized metals modification
Property and yield will be high, this can be seen that the compound and IIB gold illustrated containing aluminium from the data of embodiment 1, comparative example 1~3
Good synergy between category be present.
【Comparative example 4】
For【Embodiment 1】Comparative example.
Catalyst carrier II preparation：It is 35wt% Ludox by the aluminium-hydroxide powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursors I
On, 100 DEG C of dryings, in N2500 DEG C of roasting 4h are warming up in atmosphere, obtain the catalyst carrier II.Carrier through icp analysis,
Al content is 5.15g/L, and Zn contents are 0.59g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 73.14%, and selectivity is 82.56%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
By compared with Example 1 as can be seen that carrier is modified in dipping metallic element containing IIB, only to carrier progress
The performance for drying its catalyst prepared is better than catalyst performance to taking roasting to prepare after carrier drying, and this is from embodiment
1st, the data of comparative example 4 can be seen that.
【Comparative example 5】
For【Embodiment 1】Comparative example.
Catalyst carrier II preparation：It is 35wt% Ludox by the aluminium-hydroxide powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
Carrier is through icp analysis, Al content 5.15g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O, the zinc gluconate containing 0.60gZn
(C12H22O14Zn·3H2O) it is dissolved in pure water, obtains maceration extract 500ml, catalyst carrier II described in 1.0L is immersed in
State in maceration extract, 3h is stood in 100 DEG C of dryings, in N2500 DEG C of roasting 5h are warming up in atmosphere, obtain the major catalyst.It is main
For catalyst through icp analysis, Rh contents are 6.45g/L, and Zn contents are 0.59g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 74.26%, and selectivity is 81.87%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
By compared with Example 1 as can be seen that metal containing IIB is impregnated together with the active component of catalyst,
The performance of catalyst does not obtain preferable effect, and this can be seen that from the data of embodiment 1, comparative example 5.Illustrate the change containing aluminium
There is preferable synergy between compound and metal containing IIB.
【Embodiment 2】
Catalyst carrier II preparation：It is 35wt% Ludox by the boehmite powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursors I
On, 100 DEG C are dried to obtain the catalyst carrier II.Carrier is 0.59g/ through icp analysis, Al content 5.15g/L, Zn content
L。
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 85.04%, and selectivity is 95.31%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 3】
Catalyst carrier II preparation：It is 35wt% Ludox by the boehmite powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursors I
On, 100 DEG C are dried to obtain the catalyst carrier II.Carrier is 0.59g/ through icp analysis, Al content 5.15g/L, Zn content
L。
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 84.97%, and selectivity is 95.53%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 4】
Catalyst carrier II preparation：It is 35wt% Ludox 10.0g by the Aluminum phosphate powders of the Al containing 5.20g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
0.60gZn zinc gluconate (C12H22O14Zn·3H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100
DEG C it is dried to obtain the catalyst carrier II.Carrier is 0.59g/L through icp analysis, Al content 5.15g/L, Zn content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 85.24%, and selectivity is 95.09%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 5】
Catalyst carrier II preparation：It is 35wt% Ludox 10.0g by the Aluminum phosphate powders of the Al containing 5.20g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
0.60gCd Cd (OAC)2·2H2O aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, 100 DEG C be dried to obtain it is described
Catalyst carrier II.Carrier is 0.59g/L through icp analysis, Al content 5.15g/L, Cd content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 84.89%, and selectivity is 95.72%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 6】
Catalyst carrier II preparation：It is 35wt% Ludox 10.0g by the Aluminum phosphate powders of the Al containing 5.20g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
0.60gHg HgSO4Be dissolved in 8wt% nitric acid and obtain solution 0.6L and be immersed on 1.0L catalyst carrier precursors I, 100 DEG C
It is dried to obtain the catalyst carrier II.Carrier is 0.59g/L through icp analysis, Al content 5.15g/L, Hg content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 84.96%, and selectivity is 95.34%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 7】
Catalyst carrier II preparation：The Aluminum phosphate powders of the Al containing 1.10g are filled with concentration for 35wt% Ludox 5.0g
Divide and be mixed to get coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, in air duct slats
1h is placed under part, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.It will contain
0.10gZn zinc gluconate (C12H22O14Zn·3H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100
DEG C it is dried to obtain the catalyst carrier II.Carrier is 0.09g/L through icp analysis, Al content 1.07g/L, Zn content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 85.16%, and selectivity is 95.25%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 8】
Catalyst carrier II preparation：It is 35wt% Ludox 35.0g by the Aluminum phosphate powders of the Al containing 10.00g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
1.00gZn zinc gluconate (C12H22O14Zn·3H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100
DEG C it is dried to obtain the catalyst carrier II.Carrier is 0.99g/L through icp analysis, Al content 9.92g/L, Zn content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 85.38%, and selectivity is 95.20%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 9】
Catalyst carrier II preparation：It is 35wt% Ludox 10.0g by the Aluminum phosphate powders of the Al containing 5.20g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
0.40g Zn zinc gluconate (C12H22O14Zn·3H2O), Cd (OA containing 0.20gCdC)2·2H2O aqueous solution 0.6L impregnates
On 1.0L catalyst carrier precursors I, 100 DEG C are dried to obtain the catalyst carrier II.Carrier is through icp analysis, Al content
5.15g/L, Zn content are 0.40g/L, and Cd contents are 0.19g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 86.85%, and selectivity is 97.06%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 9 and embodiment 4 and embodiment 5, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, Zn and Cd have synergy.
【Embodiment 10】
Catalyst carrier II preparation：It is 35wt% Ludox by the aluminium-hydroxide powder of the Al containing 5.20g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the zinc gluconate (C of the Zn containing 0.40g12H22O14Zn·3H2O), Cd (OA containing 0.20gCdC)2·2H2O aqueous solution 0.6L
It is immersed on 1.0L catalyst carrier precursors I, 100 DEG C are dried to obtain the catalyst carrier II.Carrier contains through icp analysis, Al
It is 0.40g/L to measure as 5.15g/L, Zn contents, and Cd contents are 0.19g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 86.91%, and selectivity is 96.94%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 11】
Catalyst carrier II preparation：By the Aluminum phosphate powders of the Al containing 3.20g, the aluminium-hydroxide powder of the Al containing 2.00g
It is that 35wt% Ludox 10.0g is sufficiently mixed to obtain coating liquid with concentration, it is a diameter of coating liquid is uniformly sprayed at 1.0L
5.6mm spherical SiO2On carrier, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, obtains
To the catalyst carrier precursor I.By the zinc gluconate (C of the Zn containing 0.40g12H22O14Zn·3H2O), the Cd containing 0.20gCd
(OAC)2·2H2O aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100 DEG C are dried to obtain the catalyst carrier
II.For carrier through icp analysis, Al content 5.15g/L, Zn content are 0.40g/L, and Cd contents are 0.19g/L.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetate is added in 1L titanium reactors, 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 until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 108 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 98.67%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, Zn, Cd have synergy in silicon source aluminium hydroxide, aluminum phosphate and IIB metals.
【Embodiment 12】
Catalyst carrier II preparation：It is 35wt% Ludox 10.0g by the Aluminum phosphate powders of the Al containing 5.20g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
0.60gZn zinc gluconate (C12H22O14Zn·3H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100
DEG C it is dried to obtain the catalyst carrier II.Carrier is 0.59g/L through icp analysis, Al content 5.15g/L, Zn content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 73.42%, and selectivity is 79.28%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 13】
Catalyst carrier II preparation：It is 35wt% Ludox 10.0g by the Aluminum phosphate powders of the Al containing 5.20g and concentration
It is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier, divulging information
Under the conditions of place 1h, 100 DEG C of dryings, be then calcined 4h under the conditions of 450 DEG C, obtain the catalyst carrier precursor I.It will contain
0.60gZn zinc gluconate (C12H22O14Zn·3H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100
DEG C it is dried to obtain the catalyst carrier II.Carrier is 0.59g/L through icp analysis, Al content 5.15g/L, Zn content.
The preparation of major catalyst：By the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
Catalyst carrier II is immersed in above-mentioned maceration extract described in 1.0L, 3h is stood in 100 DEG C of dryings, in N2500 are warming up in atmosphere
DEG C roasting 5h, obtain the major catalyst.For major catalyst through icp analysis, Rh contents are 6.45g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol major catalysts, 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 86.12%, and selectivity is 93.44%, for convenience of description and is compared
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, 3- acetoxyl group propionic aldehyde yield and
Selectivity is listed in Tables 1 and 2 respectively.
Table 1
Table 2
Claims (10)
1.3- acetoxyl group propionic aldehyde catalyst, the catalyst include major catalyst and accelerator, and the major catalyst includes carrying
Body, active component；The active component uses the compound of rhodium；The accelerator in organic amine and organophosphor at least
It is a kind of；The carrier is that aluminized coating is contained and with the element modified silica of modified metal in its surface；The aluminium content is
1.00~10.00g/L；Modified metal constituent content is 0.010~1.00g/L；The modified metal element is selected from IIB metals member
At least one of element.
2. catalyst according to claim 1, it is characterised in that the compound of the rhodium is RhCl3。
3. catalyst according to claim 1, it is characterised in that the accelerator in pyridine and triphenyl phosphorus extremely
Few one kind.
4. catalyst according to claim 1, it is characterised in that the aluminized coating raw material is selected from aluminium hydroxide, thin water aluminium
At least one of stone, boehmite and aluminum phosphate.
5. catalyst according to claim 1, it is characterised in that the IIB metallic elements in Zn, Cd and Hg extremely
Few one kind.
6. as the preparation method of the major catalyst described in claim 1, comprise the following steps：
1. the aluminized coating raw material and Ludox are mixed to get coating liquid；
2. above-mentioned coating liquid is coated into silica surface, dry, roasting obtains the catalyst carrier precursor I；
3. the compound of the metallic element containing IIB is configured into the aqueous solution to be immersed on catalyst carrier precursor I, it is dried to obtain described
Catalyst carrier II；
4. by the composition of catalyst by RhCl3Mixed with catalyst carrier II；
5. standing, drying, roasting, the major catalyst is obtained.
7. the preparation method of catalyst according to claim 6, it is characterised in that 3. described drying temperature is 80 to step
~120 DEG C.
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 Claims 1 to 5 catalyst.
9. synthetic method according to claim 8, it is characterized in that the temperature of reaction is 50~180 DEG C, the pressure of reaction is
1.0~15.0MPa, the time of reaction is 1.0~15.0h.
10. synthetic method according to claim 8, it is characterized in that hydrogen and carbon monoxide volume ratio are 0.10~10.0.
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| CN101116816A (en) * | 2007-07-03 | 2008-02-06 | 中国石油大学(华东) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins |
| 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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