CN105503601B - The method that vinyl acetate hydroformylation synthesizes 3 acetoxyl group propionic aldehyde - Google Patents
The method that vinyl acetate hydroformylation synthesizes 3 acetoxyl group propionic aldehyde Download PDFInfo
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Abstract
The present invention relates to the method for 3 acetoxyl group propionic aldehyde of synthesis, mainly solve vinyl acetate hydroformylation in the prior art and synthesize the problem of 3 acetoxyl group propionic aldehyde catalyst activity and selectivities are relatively low.By using using vinyl acetate, carbon monoxide and hydrogen as raw material, reaction 3 acetoxyl group propionic aldehyde of synthesis are carried out using toluene as solvent, in the presence of catalyst；The catalyst includes major catalyst and accelerator, and the major catalyst includes carrier, active component；The active component uses the compound of rhodium；At least one of the accelerator in organic amine and organophosphor；The carrier is to contain cated silica with its modified surface of fluorochemical；The silica binder that the coating is bonded in the carrier surface by modified metal element and by the modified metal element is constituted；At least one technical scheme of the modified metal element in alkali metal, preferably solves the problem, in the industrial production available for 1.3 propane diols.
Description
Technical field
The present invention relates to the method that vinyl acetate hydroformylation synthesizes 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, is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its
Topmost 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 use acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd and use oxirane carbonyl
Change method (EO methods), E.I.Du Pont Company use the thorugh biologic engineering method (MF methods) of oneself innovation.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
Plus an aldehyde radical on individual carbon atom, the isomer of acetoxyl group propionic aldehyde is generated.The aldehyde can become hydroxyl by hydrogenation
Base, ester group can become hydroxyl formation glycol by hydrolysis, and such vinyl acetate is by hydroformylation, hydrogenation and hydrolyze just can be with
Prepare 1.3- propane diols.
Taught in the patents such as patent US4072709 (Production of lactic acid) and utilize vinyl acetate
Or propionate is raw material, is catalyst by using homogeneous rhodium compound, 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 during 3- acetoxyl group propionic aldehyde is prepared in the above method
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 low 3- acetoxyl group propionic aldehyde yields and not high selectivity,
A kind of method that new vinyl acetate hydroformylation synthesizes 3- acetoxyl group propionic aldehyde is provided, this method has 3- acetoxyl group propionic aldehyde
High income and to 3- acetoxyl group propionic aldehyde it is selectively high the characteristics of.
The two of the technical problems to be solved by the invention are the preparation methods of one of above-mentioned technical problem catalyst.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Vinyl acetate hydroformylation is closed
Into the method for 3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, catalyst is deposited
Reaction synthesis 3- acetoxyl group propionic aldehyde is carried out lower, the catalyst includes major catalyst and accelerator, the major catalyst bag
Include carrier, active component；The active component uses the compound of rhodium；The accelerator in organic amine and organophosphor extremely
Few one kind；The carrier is to contain cated silica with its modified surface of fluorochemical；The coating is by being modified gold
Category element and the silica binder that the modified metal element is bonded in into the carrier surface are constituted；The fluorine-containing member
Cellulose content is 0.50~5.00g/L；Modified metal constituent content is 0.010~1.00g/L；The modified metal element is selected from alkali
At least one in metallic element.It is preferred that the organophosphor has the structure such as following formula (I), more preferably R1、R2And R3For alkyl,
Further it is independently selected from C1~C20Alkyl, preferably further independently be selected from C6~C20Aryl or alkyl substituting aromatic base, for example
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 in phosphorus.At least one in the preferred ammonium fluosilicate of fluorine-containing compound, ammonium fluoride, hydrofluoric acid and sodium fluoride
Kind.The alkali metal preferably is selected from least one in Li, Na, K, Rb and Cs.More preferably described alkali metal is wrapped simultaneously
Include Rb and Cs.
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. fluorine-containing compound is configured to aqueous solution impregnation of silica, is dried to obtain the catalyst carrier precursor I；
2. the hydroxide or oxide of the modified metal element and Ludox are mixed to get coating liquid；
3. above-mentioned coating liquid is coated to precursor carrier I surfaces, dried, roasting obtains the catalyst carrier II；
4. by the composition of catalyst by RhCl3Solution is mixed with the catalyst carrier II；
5. stand, dry, be calcined, obtain the major catalyst.
The preparation key of catalyst of the present invention is the preparation of major catalyst, after major catalyst is obtained, by making master
Catalyst contacts the catalyst that can obtain the present invention with the accelerator.The mode that major catalyst is contacted with accelerator is without spy
Do not limit, the opportunity for contacting both is also not particularly limited.For example catalyst of the present invention can be used to chemically react
Before contact both and form the catalyst, both can also be made to be contacted in the reaction system that catalyst of the present invention is applied
Make catalyst in-situ preparation.
It was found by the inventors of the present invention that in above-mentioned technical proposal, activity component impregnation is used into ammonium fluosilicate, hydrogen at the same time
The catalyst obtained on fluoric acid, the compound modified carrier containing Rb and containing Cs either selectivity or 3- acetoxyl group propionic aldehyde
Yield has reached best.
The key of the present invention is the selection of catalyst, suitable skilled person will know how determining according to actual needs
Reaction temperature, the reaction time, 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, using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis, is pressed after cooling, decompression, separation
Row formula calculates the conversion ratio of vinyl acetate and the yield and selectivity of 3- acetoxyl group propionic aldehyde：
Compared with prior art, key of the invention is that catalyst carrier is entered using fluorine-containing compound and alkali metal
Row is modified, is conducive to improving the activity and stability of major catalyst, so as to improve yield and the choosing of 3- acetoxyl group propionic aldehyde
Selecting property.
Test result indicate that, during using the present invention, 3- acetoxyl group propionic aldehyde yields selectively reach up to 85.16%
95.08%, achieve preferable technique effect.Simultaneously using ammonium fluosilicate, hydrogen especially in catalyst carrier modifying process
Fluoric acid, when being cooperateed with containing Rb and containing Cs, achieve more prominent technique effect.Further is made to the present invention below by embodiment
Illustrate.
Embodiment
【Embodiment 1】
Catalyst carrier II preparation：By the ammonium fluosilicate aqueous solution 0.80L of the F containing 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.60g rubidium hydroxides powder with it is dense
Spend to be sufficiently mixed for 35wt% Ludox 5.0g and obtain coating liquid, coating liquid is uniformly sprayed at 1.0L catalyst carrier precursors
On I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, F contains
Measure as 2.45g/L, Rb contents are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 85.16%, selectivity be 95.08%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde 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
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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 72.47%, selectivity be 89.62%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 2】
For【Embodiment 1】Comparative example.
Catalyst carrier II preparation：By the ammonium fluosilicate aqueous solution 0.80L of the F containing 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.Then after 500 DEG C of roastings of Muffle furnace
Obtain catalyst carrier II.Carrier is through with IC analysis, F contents are 2.45g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 72.86%, selectivity be 91.28%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Comparative example 3】
For【Embodiment 1】Comparative example.
Catalyst carrier II preparation：It is that 35wt% Ludox 5.0g is fully mixed by 0.60g rubidium hydroxides powder and concentration
Conjunction obtains coating liquid, coating liquid is uniformly sprayed on 1.0L catalyst carrier precursors I, 100 DEG C of dryings, in Muffle furnace 500
DEG C roasting after obtain the catalyst carrier II.Carrier is through with icp analysis, Rb contents are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 74.59%, selectivity be 90.38%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
By compared with Example 1 as can be seen that the catalyst carrier that the present invention is used, contains F and alkali metal while using
The performance of modified catalysts is than the carrier without any modification, than only with the compound modified carrier containing F, than only using alkali gold
The performance for the catalyst that the modified carrier of category is made is more excellent, and the selectivity and yield of 3- acetoxyl group propionic aldehyde will be high, this from
Embodiment 1, the data of comparative example 1~3, which can be seen that, illustrates there is good association between compound and alkali metal containing F
Same-action.
【Embodiment 2】
Catalyst carrier II preparation：By the ammonium fluoride aqueous solution 0.80L's of the F containing the 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.1.07g is aoxidized into lithium powder is with concentration
35wt% Ludox 5.0g, which is sufficiently mixed, obtains coating liquid, coating liquid is uniformly sprayed on 1.0L catalyst carrier precursors I,
100 DEG C of dryings, the catalyst carrier II is obtained after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, and F contents are
2.45g/L, Li content are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 85.27%, selectivity be 95.03%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 3】
Catalyst carrier II preparation：By the hydrofluoric acid aqueous solution 0.80L's of the F containing the 0.52g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.It is by 0.16g sodium oxide molybdenas powder and concentration
35wt% Ludox 1.0g, which is sufficiently mixed, obtains coating liquid, coating liquid is uniformly sprayed on 1.0L catalyst carrier precursors I,
100 DEG C of dryings, the catalyst carrier II is obtained after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, and F contents are
0.51g/L, Na content are 0.11g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 85.44%, selectivity be 95.12%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 4】
Catalyst carrier II preparation：By the ammonium acid fluoride aqueous solution 0.80L of the F containing 5.00g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 1.43g potassium hydroxide powders with it is dense
Spend to be sufficiently mixed for 35wt% Ludox 5.0g and obtain coating liquid, coating liquid is uniformly sprayed at 1.0L catalyst carrier precursors
On I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, F contains
Measure as 4.90g/L, K contents are 0.99g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 85.38%, selectivity be 95.26%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 5】
Catalyst carrier II preparation：The 5- fluorosalicylic acid aqueous solution 0.80L and 1.0L of the F containing 2.50g is a diameter of
5.6mm spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.56g cesium hydroxide powder
It is sufficiently mixed with concentration for 35wt% Ludox 5.0g and obtains coating liquid, coating liquid is uniformly sprayed at 1.0L catalyst carriers
In precursor I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and ICP points
Analysis, F contents are 2.45g/L, and Cs contents are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 85.73%, selectivity be 95.11%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 6】
Catalyst carrier II preparation：By the ammonium fluosilicate aqueous solution 0.80L of the F containing 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.56g cesium hydroxides powder with it is dense
Spend to be sufficiently mixed for 35wt% Ludox 5.0g and obtain coating liquid, coating liquid is uniformly sprayed at 1.0L catalyst carrier precursors
On I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, F contains
Measure as 2.45g/L, Cs contents are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 85.09%, selectivity be 95.37%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 7】
Catalyst carrier II preparation：By the ammonium fluosilicate aqueous solution 0.80L of the F containing 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.60g rubidium hydroxides powder with it is dense
Spend to be sufficiently mixed for 35wt% Ludox 5.0g and obtain coating liquid, coating liquid is uniformly sprayed at 1.0L catalyst carrier precursors
On I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, F contains
Measure as 2.45g/L, Rb contents are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 0.3MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 1.0MPa, while agitating 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：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 76.16%, selectivity be 93.79%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 8】
Catalyst carrier II preparation：By the ammonium fluosilicate aqueous solution 0.80L of the F containing 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.60g rubidium hydroxides powder with it is dense
Spend to be sufficiently mixed for 35wt% Ludox 5.0g and obtain coating liquid, coating liquid is uniformly sprayed at 1.0L catalyst carrier precursors
On I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier is through with IC and icp analysis, F contains
Measure as 2.45g/L, Rb contents are 0.49g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen are until pressure 15.0MPa, improves mixing speed to 800rpm, while agitating heating is warming up to reaction temperature
Degree, controlling reaction temperature is 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 84.39%, selectivity be 92.47%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 9】
Catalyst carrier II preparation：By the ammonium fluosilicate aqueous solution 0.80L of the F containing 2.50g and a diameter of 5.6mm of 1.0L
Spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.30g cesium hydroxides, 0.29g hydrogen
Rubidium oxide powder is sufficiently mixed for 35wt% Ludox 5.0g with concentration and obtains coating liquid, and coating liquid is uniformly sprayed at 1.0L
On catalyst carrier precursor I, 100 DEG C of dryings obtain the catalyst carrier II after 500 DEG C of roastings of Muffle furnace.Carrier through with
IC and icp analysis, F contents are 2.45g/L, and Rb contents are 0.23g/L, and Cs contents are 0.26g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 86.95%, selectivity be 97.24%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis with embodiment 1 and embodiment 6 by embodiment 9, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, Rb and Cs have synergy.
【Embodiment 10】
Catalyst carrier II preparation：The 5- fluorosalicylic acid aqueous solution 0.80L and 1.0L of the F containing 2.50g is a diameter of
5.6mm spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.By 0.30g cesium hydroxides,
0.29g rubidium hydroxides powder is sufficiently mixed for 35wt% Ludox 5.0g with concentration and obtains coating liquid, and coating liquid is uniformly sprayed
It is sprinkled upon on 1.0L catalyst carrier precursors I, 100 DEG C of dryings, the catalyst carrier II is obtained after 500 DEG C of roastings of Muffle furnace.
Carrier is through with IC and icp analysis, F contents are 2.45g/L, and Rb contents are 0.23g/L, and Cs contents are 0.26g/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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 87.04%, selectivity be 97.06%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
【Embodiment 11】
Catalyst carrier II preparation：By the ammonium fluosilicate of the F containing 1.00g and the 5- fluorosalicylic acids containing 1.50gF it is water-soluble
The liquid 0.8L and a diameter of 5.6mm of 1.0L spherical SiO2Carrier is mixed, and 100 DEG C of dryings obtain the catalyst carrier precursor I.
0.30g cesium hydroxides, 0.29g rubidium hydroxides powder and concentration are sufficiently mixed for 35wt% Ludox 5.0g and obtain coating liquid,
Coating liquid is uniformly sprayed on 1.0L catalyst carrier precursors I, 100 DEG C of dryings, urged after 500 DEG C of roastings of Muffle furnace
Agent carrier II.Carrier is through with IC and icp analysis, F contents are 2.45g/L, and Rb contents are 0.23g/L, and Cs contents are 0.26g/
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 major catalyst.Major catalyst is through icp analysis, and Rh contents are 6.44g/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, are first discharged with argon gas in kettle and are pressurized to 1.0MPa after air, then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm up to pressure 5.0MPa, while agitating heating is warming up to reaction temperature,
Controlling reaction temperature is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained is cooled down, depressurized, separation, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Be computed 3- acetoxyl group propionic aldehyde yield be 88.79%, selectivity be 98.15%, for convenience of description and ratio
Compared with, by support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and
Selectivity is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis with embodiment 9 and embodiment 10 by embodiment 11, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, ammonium fluosilicate and 5- fluorosalicylic acids have synergy with alkali metal Rb, Cs.
Table 1
Table 2
Claims (10)
1. the method that vinyl acetate hydroformylation synthesizes 3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as original
Material, reaction synthesis 3- acetoxyl group propionic aldehyde is carried out using toluene as solvent, in the presence of catalyst, and the catalyst includes major catalyst
And accelerator, the major catalyst include carrier, active component；The active component uses the compound of rhodium；The accelerator
At least one in organic amine and organophosphor；The carrier is to contain cated two with its modified surface of fluorochemical
Silica；The coating is bonded in the titanium dioxide of the carrier surface by modified metal element and by the modified metal element
Silicon bonding is constituted；The fluorine-containing constituent content is 0.50~5.00g/L；Modified metal constituent content is 0.010~1.00g/
L；At least one of the modified metal element in alkali metal.
2. according to the method described in claim 1, it is characterised in that the compound of the rhodium is RhCl3。
3. according to the method described in claim 1, it is characterised in that the accelerator in pyridine and triphenyl phosphorus at least
It is a kind of.
4. according to the method described in claim 1, it is characterised in that the fluorine-containing compound be selected from ammonium fluosilicate, ammonium fluoride,
At least one in hydrofluoric acid, ammonium acid fluoride and 5- fluorosalicylic acids.
5. according to the method described in claim 1, it is characterised in that the alkali metal is in Li, Na, K, Rb and Cs
It is at least one.
6. according to the method described in claim 1, it is characterized in that the temperature of reaction is 50~180 DEG C.
7. according to the method described in claim 1, it is characterized in that the pressure of reaction is 1.0~15.0MPa.
8. according to the method described in claim 1, it is characterized in that the time of reaction is 1.0~15.0h.
9. according to the method described in claim 1, it is characterized in that carbon monoxide and hydrogen volume ratio are 0.10~10.0.
10. according to the method described in claim 1, it is characterized in that described major catalyst is using the method system comprised the following steps
It is standby：
1. fluorine-containing compound is configured to aqueous solution impregnation of silica, is dried to obtain the catalyst carrier precursor I；
2. the hydroxide or oxide of the modified metal element and Ludox are mixed to get coating liquid；
3. above-mentioned coating liquid is coated to precursor carrier I surfaces, dried, roasting obtains the catalyst carrier II；
4. by the composition of catalyst by RhCl3Mixed with the catalyst carrier II；
5. stand, dry, be calcined, obtain the major catalyst.
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