CN105268486B - Ethylidene diacetate catalyst and its application - Google Patents
Ethylidene diacetate catalyst and its application Download PDFInfo
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- CN105268486B CN105268486B CN201410329022.2A CN201410329022A CN105268486B CN 105268486 B CN105268486 B CN 105268486B CN 201410329022 A CN201410329022 A CN 201410329022A CN 105268486 B CN105268486 B CN 105268486B
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Abstract
The present invention relates to ethylidene diacetate catalyst and its application, mainly solves the problems, such as that ethylidene diacetate catalyst activity and selectivity is relatively low in the prior art.By using ethylidene diacetate catalyst, the catalyst includes major catalyst and co-catalyst, and the major catalyst includes carrier, active component；The activearm uses the compound of rhodium；The co-catalyst is iodide；The carrier is polymer；The polymer is selected from the technical scheme for being crosslinked at least one of poly- (N vinyl pyrrolidones), poly- (maleic anhydride of styrene), ammonification poly- (maleic anhydride of styrene) and benzylamine negative resin polymer and preferably solves the problem, available in the industrial production of vinyl acetate.
Description
Technical field
The present invention relates to ethylidene diacetate catalyst, preparation method and application.
Background technology
Vinyl acetate (VAc) is one of 50 kinds of maximum industrial chemicals of world wide production, is total to by autohemagglutination or with other monomers
It is poly-, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE) or common can be generated
The derivatives such as poly resin (EVA), vinyl acetate-chloride copolymer (EVC).These derivatives are widely used in adhesive, built
Cementing agent, coating, ink, leather processing, fiber process, emulsifying agent, water-solubility membrane and the soil for building coating, paper or fabric change
Good dose etc..
Ethene vapor phase method and acetylene in gas phase method technique are used inside and outside the producing country of vinyl acetate, belongs to petrochemical process
Route, from after rising C1 chemistry, in the 1980s, U.S. Ha Erkang (Halcon) companies and BP (BP) company are successively
It is proposed is prepared new technology-carbonyl process synthesizing vinyl acetate of vinyl acetate by methanol and synthesis gas.The technique is independent of oil
Work raw material, but by methyl acetate and the carbonylation of synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then pass through
Cross thermal cracking production vinyl acetate and acetic acid.The novel part of whole technique is the hydroformylation reaction of methyl acetate, is catalyzed
Agent radium chloride is simultaneously modified with beta-picoline and iodomethane, and carbon monoxide intercalation reaction is the key point of whole technology.
It is (entitled via US4,429,150 by the preparation method of methyl acetate synthesis ethylidene diacetate：
Manufacture of ethylidene diacetate) it is disclosed, i.e., with methyl acetate or methyl ether, carbon monoxide and hydrogen
For raw material, catalyst is using the double acetic acid Asias second of synthesis in the presence of VIII halide or acetate and phosphorous polar solvent
Ester.US5,354,886 is (entitled：Catalysts on inorganic carriers for producing
Ethylidene diacetate) mention RhCl3Or rhodium compound is supported on diatomite, titanium oxide, magnesia, aluminum oxide
With loaded catalyst is made on zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, under polar solvent conditions,
The reaction synthesis ethylidene diacetate under above-mentioned catalyst.Double vinegar during ethylidene diacetate is prepared be present in the above method
The problem of sour ethyl yield 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 ethylidene diacetate yield is low and selectivity is low, there is provided
A kind of new ethylidene diacetate catalyst, the catalyst have ethylidene diacetate high income to ethylidene diacetate selectivity
The characteristics of 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 double acetic acid using one of the above-mentioned technical problem catalyst
The synthetic method of ethyl.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Ethylidene diacetate catalyst,
The catalyst includes major catalyst and co-catalyst, and the major catalyst includes carrier, active component；The activearm uses
The compound of rhodium；The co-catalyst is iodide；The carrier is polymer；The polymer, which is selected from, is crosslinked poly- (N- ethene
Base pyrrolidones) (abbreviation PNVP), be crosslinked poly- (phenylethylene-maleic anhydride) (abbreviation PMAn), crosslinking the poly- (styrene-horse of ammonification
Carry out acid anhydrides) at least one of (abbreviation APMAn) and crosslinking benzylamine negative resin polymer；The preferably oxidized place of the polymer
Reason.
The compound of rhodium described in above-mentioned technical proposal is preferably RhCl3.The iodide are preferably iodomethane.It is described poly-
The degree of cross linking of compound is preferably 1~60%.
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 polymer support is carried out into oxidation processes, oxidation processes carrier is dried to obtain；
2. by the composition of catalyst by RhCl3Compound is configured to the aqueous solution and is immersed on the oxidation processes carrier；
3. standing, drying, the major catalyst is obtained.
1. and 3. described drying temperature is preferably independently 80~120 DEG C to step in above-mentioned technical proposal.More preferably 100
~120 DEG C.
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 co-catalyst.The mode that major catalyst contacts with co-catalyst does not have
There is special limitation, the opportunity for contacting both is also not particularly limited.Such as catalyst of the present invention can be used for chemistry
Contact both before reaction and form the catalyst, both can also be made in the reaction system that catalyst of the present invention is applied
Contact makes catalyst in-situ preparation.
Another key of the present invention is that oxidation processes have been carried out to polymer, the preferred dioxygen of oxidant of oxidation processes
At least one of water, nitric acid, hypochlorous acid, chloric acid and perchloric acid.More preferably hydrogen peroxide and perchloric acid hybrid oxidant.
It was found by the inventors of the present invention that in above-mentioned technical proposal, activity component impregnation is used into hydrogen peroxide and height at the same time
The catalyst obtained on the APMAn and benzylamine negative resin polymer support of chloric acid hybrid oxidant oxidation processes is either selective
Or EDDA yields have reached best.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of ethylidene diacetate, with
Methyl acetate, carbon monoxide and hydrogen are raw material, and using acetic acid as solvent, reaction in the presence of a catalyst generates double acetic acid Asias second
Ester.
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
130~200 DEG C；The pressure of reaction is preferably 3.0~10.0MPa；The time of reaction is preferably 3.0~10.0h.Carbon monoxide with
The mol ratio of hydrogen is preferably 0.1~10.0.
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 the carrier of catalyst has used oxidation processes post-consumer polymer, favorably
In the activity and stability that improve major catalyst, so as to improve the yield of ethylidene diacetate and selectivity.
Test result indicates that the ethylidene diacetate yield prepared by the present invention reaches 61.04%, selectively reach
84.81%, and on year-on-year basis using the prior art ethylidene diacetate of diatomite or silica selectively only 79.38%；Take
Obtained preferable technique effect.Especially in catalyst carrier using hydrogen peroxide and perchloric acid hybrid oxidant to APMAn and benzyl
When amine negative resin polymer carries out oxidation processes collaboration, more prominent technique effect, the work available for vinyl acetate are achieved
In industry production.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.04%, choosing
Selecting property is 84.81%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】Comparative example.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
The a diameter of 5.6mm of 1.0L spherical sio2 carrier impregnation stands 3h in 30 DEG C of dryings, obtains described sponsor in above-mentioned maceration extract
Agent.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.37g/L after measured.The yield for being computed ethylidene diacetate is 50.83%, choosing
Selecting property is 79.47%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Comparative example 2】
For【Embodiment 1】Comparative example.
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
The preparation of major catalyst：RhCl33H2O containing 7.50gRh is dissolved in pure water, obtains maceration extract 500ml,
1.0L polymer supports precursor I and above-mentioned maceration extract are sufficiently mixed, 3h 30 DEG C of dryings of vacuum is stood, obtains the main catalytic
Agent.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.37g/L after measured.The yield for being computed ethylidene diacetate is 53.73%, choosing
Selecting property is 80.21%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Comparative example 3】
For【Embodiment 1】Comparative example.
The preparation of carrier:By a diameter of 5.6mm of 1.0L spherical SiO2Concentration with double weight is 5wt% hydrogen peroxide
The aqueous solution is mixed, and carries out oxidation processes 4h, and oxidizing temperature is kept for 35 DEG C, the carrier after being dried to obtain oxidation processes at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
SiO after 1.0L oxidation processes2Carrier is sufficiently mixed with maceration extract, is stood 3h in 30 DEG C of dryings, is obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.37g/L after measured.The yield for being computed ethylidene diacetate is 50.92%, choosing
Selecting property is 79.38%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
The catalyst carrier used by can be seen that the present invention compared with Example 1, using oxidant to polymer supported
The performance of body oxidation processes rear catalyst than using conventional silica supports, than only using the not oxidised processing of polymer support
Carrier, than only, the ethylidene diacetate more excellent to the performance of catalyst made of the carrier of Normal silica with oxidant
Selectivity and yield will be high, this can be seen that from the data of embodiment 1, comparative example 1~3 illustrates to use oxidant oxygen
Polymer support after change processing has more preferable peptizaiton to catalyst activity component.
【Embodiment 2】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, PNVP
Preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.Take 13ml vinylpyrrolidones (PVP) and 7ml divinylbenzenes (DVB)
It is 35% single phase to be well mixed and be made into the degree of cross linking, adds the azodiisobutyronitrile (AIBN) of amount of monomer 0.5% (mass fraction)
Initiator be allowed to fully dissolving occur to suspend it is solidifying close reaction, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, PNVP polymer supports are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0LPNVP polymer supports are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.25%, choosing
Selecting property is 84.79%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 3】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, PMAn
Preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer
Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction) is allowed to fully dissolve generation and suspend to coagulate to close to react, through cleaning,
Wash, be dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, PMAn polymer supports are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0LPMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.38%, choosing
Selecting property is 84.64%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned,
APMAn preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer
Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates
Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0LAPMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.35g/L after measured.The yield for being computed ethylidene diacetate is 61.74%, choosing
Selecting property is 85.04%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 5】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the aqueous solution of nitric acid that the concentration of double weight is 5wt%, carries out oxidation processes
4h, oxidizing temperature are kept for 35 DEG C, benzylamine negative resin carrier are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.05%, choosing
Selecting property is 84.79%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the hypochloric acid water solution that the concentration of double weight is 2wt%, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.12%, choosing
Selecting property is 84.53%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the chloric acid aqueous solution that the concentration of double weight is 5wt%, carries out oxidation processes
4h, oxidizing temperature are kept for 35 DEG C, benzylamine negative resin carrier are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.01%, choosing
Selecting property is 84.49%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the high chloro acid solution that the concentration of double weight is 2wt%, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.56%, choosing
Selecting property is 84.93%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned,
APMAn preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl for adding aqueous phase quality 2% is warming up to 50 DEG C.18ml styrene (St) is taken to be well mixed with 2ml divinylbenzenes (DVB)
It is 1% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer
Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates
Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0LAPMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.07%, choosing
Selecting property is 84.62%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned,
APMAn preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.8ml styrene (St) is taken to be well mixed with 12ml divinylbenzenes (DVB)
It is 60% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer
Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates
Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0LAPMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 60.98%, choosing
Selecting property is 84.82%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 11】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl for adding aqueous phase quality 2% is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
By the hydrogen peroxide and perchloric acid mixed aqueous solution (wherein hydrogen peroxide of polymer support precursor I and double weight
Concentration be 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keep 35 DEG C,
100 DEG C are dried to obtain benzylamine negative resin carrier.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 62.77%, choosing
Selecting property is 85.91%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 8, in terms of EDDA selectivity and yield is improved,
Hydrogen peroxide and perchloric acid oxidation's atmosphere have synergy.
【Embodiment 12】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned,
APMAn preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer
Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates
Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
0.6L benzylamine negative resins carrier, 0.4L APMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, and it is dry to stand 30 DEG C of 3h vacuum
It is dry, obtain the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 62.64%, choosing
Selecting property is 85.97%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 4, in terms of EDDA selectivity and yield is improved,
Benzylamine negative resin carrier and APMAn polymer supports have synergy.
【Embodiment 13】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
By the hydrogen peroxide and perchloric acid mixed aqueous solution (wherein hydrogen peroxide of polymer support precursor I and double weight
Concentration be 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keep 35 DEG C,
100 DEG C are dried to obtain benzylamine negative resin carrier.
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned,
APMAn preparation process is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer
Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates
Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.
By the hydrogen peroxide and perchloric acid mixed aqueous solution (wherein hydrogen peroxide of polymer support precursor I and double weight
Concentration be 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keep 35 DEG C,
100 DEG C are dried to obtain APMAn polymer supports.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
0.6L benzylamine negative resins carrier, 0.4L APMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, and it is dry to stand 30 DEG C of 3h vacuum
It is dry, obtain the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 66.80%, choosing
Selecting property is 88.11%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12, improving EDDA selectivity and yield side
Face, benzylamine negative resin carrier, APMAn polymer supports and hydrogen peroxide, perchloric acid oxidation's atmosphere have synergy.
【Embodiment 14】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 3.0MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction
Temperature, controlling reaction temperature are 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1:After 10, sustained response 3.0h, stop anti-
Should.
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 Rh contents of the catalyst are 7.37g/L after measured.The yield for being computed ethylidene diacetate is 54.16%, choosing
Selecting property is 79.01%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
【Embodiment 15】
The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan
Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine
The preparation process of negative resin is as follows：
The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase
The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB)
It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to
Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH2OCH3、
(CH3)2After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.
Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation
4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.
The preparation of major catalyst：By the RhCl containing 7.50gRh3·3H2O is dissolved in pure water, obtains maceration extract 500ml, will
1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, are stood 3h 30 DEG C of dryings of vacuum, are obtained the major catalyst.
The synthesis of ethylidene diacetate：By 0.5mol acetic acid, 0.02mol major catalysts, 0.02mol iodomethane and
0.15mol methyl acetates are added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then
Carbon monoxide and hydrogen are passed through until pressure 10.0MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to instead
Temperature is answered, controlling reaction temperature is 200 DEG C, and the mol ratio of carbon monoxide and hydrogen is 10:After 1, sustained response 10.0h, 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 Rh contents of the catalyst are 7.36g/L after measured.The yield for being computed ethylidene diacetate is 61.98%, choosing
Selecting property is 84.25%, for convenience of description and is compared, and prepared by polymer support into the preparation with oxidation processes condition, catalyst
Condition, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in Tables 1 and 2 respectively.
Table 1
Table 2 (continued)
The (Continued) of table 2
| Yield Y (EDDA), % | Sel (EDDA), % | |
| Embodiment 1 | 61.04 | 84.81 |
| Comparative example 1 | 50.83 | 79.47 |
| Comparative example 2 | 53.73 | 80.21 |
| Comparative example 3 | 50.92 | 79.38 |
| Embodiment 2 | 61.25 | 84.79 |
| Embodiment 3 | 61.38 | 84.64 |
| Embodiment 4 | 61.74 | 85.04 |
| Embodiment 5 | 61.05 | 84.79 |
| Embodiment 6 | 61.12 | 84.53 |
| Embodiment 7 | 61.01 | 84.49 |
| Embodiment 8 | 61.56 | 84.93 |
| Embodiment 9 | 61.07 | 84.62 |
| Embodiment 10 | 60.98 | 84.82 |
| Embodiment 11 | 62.77 | 85.91 |
| Embodiment 12 | 62.64 | 85.97 |
| Embodiment 13 | 66.80 | 88.11 |
| Embodiment 14 | 54.16 | 79.01 |
| Embodiment 15 | 61.98 | 84.25 |
Claims (10)
1. the catalyst for synthesizing ethylidene diacetate, the catalyst includes major catalyst and co-catalyst, described to sponsor
Agent includes carrier, active component；The activearm uses the compound of rhodium；The co-catalyst is iodide；The carrier
For polymer；It is poly- that the polymer is selected from crosslinking（NVP）, crosslinking it is poly-（Phenylethylene-maleic anhydride）, crosslinking
Ammonification gathers（Phenylethylene-maleic anhydride）With crosslinking at least one of benzylamine negative resin polymer；The catalyst, which uses, to be included
It is prepared by the method for following steps：
1. the polymer support is carried out into oxidation processes, oxidation-treated carrier is dried to obtain；
2. by the composition of catalyst by RhCl3Compound is configured to the aqueous solution and is immersed on the oxidation-treated carrier；
3. standing, drying, the major catalyst is obtained.
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 iodide are iodomethane.
4. catalyst according to claim 1, it is characterised in that the degree of cross linking of the polymer is 1~60%.
5. as the preparation method of the catalyst described in claim 1, comprise the following steps：
1. the polymer support is carried out into oxidation processes, oxidation-treated carrier is dried to obtain；
2. by the composition of catalyst by RhCl3Compound is configured to the aqueous solution and is immersed on the oxidation-treated carrier；
3. standing, drying, the major catalyst is obtained.
6. the preparation method of catalyst according to claim 5, it is characterised in that step 1. and 3. described drying temperature
Independently elect 80~120 DEG C as.
7. the synthetic method of ethylidene diacetate, using methyl acetate, carbon monoxide and hydrogen as raw material, using acetic acid as solvent,
Ethylidene diacetate is synthesized in the presence of catalyst any one of Claims 1 to 4.
8. synthetic method according to claim 7, it is characterized in that the temperature of reaction is 130~200 DEG C, the pressure of reaction is
3.0~10.0MPa.
9. synthetic method according to claim 7, it is characterized in that the time of reaction is 3.0~10.0h.
10. synthetic method according to claim 7, it is characterized in that carbon monoxide and hydrogen volume ratio are 0.1~10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086741A (en) * | 1992-08-31 | 1994-05-18 | 赫希斯特人造丝公司 | Polymeric carbonylation catalyst system |
| CN1834083A (en) * | 2005-03-14 | 2006-09-20 | 北京化工大学 | Prepn. of vinyl acetate by carbinol and synthetic gas |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
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| JP2013544629A (en) * | 2010-09-29 | 2013-12-19 | ビーエーエスエフ ソシエタス・ヨーロピア | Polymer-assisted synthesis of supported metal catalysts |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086741A (en) * | 1992-08-31 | 1994-05-18 | 赫希斯特人造丝公司 | Polymeric carbonylation catalyst system |
| CN1834083A (en) * | 2005-03-14 | 2006-09-20 | 北京化工大学 | Prepn. of vinyl acetate by carbinol and synthetic gas |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
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