CN105585500B - The method that methyl acetate prepares vinyl acetate - Google Patents
The method that methyl acetate prepares vinyl acetate Download PDFInfo
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- CN105585500B CN105585500B CN201410577444.1A CN201410577444A CN105585500B CN 105585500 B CN105585500 B CN 105585500B CN 201410577444 A CN201410577444 A CN 201410577444A CN 105585500 B CN105585500 B CN 105585500B
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Abstract
The present invention relates to the method that methyl acetate prepares vinyl acetate, mainly solves the problems, such as that methyl acetate is successively low through being carbonylated, cracking the yield of vinyl acetate and selectivity when route prepares vinyl acetate.It is main to use the technical scheme comprised the following steps：Methyl acetate carbonylation obtains ethylidene diacetate；Ethylidene diacetate obtains vinyl acetate through cracking；Carbonylating catalyst includes major catalyst and co-catalyst, and major catalyst includes carrier, active component；Active component uses the compound of rhodium；The co-catalyst is iodide；The carrier is that aluminized coating is contained and with the element modified silica of modified metal in its surface；The aluminium content is 1.00~10.00g/L；Modified metal constituent content is 0.010~1.00g/L；The modified metal element is selected from least one of IVB metallic elements.
Description
Technical field
The present invention relates to the method that methyl acetate prepares vinyl acetate.
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.
United States Patent (USP) US5354886 is (entitled：Catalysts on inorganic carriers for
Producing ethylidene diacetate) mention RhCl3Or rhodium compound is supported on diatomite, titanium oxide, oxygen
Change and loaded catalyst is made on magnesium, aluminum oxide and zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, in polarity
Under solvent condition, the reaction synthesis ethylidene diacetate under above-mentioned catalyst.US4843170 is (entitled：Process for
Produing vinyl acetate) in mention utilize halogen acids, sulfuric acid, nitric acid, polyphosphoric acid, benzene sulfonic acid, alkyl sulfonic acid etc. make
The catalyst of vinyl acetate is prepared for ethylidene diacetate cracking.Acetic acid second during synthesizing vinyl acetate be present in the above method
The problem of alkene yield is low and selective not high.
The content of the invention
The problem of technical problems to be solved by the invention are that vinyl acetate yield is low and selectivity is not high, there is provided Yi Zhongxin
The methyl acetate method for preparing vinyl acetate, this method has the characteristics of vinyl acetate high income and high selectivity.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Methyl acetate prepares vinyl acetate
Method, comprise the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, carried out in the presence of carbonylating catalyst
Carbonylation obtains ethylidene diacetate；(2) in the presence of catalyst for cracking, ethylidene diacetate cracking is made to obtain acetic acid second
Alkene；Wherein, the carbonylating catalyst includes major catalyst and co-catalyst, and major catalyst includes carrier, active component；Activity
Component uses the compound of rhodium；The co-catalyst is iodide；The carrier is that aluminized coating is contained and with modified golden in its surface
Belong to element modified silica；The aluminium content is 1.00~10.00g/L；Modified metal constituent content be 0.010~
1.00g/L；The modified metal element is selected from least one of IVB metallic elements.
The compound of rhodium described in above-mentioned technical proposal is preferably RhCl3.The iodide are preferably iodomethane.The aluminium
Coating material is selected from least one of aluminium hydroxide, boehmite, boehmite and aluminum phosphate.More preferably described aluminized coating
Include aluminium hydroxide and aluminum phosphate simultaneously.The IVB metallic elements are selected from least one of Ti, Zr and Hf.It is more preferably described
IVB metallic elements include Hf and Zr simultaneously.
In above-mentioned technical proposal, the optional preparation method of the major catalyst, comprise the following steps：
1. the aluminized coating raw material and Ludox are mixed to get coating liquid；
2. above-mentioned coating liquid is coated into silica surface, dry, roasting obtains the catalyst carrier precursor I；
3. the compound of the metallic element containing IVB is configured into the aqueous solution to be immersed on catalyst carrier precursor I, it is dried to obtain
The catalyst carrier II；
4. by the composition of catalyst by RhCl3Mixed with catalyst carrier II；
5. standing, drying, roasting, the major catalyst is obtained.
3. described drying temperature is preferably 80~120 DEG C to step in above-mentioned technical proposal.More preferably 100~120 DEG C.
The key of the inventive method is the selection of major catalyst, after major catalyst is obtained, by making major catalyst
Contacted with the co-catalyst and can obtain heretofore described carbonylating catalyst.Major catalyst contacts with co-catalyst
Mode is not particularly limited, and the opportunity for contacting both is also not particularly limited.Such as it can be used by catalyst of the present invention
Contact both before chemical reaction and form the catalyst, the reaction that both can also be made to be applied in catalyst of the present invention
Contact makes catalyst in-situ preparation in system.
It was found by the inventors of the present invention that in above-mentioned technical proposal, by activity component impregnation at the same time using aluminum phosphate, hydrogen-oxygen
Change aluminium and do aluminized coating raw material and with the catalyst obtained on Hf and Zr compound modified carrier either selectivity or vinegar
Sour yield of ethene has reached best.
The key of the present invention is the selection of carbonylating catalyst, and skilled person will know how true according to being actually needed
Determine the proportioning of suitable reaction temperature, reaction time, reaction pressure and material.But the temperature reacted in above-mentioned technical proposal
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.One oxygen
The mol ratio for changing carbon and hydrogen is preferably 0.10~10.0.
In the method for methyl acetate synthesis vinyl acetate of the present invention, after step (1) terminates, carbonylation can be mixed
Compound carries out separation acquisition target product ethylidene diacetate and carries out step (2) again, can also the double acetic acid Asias second of step (1) generation
Do not separated after ester and directly carry out step (2).The suitable catalyst for cracking of the known selection of those skilled in the art and determination are closed
Suitable cracking reaction temperature, time and material proportion.Conventional catalyst for cracking have Bronsted acid (such as HI, HBr, HCl, HF,
H2SO4、H3PO4、HNO3、H3BO3、HClO3、HBrO3、HIO3, polyphosphoric acid, alkyl sulfonic acid, benzene sulfonic acid etc.), lewis acid (such as
IIA, IIIA, IVA, VA, VIA, IIIB, IVB, VB, VIB, VIIB, VIII metal halogen compound).Preferred benzene sulphur in the present invention
Acid is used as catalyst for cracking, and suitable cracking temperature is preferably 100~180 DEG C；Cleavage reaction pressure preferably 0~1.0MPa；Split
It is preferably 10~60min to solve the reaction time；Benzene sulfonic acid catalyst for cracking accounts for the 3.0~7.0% of raw material total amount；The preferred acetic acid of solvent
At least one of with aceticanhydride.
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 vinyl acetate：
Compared with prior art, key of the invention is step (1) carbonylation catalyst agent carrier using containing aluminized coating and use
After IVB metallic elements are modified, be advantageous to improve the activity and stability of major catalyst, so as to improve the receipts of vinyl acetate
Rate and selectivity.
Test result indicates that the vinyl acetate yield prepared by the present invention selectively reaches 83.35%, taken up to 60.38%
Obtained preferable technique effect.Especially aluminium painting is done in step (1) carbonylation catalyst agent carrier using aluminum phosphate and aluminium hydroxide
Layer raw material and during with being modified collaboration containing Hf and metallic element containing Zr, achieves the technique effect more protruded.Below by implementation
The present invention is further elaborated for example.
Embodiment
【Embodiment 1】
Carbonylation catalyst agent carrier II preparation：The aluminium-hydroxide powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 0.6gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
100 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/
L。
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.38%, and selectivity is 83.35%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Comparative example 1】
For【Embodiment 1】Comparative example.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, by a diameter of 5.6mm of 1.0L spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings in above-mentioned maceration extract,
500 DEG C of roasting 5h are warming up in N2 atmosphere, obtain the major catalyst.The major catalyst is through icp analysis, Rh contents
7.20g/L。
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 50.27%, and selectivity is 75.78%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Comparative example 2】
For【Embodiment 1】Comparative example.
Carbonylation catalyst agent carrier II preparation：The aluminium-hydroxide powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier II.
The carrier is through with icp analysis, Al content 3.40g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 54.63%, and selectivity is 80.20%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Comparative example 3】
For【Embodiment 1】Comparative example.
Carbonylation catalyst agent carrier II preparation：By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L
It is immersed in a diameter of 5.6mm of 1.0L spherical SiO2On carrier, 100 DEG C are dried to obtain the catalyst carrier II.The carrier
Through with icp analysis, Zr contents 0.60g/L.
The preparation of major catalyst is carbonylated：RhCl33H2O containing 7.20gRh is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 54.78%, and selectivity is 80.42%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
The catalyst carrier used by can be seen that the present invention compared with Example 1, while use and contain aluminized coating and use
IVB metallic elements be modified the performance of rear catalyst than the carrier without any modification, than only using the compound modified of aluminium
Carrier, than only use catalyst made of the metal-modified carriers of IVB performance it is more excellent, the selectivity and yield of vinyl acetate are all
High, this can be seen that from the data of embodiment 1, comparative example 1~3 illustrates exist between the compound containing aluminium and IVB metals
Good synergy.
【Comparative example 4】
For【Embodiment 1】Comparative example.
Carbonylation catalyst agent carrier II preparation：The aluminium-hydroxide powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
100 DEG C of dryings, in N2500 DEG C of roasting 4h are warming up in atmosphere, obtain the catalyst carrier II.The carrier is through with ICP points
Analysis, Al content 3.40g/L, Zr content 0.60g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 55.04%, and selectivity is 80.36%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
By compared with Example 1 as can be seen that carrier is modified in dipping metallic element containing IVB, only to carrier progress
The performance for drying its catalyst prepared is better than catalyst performance to taking roasting to prepare after carrier drying, and this is from embodiment
1st, the data of comparative example 4 can be seen that.
【Comparative example 5】
For【Embodiment 1】Comparative example.
Carbonylation catalyst agent carrier II preparation：The aluminium-hydroxide powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier II.
The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 6.80gRh3·3H2O, the basic zirconium chloride containing 0.60gZr
(ZrOCl2·8H2O) it is dissolved in pure water, obtains maceration extract 500ml, catalyst carrier II described in 1.0L is immersed in above-mentioned leaching
In stain liquid, 3h is stood in 100 DEG C of dryings, in N2500 DEG C of roasting 5h are warming up in atmosphere, obtain the major catalyst.The master
For catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 54.43%, and selectivity is 80.53%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
By compared with Example 1 as can be seen that metal containing IVB is impregnated together with the active component of catalyst,
The performance of catalyst does not obtain preferable effect, and this can be seen that from the data of embodiment 1, comparative example 5.Illustrate the change containing aluminium
There is preferable synergy between compound and metal containing IVB.
【Embodiment 2】
Carbonylation catalyst agent carrier II preparation：It is 35wt% silicon by the boehmite powder of the Al containing 3.40g and concentration
Colloidal sol 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
100 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/
L。
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.40%, and selectivity is 83.14%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 3】
Carbonylation catalyst agent carrier II preparation：The boehmite powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
100 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/
L。
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.32%, and selectivity is 83.17%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 4】
Carbonylation catalyst agent carrier II preparation：It is 35wt% Ludox by the Aluminum phosphate powders of the Al containing 3.40g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I, 100 DEG C
It is dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, risen in N2 atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.51%, and selectivity is 83.48%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 5】
Carbonylation catalyst agent carrier II preparation：It is 35wt% Ludox by the Aluminum phosphate powders of the Al containing 3.40g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
Titanium tetrachloride hydrochloric acid solution 0.6L containing 0.60gTi is immersed on 1.0L catalyst carrier precursors I, 100 DEG C are dried to obtain institute
State catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Ti content 0.60g/L.
The preparation of major catalyst is carbonylated：RhCl33H2O containing 7.20gRh is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.34%, and selectivity is 83.26%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 6】
Carbonylation catalyst agent carrier II preparation：It is 35wt% Ludox by the Aluminum phosphate powders of the Al containing 3.40g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
The hydrochloric acid solution 0.6L of hafnium tetrachloride containing 0.60gHf is immersed on 1.0L catalyst carrier precursors I, 100 DEG C are dried to obtain
The catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Hf content 0.60g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.43%, and selectivity is 83.37%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 7】
Carbonylation catalyst agent carrier II preparation：It is 35wt% Ludox by the Aluminum phosphate powders concentration of the Al containing 1.00g
5.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.Will
Basic zirconium chloride (ZrOCl containing 0.10gZr2·8H2O) aqueous solution 0.1L is immersed on 1.0L catalyst carrier precursors I, and 80 DEG C dry
It is dry to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 1.00g/L, Zr content 0.10g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, risen in N2 atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 59.56%, and selectivity is 82.98%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 8】
Carbonylation catalyst agent carrier II preparation：The Aluminum phosphate powders of the Al containing 10.00g are molten for 35wt% silicon with concentration
Glue 40.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 1.00gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
120 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 10.00g/L, Zr content 1.00g/
L。
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, risen in N2 atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.55%, and selectivity is 83.19%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 9】
Carbonylation catalyst agent carrier II preparation：It is 35wt% Ludox by the Aluminum phosphate powders of the Al containing 3.40g and concentration
10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2On carrier,
1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined 4h under the conditions of 450 DEG C, obtains the catalyst carrier precursor I.
By the basic zirconium chloride (ZrOCl containing 0.2gZr2·8H2O), the hafnium tetrachloride hydrochloric acid solution 0.6L containing 0.4gHf is immersed in 1.0L and urged
On agent precursor carrier I, 100 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content
3.40g/L, Zr content 0.20g/L, Hf content 0.40g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 62.70%, and selectivity is 85.45%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
Found out on year-on-year basis by embodiment 9 and embodiment 4 and embodiment 6, improving the selectivity of vinyl acetate and yield side
Face, Zr and Hf have synergy.
【Embodiment 10】
Carbonylation catalyst agent carrier II preparation：By the Aluminum phosphate powders of the Al containing 2.00g, the hydroxide of the Al containing 1.40g
Aluminium powder is that 35wt% Ludox 10.0g is sufficiently mixed to obtain coating liquid with concentration, and it is straight coating liquid to be uniformly sprayed at 1.0L
Footpath is on 5.6mm spherical sio2 carrier, and 1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined under the conditions of 450 DEG C
4h, obtain the catalyst carrier precursor I.By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in
On 1.0L catalyst carrier precursors I, 100 DEG C are dried to obtain the catalyst carrier II.The carrier with icp analysis, Al through being contained
Measure 3.40g/L, Zr contents 0.60g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 62.61%, and selectivity is 85.27%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
Found out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 4, improving the selectivity of vinyl acetate and yield side
Face, aluminium hydroxide and aluminum phosphate have synergy.
【Embodiment 11】
Carbonylation catalyst agent carrier II preparation：By the Aluminum phosphate powders of the Al containing 2.00g, the hydroxide of the Al containing 1.40g
Aluminium powder is that 35wt% Ludox 10.0g is sufficiently mixed to obtain coating liquid with concentration, and it is straight coating liquid to be uniformly sprayed at 1.0L
Footpath is 5.6mm spherical SiO2On carrier, 1h is placed under ventilation condition, 100 DEG C of dryings, is then calcined under the conditions of 450 DEG C
4h, obtain the catalyst carrier precursor I.By the basic zirconium chloride (ZrOCl28H2O) containing 0.60gZr, four containing 0.40gHf
Hafnium chloride hydrochloric acid solution 0.6L is immersed on 1.0L catalyst carrier precursors I, and 100 DEG C are dried to obtain the catalyst carrier II.
The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.20g/L, Hf content 0.40g/L.
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 7.5MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 168 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.5h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 64.80%, and selectivity is 87.44%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, improving the selectivity and yield of vinyl acetate
Aspect, aluminium hydroxide, aluminum phosphate and Zr, Hf have synergy.
【Embodiment 12】
Carbonylation catalyst agent carrier II preparation：The aluminium-hydroxide powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
100 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/
L。
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 3.0MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 130 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 1:After 10, sustained response 3.0h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 53.22%, and selectivity is 82.65%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 13】
Carbonylation catalyst agent carrier II preparation：The aluminium-hydroxide powder of the Al containing 3.40g is molten for 35wt% silicon with concentration
Glue 10.0g is sufficiently mixed to obtain coating liquid, coating liquid is uniformly sprayed at a diameter of 5.6mm of 1.0L spherical SiO2Carrier
On, 1h is placed under ventilation condition, 100 DEG C of dryings, then 4h is calcined under the conditions of 450 DEG C, before obtaining the catalyst carrier
Body I.By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed on 1.0L catalyst carrier precursors I,
100 DEG C are dried to obtain the catalyst carrier II.The carrier is through with icp analysis, Al content 3.40g/L, Zr content 0.60g/
L。
The preparation of major catalyst is carbonylated：By the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract
580ml, catalyst carrier II described in 1.0L is immersed in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, in N2Risen in atmosphere
Temperature obtains the major catalyst to 500 DEG C of roasting 5h.For the major catalyst through icp analysis, Rh contents are 7.20g/L.
The synthesis of vinyl acetate：
Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid
Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide
With hydrogen until pressure 10.0MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti-
It is 200 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 10:After 1, sustained response 10.0h, stop reaction.By reactor
Room temperature is down to, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.96%, and selectivity is 83.03%, for convenience of description and compares, will carry
Modifies condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of vinyl acetate and selectivity arrange respectively
In Tables 1 and 2.
Table 1
Table 2
Claims (9)
1. the method for methyl acetate synthesis vinyl acetate, comprises the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as
Raw material, carbonylation acquisition ethylidene diacetate is carried out in the presence of carbonylating catalyst；(2) exist in catalyst for cracking
Under, ethylidene diacetate cracking is obtained vinyl acetate；Wherein, the carbonylating catalyst includes major catalyst and co-catalysis
Agent, major catalyst include carrier, active component；Active component uses the compound of rhodium；The co-catalyst is iodide；It is described
Carrier is that aluminized coating is contained and with the element modified silica of modified metal in its surface；The aluminized coating raw material is aluminium hydroxide
And aluminum phosphate, the aluminium content are 1.00~10.00g/L；Modified metal constituent content is 0.010~1.00g/L；The modification
Metallic element is selected from least one of IVB metallic elements.
2. according to the method for claim 1, it is characterised in that the compound of the rhodium is RhCl3。
3. according to the method for claim 1, it is characterised in that the iodide are iodomethane.
4. according to the method for claim 1, it is characterised in that the IVB metallic elements in Ti, Zr and Hf at least
It is a kind of.
5. according to the method for claim 1, it is characterised in that the temperature of the carbonylation is 130~200 DEG C.
6. according to the method for claim 1, it is characterised in that the pressure of the carbonylation is 3.0~10.0MPa.
7. according to the method for claim 1, it is characterised in that carbon monoxide and hydrogen volume ratio in the carbonylation
For 0.10~10.0.
8. according to the method for claim 1, it is characterized in that the time of the carbonylation is 3.0~10.0h.
9. according to the method for claim 1, it is characterised in that the preparation method of major catalyst, comprise the following steps：
1. the aluminized coating raw material and Ludox are mixed to get coating liquid；
2. above-mentioned coating liquid is coated into silica surface, dry, roasting obtains the catalyst carrier precursor I；
3. the compound of the metallic element containing IVB is configured into the aqueous solution to be immersed on catalyst carrier precursor I, it is dried to obtain described
Catalyst carrier II；
4. by the composition of catalyst by RhCl3Mixed with catalyst carrier II；
5. standing, drying, roasting, the major catalyst is obtained.
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|---|---|---|---|---|
| EP0108539A1 (en) * | 1982-10-30 | 1984-05-16 | BP Chemicals Limited | Preparation of esters |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| CN101124043A (en) * | 2004-12-20 | 2008-02-13 | 国际人造丝公司 | Modified support materials for catalysts |
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2014
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|---|---|---|---|---|
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| EP0108539A1 (en) * | 1982-10-30 | 1984-05-16 | BP Chemicals Limited | Preparation of esters |
| CN101124043A (en) * | 2004-12-20 | 2008-02-13 | 国际人造丝公司 | Modified support materials for catalysts |
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