CN105585492B - Vinyl acetate prepares method used - Google Patents
Vinyl acetate prepares method used Download PDFInfo
- Publication number
- CN105585492B CN105585492B CN201410575045.1A CN201410575045A CN105585492B CN 105585492 B CN105585492 B CN 105585492B CN 201410575045 A CN201410575045 A CN 201410575045A CN 105585492 B CN105585492 B CN 105585492B
- Authority
- CN
- China
- Prior art keywords
- vinyl acetate
- catalyst
- reaction
- method used
- prepares method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Method used is prepared the present invention relates to 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.Method used is prepared by using vinyl acetate, is comprised the following steps：Methyl acetate carbonylation obtains ethylidene diacetate；Ethylidene diacetate obtains vinyl acetate through cracking；The carbonylating catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline-earth metal and the technical scheme selected from least one of VIB and VA metallic element, the technical problem is preferably resolved, available in the industrial production of vinyl acetate.
Description
Technical field
Method used is prepared the present invention relates to vinyl acetate.
Background technology
Vinyl acetate, i.e. vinyl acetate (vinyl acetate, abbreviation VAC or VAM), are water white transparency at room temperature
Inflammable liquid, the ether fragrance with sweet tea.It is one of Organic Chemicals that yield is larger in the world, and it is poly- to be widely used in production
Vinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal resin etc.
A series of chemical industry and fiber product, are widely used in all trades and professions.
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
Vinyl acetate prepare method used, 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：Vinyl acetate prepares method used,
Comprise the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, carbonyl is carried out in the presence of carbonylating catalyst
Change reaction and obtain ethylidene diacetate；(2) in the presence of catalyst for cracking, ethylidene diacetate cracking is made to obtain vinyl acetate；
Wherein, the carbonylating catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline-earth metal
With selected from least one of VIB and VA metallic element.It is preferred that the active component is simultaneously including rhodium, alkaline-earth metal, selected from VIB
At least one of metallic element and selected from least one of VA metallic elements.Now VIB metallic element and VA metal
There is synergy in terms of vinyl acetate selectivity and yield is improved between element.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, the vib metal preferably is selected from least one of chromium, molybdenum and tungsten.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, as most preferred technical scheme, the active component simultaneously including rhodium, alkaline-earth metal,
Chromium and antimony element；Such as the active component rhodium, magnesium, strontium, chromium and antimony element when being made up of.
In above-mentioned technical proposal, the content of rhodium is preferably 3.00~15.00g/L in the carbonylating catalyst, more preferably
For 5.0~10.0g/L；The content of alkaline-earth metal is preferably 0.10~5.00g/L in the carbonylating catalyst, more preferably
0.50~3.00g/L；In the carbonylating catalyst selected from VIB and VA at least one content of metal be preferably 0.50
~8.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the carbonylating catalyst is preferably 50~
300m2/ g, more preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.Above-mentioned technology
Iodide described in scheme are preferably iodomethane.
In above-mentioned technical proposal, the optional preparation method of the carbonylating catalyst, comprise the following steps：
1. by catalyst composition by the compound of rhodium, the compound of alkaline-earth metal, VIB and VA metallic compound it is molten
Liquid mixes with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. rhodium preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate
At least one of.The compound of the step 1. alkaline-earth metal preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkali
At least one of earth metal nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate.The step 1. vib metal chemical combination
At least one of the preferred chromic acetate of thing, chromic nitrate, chromium chloride, molybdenum pentachloride and sodium tungstate.1. step metallizes in the VA
Compound preferably is selected from least one of basic bismuth carbonate, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride.
2. the drying temperature is 80~120 DEG C, more preferably 100~120 DEG C to step.
In above-mentioned technical proposal, by catalyst composition by the compound including rhodium, the compound of alkaline-earth metal, VIB and
Metallic compound is not particularly limited with carrier hybrid mode in VA, and the opportunity that their aqueous solution contacts with carrier is also without spy
Do not limit.Such as can by the present invention by the composition of catalyst by the compound including rhodium, the compound of alkaline-earth metal, VIB
First mixed with metallic compound in VA and be dissolved in water or mixed again after their compound is sequentially formed into the aqueous solution
Contacted with carrier, can contact with carrier to obtain the catalyst with different order.
The key of the inventive method is the selection of carbonylating catalyst, after carbonylating catalyst is obtained, by making
Carbonylating catalyst contacts with the co-catalyst and can be used to carbonylation.Carbonylating 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 urged by present invention carbonylation
Agent is used to before chemically reacting make both contact form the catalyst, and both can also be made to be applied in catalyst of the present invention
Reaction system in contact make catalyst in-situ preparation.
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 that the active component of step (1) carbonylating catalyst is included necessarily
Amount rhodium, alkaline-earth metal and selected from least one of VIB and VA metallic element, be advantageous to improve the active of catalyst and stably
Property, so as to improve the yield of vinyl acetate and selectivity.
Test result indicates that the vinyl acetate yield prepared by the present invention selectively reaches 83.34%, taken up to 60.45%
Obtain active component in preferable technique effect, especially carbonylating catalyst while include rhodium, alkaline-earth metal, in VIB
At least one metallic element and during selected from least one of VA metallic elements, achieve more prominent technique effect, can
For in the synthesis of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and the Cr containing 3.40g RhCl3·3H2O、
MgCl2And CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g,
Pore volume is 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
The catalyst.The carbonylating catalyst is through icp analysis, and Rh contents are 6.50g/L, Mg contents 1.70g/L, Cr content
3.40g/L。
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.45%, and selectivity is 83.34%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 2】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and the Sb containing 3.40g RhCl3·3H2O、
MgCl2And Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, pore volume are
0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/L, Sb content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.29%, and selectivity is 83.53%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of carbonylating catalyst：By Rh containing the 6.50g and Mg containing 1.70g RhCl3·3H2O and MgCl2It is fully mixed
Conjunction is dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, pore volume 0.96, a diameter of 5.6mm's
Spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylation is urged
For agent through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 51.31%, and selectivity is 71.67%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
By compared with embodiment 1~2 as can be seen that the carbonylating catalyst that uses of the present invention, using containing Rh, Mg simultaneously
With Cr active components while property of the ratio of the catalyst performance containing Rh, Mg and Sb active component containing only Rh, Mg active constituent catalyst
Can be more excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：By Rh containing 5.00g, Be containing 0.50g and the Cr containing 1.00g Rh (OAc)3、
BeSO4·4H2O and Cr (OAc)3·6H2O, which is sufficiently mixed, to be dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract 400ml,
Than surface it is 150m by 1.0L2/ g, pore volume 0.90, a diameter of 5.6mm spherical Al2O3Carrier impregnation in above-mentioned maceration extract,
2h is stood in 80 DEG C of dryings, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 5.00g/L, Be
Content 0.50g/L, Cr content 1.00g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 59.63%, and selectivity is 83.08%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of carbonylating catalyst：By Rh containing 10.00g, Ca containing 3.00g and the Cr containing 5.00g Rh (NO3)3、Ca
(NO3)2·4H2O and Cr (NO3)3·9H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
200m2/ g, pore volume 1.00, a diameter of 5.6mm spherical SiO2It is dry in 120 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 10.00g/L, Ca contents 3.00g/L, Cr
Content 5.00g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.81%, and selectivity is 83.23%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 5】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Sr containing 1.70g and the Mo containing 3.40g RhCl3·3H2O、Sr
(OAC)2·0.5H2O and MoCl5It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 175m by 1.0L2/
G, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.The carbonylating catalyst is through icp analysis, and Rh contents are 6.50g/L, Sr contents 1.70g/L, Mo content
3.40g/L。
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 83.50%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Ba containing 1.70g and the W containing 3.40g Rh (SO4)3, BaO and
(NH4)10W12O41·4H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, hole
Hold for 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Ba content 1.70g/L, W content 3.40g/
L。
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.37%, and selectivity is 83.87%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g RhCl3·3H2O、
MgCl2(BiO)2CO3·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
175m2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/L, Bi
Content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.25%, and selectivity is 83.30%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g RhCl3·3H2O、
MgCl2And Bi2(SO4)3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L
It is 175m than surface2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, and Rh contents are 6.50g/L, Mg contents
1.70g/L, Bi content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.41%, and selectivity is 83.22%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g RhCl3·3H2O、
MgCl2And Bi2O3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 175m2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/
L, Bi content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.28%, and selectivity is 83.54%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g RhCl3·3H2O、
MgCl2And BiCl3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 175m2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/
L, Bi content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 3.0MPa
Temperature is 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1:After 10, sustained response 3.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 57.89%, and selectivity is 78.85%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 11】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and RhCl containing 3.40gSb3·3H2O、
MgCl2And Sb2O3It is sufficiently mixed and is dissolved in the aqueous solution of nitric acid that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 175m2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/
L, Sb content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 10.0MPa
Temperature is 200 DEG C, and the mol ratio of carbon monoxide and hydrogen is 10:After 1, sustained response 10.0h, 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 0.35MPa 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 60.92%, and selectivity is 82.94%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 12】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 1.70g and RhCl containing 3.40gSb3·3H2O、
MgCl2And Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, pore volume are
0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg contents 1.70g/L, Sb content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.42%, and selectivity is 83.49%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 13】
The preparation of carbonylating catalyst：By Rh containing 6.50g, the RhCl containing the 1.70gSr and Cr containing 3.40g3·3H2O、
SrCl2·6H2O and CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
175m2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Sr contents 1.70g/L, Cr
Content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 60.35%, and selectivity is 83.28%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 14】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 0.73g, containing the 0.97gSr's and Sb containing 3.40g
RhCl3·3H2O、MgCl2、SrCl2·6H2O and Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L
It is 175m than surface2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, and Rh contents are 6.50g/L, Mg contents
0.73g/L, Sr content 0.97g/L, Sb content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 61.27%, and selectivity is 84.86%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 15】
The preparation of carbonylating catalyst：By Rh containing 6.50g, Mg containing 0.73g, containing the 0.97gSr's and Cr containing 3.40g
RhCl3·3H2O、MgCl2、SrCl2·6H2O and CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml,
Than surface it is 175m by 1.0L2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract,
2h is stood in 100 DEG C of dryings, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.50g/L, Mg
Content 0.73g/L, Sr content 0.97g/L, Cr content 3.40g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 61.55%, and selectivity is 84.55%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 16】
The preparation of carbonylating catalyst：6.50g Rh, Mg containing 0.73g will be contained, containing 0.97gSr, Cr containing 1.07g and contained
2.33gSb RhCl3·3H2O、MgCl2、SrCl2·6H2O、CrCl3·6H2O and Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, is obtained
Than surface it is 175m by 1.0L to maceration extract 400ml2/ g, pore volume 0.96, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst contains through icp analysis, Rh
Measure as 6.50g/L, Mg contents 0.73g/L, Sr content 0.97g/L, Cr content 1.07g/L, Sb content 2.33g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.5MPa
Temperature is 175 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
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 0.35MPa 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 63.76%, and selectivity is 86.62%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
The catalyst that the present invention uses, active component is simultaneously containing Rh, Mg, Sr, Cr and Sb active component specific activity component
Containing Rh, Mg and Cr, containing only Rh, Mg and Sb, containing only Rh, Sr and Cr, containing only Rh, Mg, Sr and Sb, containing only urging for Rh, Mg, Sr and Cr
The performance of agent is more excellent, and the selectivity and yield of vinyl acetate will be high, and this is from embodiment 16, embodiment 1, embodiment 2, real
The data for applying example 13, embodiment 14 and embodiment 15 can be seen that and illustrate between five kinds of active components of Rh, Mg, Sr, Cr and Sb
In the presence of good synergy.
Table 1
Table 2
Claims (10)
1. vinyl acetate prepares method used, comprise the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material,
Carbonylation is carried out in the presence of carbonylating catalyst, co-catalyst and obtains ethylidene diacetate；(2) deposited in catalyst for cracking
Under, ethylidene diacetate cracking is set to obtain vinyl acetate；Wherein, the carbonylating catalyst uses SiO2、Al2O3Or its
Mixture is carrier, and the ratio surface of the carrier is 50~300m2/ g, pore volume are 0.80~1.20, and active component includes rhodium, alkali
Earth metal and selected from least one of VIB and VA metallic element, the co-catalyst is iodide.
2. vinyl acetate prepares method used according to claim 1, it is characterised in that the alkaline-earth metal be selected from beryllium,
At least one of magnesium, calcium, strontium and barium.
3. vinyl acetate prepares method used according to claim 1, it is characterised in that the vib metal is selected from chromium, molybdenum
At least one of with tungsten.
4. vinyl acetate prepares method used according to claim 1, it is characterised in that the VA metals are selected from antimony and bismuth
At least one of.
5. vinyl acetate prepares method used according to claim 1, it is characterised in that the content of rhodium is in catalyst：
3.00~15.00g/L, the content of alkaline-earth metal are：0.10~5.00g/L.
6. vinyl acetate prepares method used according to claim 1, it is characterised in that described in catalyst selected from VIB and
At least one content of metal is 0.5~8.0g/L in VA.
7. vinyl acetate prepares method used according to claim 1, it is characterised in that the iodide are iodomethane.
8. vinyl acetate according to claim 1 prepares method used, it is characterised in that the temperature of the carbonylation
Spend for 130~200 DEG C.
9. vinyl acetate according to claim 1 prepares method used, the pressure of reaction is 3.0~10.0Mpa；Reaction
Middle carbon monoxide and hydrogen volume ratio is 0.10~10.0；The time of reaction is 3.0~10.0h.
10. vinyl acetate according to claim 1 prepares method used, it is characterised in that the preparation of carbonylating catalyst
Method, comprise the following steps：
1. by catalyst composition by the solution of metallic compound in the compound of rhodium, the compound of alkaline-earth metal, VIB and VA with
Carrier mixes；
2. dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410575045.1A CN105585492B (en) | 2014-10-24 | 2014-10-24 | Vinyl acetate prepares method used |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410575045.1A CN105585492B (en) | 2014-10-24 | 2014-10-24 | Vinyl acetate prepares method used |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105585492A CN105585492A (en) | 2016-05-18 |
| CN105585492B true CN105585492B (en) | 2018-01-09 |
Family
ID=55925434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410575045.1A Active CN105585492B (en) | 2014-10-24 | 2014-10-24 | Vinyl acetate prepares method used |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105585492B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774318B (en) * | 2016-08-29 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-10-24 CN CN201410575045.1A patent/CN105585492B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105585492A (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105585492B (en) | Vinyl acetate prepares method used | |
| CN105478127B (en) | Ethylidene diacetate prepares used catalyst | |
| CN105585491B (en) | Method used in vinyl acetate synthesis | |
| CN105585496B (en) | Method for synthesizing vinyl acetate | |
| CN105585493B (en) | Method used in vinyl acetate production | |
| CN105523929B (en) | The method of methyl acetate hydroformylation synthesizing vinyl acetate | |
| CN105523931B (en) | Prepare the method used in vinyl acetate | |
| CN105523927B (en) | The method that methyl acetate hydroformylation prepares vinyl acetate | |
| CN105478116B (en) | For synthesizing the catalyst of ethylidene diacetate | |
| CN105523930B (en) | Produce the method used in vinyl acetate | |
| CN105413684B (en) | Ethylidene diacetate catalyst and its production method | |
| CN105268454B (en) | Support type ethylidene diacetate catalyst | |
| CN105585494B (en) | The method of methyl acetate carbonylation production vinyl acetate | |
| CN105523932B (en) | Method used in synthesizing vinyl acetate | |
| CN105585490B (en) | method for preparing vinyl acetate | |
| CN105585499B (en) | The method that methyl acetate hydroformylation produces vinyl acetate | |
| CN105523886B (en) | Synthesize the method used in 1,3 propane diols | |
| CN105585495B (en) | The method of methyl acetate carbonylation acetic acid ethene | |
| CN105585420B (en) | Method for preparing 1,3 propane diols | |
| CN105413701B (en) | For producing the catalyst of ethylidene diacetate | |
| CN105312057B (en) | Ethylidene diacetate catalyst and ethylidene diacetate synthetic method | |
| CN105585489B (en) | method for producing vinyl acetate | |
| CN105585500B (en) | The method that methyl acetate prepares vinyl acetate | |
| CN105413700B (en) | For preparing the catalyst of ethylidene diacetate | |
| CN105585498B (en) | The method of methyl acetate synthesis vinyl acetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |