CN105585490A - Method for preparing vinyl acetate - Google Patents
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Abstract
The invention relates to a method for preparing vinyl acetate to mainly solve the problems of low yield and low selectivity of vinyl acetate in the process of preparing vinyl acetate according to a route of carrying out carbonylation on methyl acetate at first and then carrying out cracking. By adoption of the technical scheme that the method for preparing vinyl acetate comprises the following steps: carrying out carbonylation on methyl acetate to obtain ethylidene diacetate, and carrying out cracking on ethylidene diacetate to obtain vinyl acetate, wherein a carbonylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and the active components comprise at least one of iron series elements, a lanthanide and at least one metal element selected from IIB and alkaline earth metals, the technical problems are well solved, and the method can be used for industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the method for the preparation of vinyl acetate.
Background technology
Vinyl acetate, vinyl acetate (vinylacetate is called for short VAC or VAM), is at room temperature water white transparencyInflammable liquid, with sweet ether fragrance. It is one of Organic Chemicals that output is larger in the world, is widely used in lifeProduce polyvinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resins,A series of chemical industry such as acetal resin and fiber product, be widely used in all trades and professions.
Inside and outside the producing country of vinyl acetate, all adopt ethene vapor phase method and acetylene in gas phase method technique, belong to petrochemical process roadLine, after C1 chemistry rises, the eighties in 20th century, U.S. Ha Erkang (Halcon) company and BP (BP)Company successively proposes to be prepared by methyl alcohol and synthesis gas new technology-carbonyl process synthesizing vinyl acetate of vinyl acetate. This technique is notRely on petrochemical materials, but by the carbonylation of methyl acetate and synthesis gas, the sub-second of the two acetic acid of synthetic intermediateEster (EDDA), then produce vinyl acetate and acetic acid through thermal cracking. The novel part of whole technique is adding of methyl acetateHydroformylation reaction, catalyst is with radium chloride and use beta-picoline and iodomethane modification, and carbon monoxide inserts reaction and isThe key point of whole technology.
(title is US Patent No. 5354886: CatalystsoninorganiccarriersforproducingethylideneDiacetate) mention RhCl3Or rhodium compound loads on diatomite, titanium oxide, magnesia, aluminium oxide and oxidationOn zinc, make loaded catalyst. Taking methyl acetate, carbon monoxide and hydrogen as raw material, under polar solvent condition,The synthetic ethylidene diacetate of reaction under above-mentioned catalyst. (title is US4843170: ProcessforproduingvinylAcetate) in, mention and utilize halogen acids, sulfuric acid, nitric acid, polyphosphoric acid, benzene sulfonic acid, alkyl sulfonic acid etc. as two acetic acid AsiaEthyl ester cracking is for the catalyst of vinyl acetate. Said method exists vinyl acetate yield low in synthesizing vinyl acetate processWith selective not high problem.
Summary of the invention
Technical problem to be solved by this invention is the low and selective not high problem of vinyl acetate yield, provides a kind of newFor the preparation of the method for vinyl acetate, the method has vinyl acetate yield height and selective high feature.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: for the preparation of the method for vinyl acetate,Comprise the following steps: (1), taking methyl acetate, carbon monoxide and hydrogen as raw material, is entered under carbonylating catalyst existsRow carbonylation obtains ethylidene diacetate; (2) under catalyst for cracking exists, ethylidene diacetate cracking is obtainedObtain vinyl acetate; Wherein, described carbonylating catalyst adopts SiO2、Al2O3Or its mixture is carrier, active groupPoint comprise chosen from Fe series elements at least one, lanthanide series and be selected from IIB and alkaline-earth metal at least one metal unitElement. Preferred described active component comprises iron series element, lanthanide series simultaneously, is selected from least one metallic element in IIBWith at least one metallic element being selected from alkaline-earth metal. Now the metallic element of IIB and the metallic element of alkaline-earth metal itBetween there is synergy improving aspect the selective and yield of vinyl acetate.
In technique scheme, at least one in the excellent chosen from Fe of described iron series element, cobalt and nickel.
In technique scheme, described lanthanide series preferably in lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium at leastA kind of. In technique scheme, as most preferred technical scheme, described active component lanthanide series more preferably lanthanum andSamarium metal.
In technique scheme, preferably at least one in zinc, cadmium and mercury of described IIB metal.
In technique scheme, described alkaline-earth metal is at least one in beryllium, magnesium, calcium, strontium and barium preferably.
In technique scheme, as most preferred technical scheme, described active component comprises iron series element, group of the lanthanides simultaneouslyElement, when being selected from least one element in IIB metal and being selected from least one element in alkaline-earth metal; For example, described inActive component comprises cobalt, lanthanum, samarium, zinc and strontium, or comprises cobalt, lanthanum, samarium, zinc, barium and strontium, or comprise cobalt,Nickel, lanthanum, samarium, zinc, barium and strontium.
In technique scheme, in described carbonylating catalyst, the content of iron series element is preferably 3.00～15.00g/L, more excellentElect 7.00～12.00g/L as; In described carbonylating catalyst, the content of lanthanide series is preferably 0.10～5.00g/L, more preferablyBe 1.00～3.00g/L; In described carbonylating catalyst, be selected from IIB and alkaline-earth metal at least one content of metal preferredBe 0.50～8.00g/L, more preferably 1.00～5.00g/L. Described carbonylating catalyst carrier specific surface used is preferably50～300m2/ g, more preferably 150～200m2/ g, pore volume is preferably 0.80～1.20, and more preferably 0.90～1.00. Above-mentionedDescribed in technical scheme, iodide are preferably iodomethane.
In technique scheme, the preparation method that described carbonylating catalyst can adopt, comprises the steps:
1. press the composition of catalyst by gold in the compound of the compound of iron series element, lanthanide series, IIB and alkaline-earth metalThe solution of the compound belonging to mixes with carrier;
2. dry.
In technique scheme, step 1. described iron series element compound preferably from ferrocene, carbonyl cobalt, cobalt acetate,At least one in cobalt nitrate, cobalt chloride, carbonyl nickel and nickel chloride. Step 1. described lanthanide series compound preferably fromLanthanum acetate, lanthanum chloride, lanthanum nitrate, cerous acetate, cerous nitrate, cerium chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, chlorinationAt least one in ytterbium, Europium chloride and lutecium chloride. Step 1. described IIB metallic compound preferably from zinc chloride, zinc acetate,At least one in zinc citrate, cadmium acetate, caddy, cadmium nitrate, mercurous nitrate and mercuric sulfate. Step is described alkali 1.Earth metal compound is preferably from alkaline earth oxide, alkaline earth metal chloride, alkaline earth nitrate, alkaline-earth metal sulphurAt least one in hydrochlorate and Alkaline Earth Metal Acetate. Step 2. described baking temperature is preferably 80～120 DEG C, more preferably100～120℃。
In technique scheme, by the composition of catalyst by comprise iron series element compound, lanthanide series compound,In IIB and alkaline-earth metal, the compound of metal and carrier hybrid mode are not particularly limited, and their aqueous solution and carrier connectAlso be not particularly limited tactile opportunity. For example the present invention will can comprised to the chemical combination of iron series element by the composition of catalystIn compound, IIB and the alkaline-earth metal of thing, lanthanide series, the compound of metal first mixes water-solublely, can be also by itCompound form successively after the aqueous solution and mix again and contact with carrier, can also different order contact and obtain with carrierDescribed catalyst.
The key of the inventive method is carbonylating catalyst, after obtaining carbonylating catalyst, by carbonylation is urgedAgent contacts and can be used for carbonylation with described co-catalyst. The mode that carbonylating catalyst contacts with co-catalyst does not haveThere is special restriction, to be also not particularly limited the opportunity that both contact. For example can be by carbonylating catalyst of the present inventionForm described catalyst for making both contact before chemical reaction, can also make both applied at catalyst of the present inventionIn reaction system, contact generates catalyst original position.
Key of the present invention is the selection of carbonylating catalyst, those skilled in the art will know that and how to determine according to actual needsThe proportioning of suitable reaction temperature, reaction time, reaction pressure and material. But, the temperature of reacting in technique schemeDegree is preferably 130～200 DEG C; The pressure of reaction is preferably 3.0～10.0MPa; The time of reaction is preferably 3.0～10.0h.The mol ratio of carbon monoxide and hydrogen is preferably 0.10～10.0.
In the method for methyl acetate synthesis vinyl acetate of the present invention, after step (1) finishes, can be to carbonylationMixture separates acquisition target product ethylidene diacetate and carries out step (2) again, also can step (1) generate twoAfter acetic acid ethyl, do not separate and directly carry out step (2). Those skilled in the art know the suitable cracking and catalyzing of selectionAgent and definite suitable cracking reaction temperature, time and material proportion. Conventional catalyst for cracking have Bronsted acid (as HI,HBr、HCl、HF、H2SO4、H3PO4、HNO3、H3BO3、HClO3、HBrO3、HIO3, polyphosphoric acid, alkaneBase sulfonic acid, benzene sulfonic acid etc.), lewis acid (as IIA, IIIA, IVA, VA, VIA, IIIB, IVB, VB, VIB,VIIB, VIII metal halogen compound). In the present invention preferably benzene sulfonic acid as catalyst for cracking, suitable cracking temperatureBe preferably 100～180 DEG C; Cleavage reaction pressure is 0～1.0MPa preferably; The cracking reaction time is preferably 10～60min;Benzene sulfonic acid catalyst for cracking accounts for 3.0～7.0% of raw material total amount; At least one in the preferred acetic acid of solvent and aceticanhydride.
Product of the present invention adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis after cooling, decompression, separation,Calculate the conversion ratio of methyl acetate and the yield of vinyl acetate and selective by following formula:
Compared with prior art, key of the present invention is that the active component of step (1) carbonylating catalyst comprises necessarilyAmount iron series element, lanthanide series and be selected from IIB and alkaline-earth metal at least one metallic element, be conducive to improve urgeThe activity of agent and stability, thus the yield that has improved vinyl acetate is with selective.
Experimental result shows, the prepared vinyl acetate yield of the present invention reaches 58.27%, selectively reaches 81.36%, obtainsIn good technique effect, especially carbonylating catalyst active component comprise iron series element, lanthanide series, choosing simultaneouslyAt least one metallic element in IIB and while being selected from least one metallic element in alkaline-earth metal, has obtained more prominentThe technique effect going out, can be in vinyl acetate synthetic. Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gLa and the Co (OAc) containing 3.25gZn2·4H2O、La(OAc)3·5H2O and zinc citrate (Zn3(C6H5O7)2·2H2O) hydrochloric acid that fully mixed dissolution is 8wt% in concentrationIn, obtain maceration extract 400ml, be 165m by 1.0L specific surface2/ g, pore volume is 0.98, the ball that diameter is 5.6mmShape SiO2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylChange catalyst through icp analysis, Co content is 8.98g/L, La content 2.75g/L, Zn content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.27% as calculated, is selectively 81.36%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 2]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gLa and the Co (OAc) containing 3.25gSr2·4H2O、La(OAc)3·5H2O and Sr (OAc)2·0.5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0LSpecific surface is 165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is8.98g/L, La content 2.75g/L, Sr content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.36% as calculated, is selectively 81.29%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of carbonylating catalyst: will contain 8.98gCo and the Co (OAc) containing 2.75gLa2·4H2O and La (OAc)3·5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry,To described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L, La content 2.75g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 50.55% as calculated, is selectively 70.63%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
By finding out compared with embodiment 1～2, the catalyst that the present invention adopts, uses simultaneously containing Co, La and ZnActive component, simultaneously containing the catalyst performance of Co, La and Sr active component than only containing Co, La active constituent catalystPerformance more excellent, the selective and yield of vinyl acetate is all wanted height.
[embodiment 3]
The preparation of carbonylating catalyst: will contain 7.00gCo, contain 1.00gCe and the Co containing 1.00gZn2(CO)8、Ce(OAc)3·6H2O and Zn (OAc)2·2H2In the acetic acid that the abundant mixed dissolution of O is 10wt% in concentration, obtain maceration extract400ml is 150m by 1.0L specific surface2/ g, pore volume is 0.90, the spherical Al that diameter is 5.6mm2O3Carrier impregnationIn above-mentioned maceration extract, leave standstill 2h in 80 DEG C dry, obtain described catalyst. Described carbonylating catalyst divides through ICPAnalyse, Co content is 7.00g/L, Ce content 1.00g/L, Zn content 1.00g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.34% as calculated, is selectively 80.83%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 4]
The preparation of carbonylating catalyst: will contain 12.00gFe, contain 3.00gCe and the ferrocene containing 5.00gCd(Fe(C5H5)2)、CeCl3·6H2O and Cd (OAc)2·2H2In the nitric acid that the abundant mixed dissolution of O is 8wt% in concentration,Obtaining maceration extract 400ml, is 200m by 1.0L specific surface2/ g, pore volume is 1.00, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 120 DEG C dry, obtain described catalyst. Described carbonylating catalystThrough icp analysis, Fe content is 12.00g/L, Ce content 3.00g/L, Cd content 5.00g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.25% as calculated, is selectively 81.42%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 5]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gCe and the CoCl containing 3.25gCd2·6H2O、Ce(NO3)3·6H2O and CdCl2Fully mixed dissolution, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2hIn 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L,Ce content 2.75g/L, Cd content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.39% as calculated, is selectively 81.24%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 6]
The preparation of carbonylating catalyst: will contain 8.98gNi, contain 2.75gPr and the Ni (NO containing 3.25gHg3)2·6H2O、Pr(OAc)3·5H2O and HgSO4In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml,Be 165m by 1.0L specific surface2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis,Co content is 8.98g/L, Pr content 2.75g/L, Hg content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.41% as calculated, is selectively 81.31%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 7]
The preparation of carbonylating catalyst: will contain 8.98gNi, contain 2.75gNd and the NiCl containing 3.25gBe2·6H2O、Nd(OAc)3·5H2O and BeCl2Fully mixed dissolution, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2hIn 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L,Nd content 2.75g/L, Be content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.22% as calculated, is selectively 81.30%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 8]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gYb and the Co (NO containing 3.25gMg3)2·6H2O、YbCl3·6H2O and MgSO4Fully mixed dissolution, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2hIn 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L,Yb content 2.75g/L, Mg content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 3.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 130 DEG C, the mol ratio of carbon monoxide and hydrogen is 1:10, after sustained response 3.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 55.63% as calculated, is selectively 78.19%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 9]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gEu and the Co (NO containing 3.25gCa3)2·6H2O、EuCl3·6H2In the aqueous hydrochloric acid solution that the abundant mixed dissolution of O and CaO is 8wt% in concentration, obtain maceration extract 400ml,Be 165m by 1.0L specific surface2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis,Co content is 8.98g/L, Eu content 2.75g/L, Ca content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 10.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 200 DEG C, and the mol ratio of carbon monoxide and hydrogen is 10:1, after sustained response 10.0h,Stop reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, warpRectification and purification, except desolventizing, ethyl acetate, acetaldehyde and other accessory substances, obtains ethylidene diacetate.
Step (2): it is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.70% as calculated, is selectively 80.98%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 10]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gLu and the Co containing 3.25gBa2(CO)8、LuCl3·6H2O and Ba (NO3)2In the acetic acid that fully mixed dissolution is 10wt% in concentration, obtain maceration extract 400ml, by 1.0LSpecific surface is 165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is8.98g/L, Lu content 2.75g/L, Ba content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.15% as calculated, is selectively 81.40%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 11]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gLa and the CoCl containing 3.25gSr2·6H2O、La(OAc)3·5H2O and Sr (OAc)2·0.5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0LSpecific surface is 165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is8.98g/L, La content 2.75g/L, Sr content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.20% as calculated, is selectively 81.41%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 12]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gSm and the Co (OAc) containing 3.25gSr2·4H2O、SmCl3·6H2O and Sr (OAc)2·0.5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0L ratioSurface is 165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is8.98g/L, Sm content 2.75g/L, Sr content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.31% as calculated, is selectively 81.37%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 13]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gSm and the Co (OAc) containing 3.25gZn2·4H2O、SmCl3·6H2O and zinc citrate (Zn3(C6H5O7)2·2H2O) in the hydrochloric acid that fully mixed dissolution is 8wt% in concentration,Obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalystThrough icp analysis, Co content is 8.98g/L, Sm content 2.75g/L, Zn content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.28% as calculated, is selectively 81.38%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 14]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 2.75gLa, contain 1.38gZn and contain 1.87gSr'sCo(OAc)2·4H2O、La(OAc)3·5H2O, zinc citrate (Zn3(C6H5O7)2·2H2And Sr (OAc) O)2·0.5H2OIn the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/g，Pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h dry in 100 DEG CDry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L, La content 2.75G/L, Zn content 1.38g/L, Sr content 1.87g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 59.24% as calculated, is selectively 82.75%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment and embodiment 1, embodiment 2 relatively can find out, IIB Metal Zn and alkaline-earth metal Sr are improving vinegarAcid ethene yield and selectively there is good synergy.
[embodiment 15]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 1.32gLa, contain 1.43gSm and contain 3.25gZn's Co(OAc)2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O and zinc citrate (Zn3(C6H5O7)2·2H2O) abundantIn the hydrochloric acid that mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, holeAppearance is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry,Obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L, La content 1.32g/L,Sm content 1.43g/L, Zn content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.48% as calculated, is selectively 82.53%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment and embodiment 1, embodiment 13 relatively can find out, lanthanide series metal La and Sm are improving two acetic acidThe yield of ethene and selectively there is good synergy.
[embodiment 16]
The preparation of carbonylating catalyst: will contain 8.98gCo, contain 1.32gLa, contain 1.43gSm and contain 3.25gSr'sCo(OAc)2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O and Sr (OAc)2·0.5H2The abundant mixed dissolution of O is in denseIn the hydrochloric acid of degree for 8wt%, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.98, straightFootpath is the spherical SiO of 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, described in obtaining, urgeAgent. Described carbonylating catalyst is through icp analysis, and Co content is 8.98g/L, La content 1.32g/L, Sm content1.43g/L, Sr content 3.25g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 59.34% as calculated, is selectively 82.51%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 17]
The preparation of carbonylating catalyst: will be containing 8.98gCo, containing 1.32gLa, containing 1.43gSm, containing 1.38gZn and containingThe Co (OAc) of 1.87gSr2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3(C6H5O7)2·2H2And Sr (OAc) O)2·0.5H2In the hydrochloric acid that the abundant mixed dissolution of O is 8wt% in concentration, obtain maceration extract 400ml,Be 165m by 1.0L specific surface2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis,Co content is 8.98g/L, La content 1.32g/L, Sm content 1.43g/L, Zn content 1.38g/L, Sr content 1.87g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 60.85% as calculated, is selectively 84.03%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment is compared and can be found out with embodiment 15, embodiment 16, when lanthanide series metal in catalyst activity componentWhile being selected from La, Sm, and be selected from IIB Metal Zn and while being selected from alkaline-earth metal Sr, the selective and yield of vinyl acetateAll want high, illustrated between Co, La, Sm, Zn and Sr active component and existed well and act synergistically.
[embodiment 18]
The preparation of carbonylating catalyst: will be containing 8.98gCo, containing 1.32gLa, containing 1.43gSm, containing 1.38gZn and containingThe Co (OAc) of 1.87gBa2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3(C6H5O7)2·2H2And Ba (NO O)3)2In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml, by 1.0LSpecific surface is 165m2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is8.98g/L, La content 1.32g/L, Sm content 1.43g/L, Zn content 1.38g/L, Ba content 1.87g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 61.02% as calculated, is selectively 84.11%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 19]
The preparation of carbonylating catalyst: will containing 8.98gCo, containing 1.32gLa, containing 1.43gSm, containing 1.38gZn, contain1.14gSr and containing the Co (OAc) of 0.73gBa2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate(Zn3(C6H5O7)2·2H2O)、Sr(OAc)2·0.5H2O and Ba (NO3)2The salt that fully mixed dissolution is 8wt% in concentrationIn acid, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.98, diameter is 5.6mmSpherical SiO2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylBase catalyst is through icp analysis, and Co content is 8.98g/L, La content 1.32g/L, Sm content 1.43g/L, ZnContent 1.38g/L, Sr content 1.14g/L, Ba content 0.73g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 62.76% as calculated, is selectively 85.62%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment is compared and can be found out with embodiment 17, embodiment 18, catalyst activity component of iron series elements, lanthanumSeries elements and be selected from IIB metal when fixing, the collaborative favourable raising vinyl acetate of alkaline-earth metal Sr and Ba selective and receivingRate, has illustrated between Co, La, Sm, Zn, Ba and Sr active component and has existed well and act synergistically.
[embodiment 20]
The preparation of carbonylating catalyst: will containing 8.98gNi, containing 1.32gLa, containing 1.43gSm, containing 1.38gZn, contain1.14gSr and containing the NiCl of 0.73gBa2·6H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3(C6H5O7)2·2H2O)、Sr(OAc)2·0.5H2O and Ba (NO3)2In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, soakedStain liquid 400ml is 165m by 1.0L specific surface2/ g, pore volume is 0.98, the spherical SiO that diameter is 5.6mm2CarrierBe immersed in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst warpIcp analysis, Ni content is 8.98g/L, La content 1.32g/L, Sm content 1.43g/L, Zn content 1.38g/L,Sr content 1.14g/L, Ba content 0.73g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 62.57% as calculated, is selectively 85.73%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 21]
The preparation of carbonylating catalyst: will containing 5.98gCo, containing 3.00gNi, containing 1.32gLa, containing 1.43gSm, contain1.38gZn, containing 1.14gSr with containing the Co (OAc) of 0.73gBa2·4H2O、NiCl2·6H2O、La(OAc)3·5H2O、 SmCl3·6H2O, zinc citrate (Zn3(C6H5O7)2·2H2O)、Sr(OAc)2·0.5H2O and Ba (NO3)2Fully mixBeing dissolved in the hydrochloric acid that concentration is 8wt%, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is0.98, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry,To described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 5.98g/L, and Ni content is 3.00g/L,La content 1.32g/L, Sm content 1.43g/L, Zn content 1.38g/L, Sr content 1.14g/L, Ba content 0.73g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 147 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 64.03% as calculated, is selectively 86.80%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment is compared and can be found out with embodiment 19, embodiment 20, lanthanide series in catalyst activity component,Be selected from IIB metal and alkaline-earth metal when fixing, the collaborative favourable raising vinyl acetate of iron series element Co and Ni selective andYield, has illustrated between Co, Ni, La, Sm, Zn, Ba and Sr active component and has existed well and act synergistically.
Table 1
Table 2
Claims (10)
1. for the preparation of the method for vinyl acetate, comprise the following steps: (1) is taking methyl acetate, carbon monoxide and hydrogen as formerMaterial, carries out carbonylation at carbonylating catalyst, co-catalyst and obtains ethylidene diacetate under existing; (2) in crackingUnder catalyst exists, make ethylidene diacetate cracking obtain vinyl acetate; Wherein, described carbonylating catalyst adopts SiO2、Al2O3Or its mixture is carrier, active component comprise chosen from Fe series elements at least one, lanthanide series and being selected fromAt least one metallic element in IIB and alkaline-earth metal; Described co-catalyst is iodide.
2. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that described iron series element chosen from Fe,At least one in cobalt and nickel.
3. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that described lanthanide series be selected from lanthanum,At least one in cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium.
4. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that described IIB metal be selected from zinc,At least one in cadmium and mercury.
5. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that described alkaline-earth metal be selected from beryllium,At least one in magnesium, calcium, strontium and barium.
6. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that containing of iron series element in catalystAmount is: 3.00～15.00g/L, the content of lanthanide series is: 0.10～5.00g/L.
7. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that being selected from described in catalyst IIBWith at least one content of metal in alkaline-earth metal be 0.50～8.00g/L.
8. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that described iodide are iodomethane.
9. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that the temperature of described carbonylationIt is 130～200 DEG C; The pressure of reaction is 3.0～10.0MPa; In reaction carbon monoxide and hydrogen volume ratio be 0.10～10.0; The time of reaction is 3.0～10.0h.
10. according to claim 1 for the preparation of the method for vinyl acetate, it is characterized in that the system of carbonylation reaction catalystPreparation Method, comprises the steps:
1. press the composition of catalyst by gold in the compound of the compound of iron series element, lanthanide series, IIB and alkaline-earth metalThe solution of the compound belonging to mixes with carrier;
2. dry.
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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 |
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| 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 |
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