CN105478137A - Catalyst for preparing ethylidene diacetate - Google Patents
Catalyst for preparing ethylidene diacetate Download PDFInfo
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- CN105478137A CN105478137A CN201410474679.8A CN201410474679A CN105478137A CN 105478137 A CN105478137 A CN 105478137A CN 201410474679 A CN201410474679 A CN 201410474679A CN 105478137 A CN105478137 A CN 105478137A
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Abstract
The invention relates to a catalyst for preparing ethylidene diacetate. The catalyst is mainly used for solving the problem in the prior art that catalysts for ethylidene diacetate are relatively low in activity and selectivity. Through adopting the technical scheme that the catalyst for ethylidene diacetate adopts SiO2, Al2O3 or a mixture of SiO2 and Al2O3 as a carrier, and active ingredients comprise at least one element selected from ferrous elements, at least one element selected from metalloid elements and at least one metal element selected from IB and alkaline-earth metals, the technical problem is better solved, and the catalyst can be applied to the industrial production of vinyl acetate.
Description
Technical field
The present invention relates to and prepare ethylidene diacetate catalyst used, prepare the preparation method of ethylidene diacetate catalyst used and the synthetic method of ethylidene diacetate.
Background technology
Vinyl acetate, i.e. vinyl acetate (vinylacetate, be called for short VAC or VAM) are at room temperature the inflammable liquid of water white transparency, with sweet ether fragrance.It is one of Organic Chemicals that output is larger in the world, be widely used in a series of chemical industry and fiber products such as producing polyvinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal resin, be widely used in all trades and professions.
Ethene vapor phase method and acetylene in gas phase method technique is all adopted inside and outside the producing country of vinyl acetate, belong to petrochemical process route, after C1 chemistry rises, the eighties in 20th century, U.S. Ha Erkang (Halcon) company and BP (BP) company successively propose the new technology-carbonyl process synthesizing vinyl acetate being prepared vinyl acetate by methyl alcohol and synthesis gas.This technique does not rely on petrochemical materials, but by the carbonylation of methyl acetate and synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then produce vinyl acetate and acetic acid through thermal cracking.The novel part of whole technique is the hydroformylation reaction of methyl acetate, and catalyst radium chloride also uses beta-picoline and iodomethane modification, and carbon monoxide intercalation reaction is the key point of whole technology.
By the preparation method of methyl acetate synthesis ethylidene diacetate by US4,429,150 (title for: Manufactureofethylidenediacetate), namely with methyl acetate or methyl ether, carbon monoxide and hydrogen for raw material, catalyst synthesizes ethylidene diacetate under adopting VIII halide or acetate and phosphorous polar solvent to exist.US5,354,886 (title is: Catalystsoninorganiccarriersforproducingethylidenediacet ate) are mentioned RhCl
3or rhodium compound load makes loaded catalyst on diatomite, titanium oxide, magnesia, aluminium oxide and zinc oxide.With methyl acetate, carbon monoxide and hydrogen for raw material, under polar solvent conditions, Reactive Synthesis ethylidene diacetate under above-mentioned catalyst.All there is the low and selective not high problem of ethylidene diacetate yield preparing in ethylidene diacetate process in said method.
Summary of the invention
One of technical problem to be solved by this invention is the low and selective low problem of ethylidene diacetate yield, there is provided a kind of and prepare ethylidene diacetate catalyst used, it is high to the selective high feature of ethylidene diacetate that this catalyst has ethylidene diacetate yield.
Two of technical problem to be solved by this invention is the preparation methods adopting one of above-mentioned technical problem described catalyst.
Three of technical problem to be solved by this invention is the synthetic methods of the ethylidene diacetate adopting one of above-mentioned technical problem described catalyst.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: prepare the catalyst that ethylidene diacetate is used, and described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprise chosen from Fe series elements at least one, be selected from metalloid element at least one and be selected from least one metallic element in IB and alkaline-earth metal.Preferred described active component comprises iron series element, metalloid element, at least one metallic element that is selected from least one metallic element in IB and is selected from alkaline-earth metal simultaneously.Now there is synergy improving in the selective and yield of EDDA between the metallic element of IB and the metallic element of alkaline-earth metal.
In technique scheme, at least one in the excellent chosen from Fe of described iron series element, cobalt and nickel.
In technique scheme, at least one of described metalloid element preferably in boron, arsenic and tellurium.
In technique scheme, as most preferred technical scheme, described active component metalloid element is more preferably boron and tellurium metalloid.
In technique scheme, at least one of described IB metal preferably in copper, silver and gold.
In technique scheme, at least one of described alkaline-earth metal preferably in beryllium, magnesium, calcium, strontium and barium.
In technique scheme, as most preferred technical scheme, described active component comprises iron series element, metalloid element, IB metal and alkaline-earth metal simultaneously; Such as described active component comprises cobalt, boron, Jin Hesi, or comprises cobalt, boron (or tellurium), copper, Jin Hesi, or comprises cobalt, boron, tellurium, copper, Jin Hesi (or beryllium), or comprises cobalt, boron, tellurium, copper, gold, strontium and beryllium.
In technique scheme, in described catalyst, the content of iron series element is preferably 3.00 ~ 15.00g/L, is more preferably 7.00 ~ 12.00g/L; In described catalyst, the content of metalloid element is preferably 0.10 ~ 5.00g/L, is more preferably 1.00 ~ 4.00g/L; At least one content being selected from metal in IB and alkaline-earth metal in described catalyst is preferably 0.50 ~ 8.00g/L, is more preferably 1.00 ~ 5.00g/L.Described catalyst carrier specific surface used is preferably 50 ~ 300m
2/ g, is more preferably 150 ~ 200m
2/ g, pore volume is preferably 0.80 ~ 1.20, is more preferably 0.90 ~ 1.00.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
1., by the composition of catalyst, the solution of the compound of metal in the compound of the compound of iron series element, metalloid element, IB and alkaline-earth metal is mixed with carrier;
2., dry.
In technique scheme, at least one of compound preferably in carbonyl cobalt, cobalt nitrate, cobalt chloride, cobalt acetate, ferrocene, carbonyl nickel, nickel chloride and nickel acetate of step 1. described iron series element.At least one of compound preferably in boric acid, ammonium pentaborate, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, tellurium dioxide and telluric acid of step 1. described metalloid element.Step is at least one of described IB metallic compound preferably in copper citrate, copper chloride, Schweinfurt green, silver ammino solution, silver tetrafluoroborate, gold chloride and tetra chlorauric acid ammonium 1..Step is at least one of described alkaline earth metal compound preferably in alkaline earth oxide, alkaline earth metal chloride, alkaline earth nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate 1..Step 2. described baking temperature is preferably 80 ~ 120 DEG C, is more preferably 100 ~ 120 DEG C.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the synthetic method of ethylidene diacetate, with methyl acetate, carbon monoxide and hydrogen for raw material, take acetic acid as solvent, under catalyst and co-catalyst iodide exist, reaction generates ethylidene diacetate.The preferred iodomethane of described iodide.
Key of the present invention is the selection of catalyst, those skilled in the art will know that the proportioning determining suitable reaction temperature, reaction time, reaction pressure and material how according to actual needs.But the temperature of reacting in technique scheme 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 0.1 ~ 10.0.
Product of the present invention through cooling, decompression, be separated after adopt gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) to analyze, by the following conversion ratio of formulae discovery methyl acetate and the yield of ethylidene diacetate and selective:
Compared with prior art, key of the present invention is that the active component of catalyst comprises a certain amount of iron series element, metalloid element and is selected from least one metallic element in IB and alkaline-earth metal, be conducive to improving the activity of major catalyst and stability, thus improve the yield of ethylidene diacetate and selective.
Experimental result shows, ethylidene diacetate yield prepared by the present invention reaches 61.02%, selectively reach 85.71%, achieve good technique effect, especially when in catalyst, active component comprises iron series element, metalloid element simultaneously, is selected from least one metallic element in IB and is selected from least one metallic element in alkaline-earth metal, achieve more outstanding technique effect, may be used in the synthesis of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB with containing the CoCl of 2.90gAu
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2and NH O)
4auCl
42H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Au content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.02% as calculated, and selective is 85.71%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 2]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB with containing the CoCl of 2.90gSr
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2and Sr (OAc) O)
20.5H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Sr content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.17% as calculated, and selective is 85.40%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst: will 8.50gCo and the CoCl containing 3.20gB be contained
26H
2o and ammonium pentaborate ((NH
4) B
5o
88H
2o) fully mixed dissolution is in pure water, and obtaining maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 51.53% as calculated, and selective is 74.66%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
By finding out compared with embodiment 1 ~ 2, the catalyst that the present invention adopts, use simultaneously more excellent than the performance only containing Co, B active constituent catalyst containing Co, B and Au active component, catalyst performance simultaneously containing Co, B and Sr active component, the selective and yield of ethylidene diacetate all wants height.
[embodiment 3]
The preparation of catalyst: by containing 7.00gNi, containing 1.00gB with containing the NiCl of 1.00gCu
26H
2o, boric acid (H
3bO
3) and cupric tartrate (C
4h
4o
6cuXH
2o) fully mixed dissolution is in the hydrochloric acid of 8wt% in concentration, and obtaining maceration extract 400ml, is 150m by 1.0L specific surface
2/ g, pore volume is 0.90, and diameter is the spherical Al of 5.6mm
2o
3carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 80 DEG C of dryings, obtains described catalyst.The Ni content analyzing this catalyst through ICP-MS is 7.00g/L, B content 1.00g/L, Cu content 1.00g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 58.13% as calculated, and selective is 85.42%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 4]
The preparation of catalyst: by containing 12.00gNi, containing 4.00gB with containing the Ni (OAc) of 5.00gCu
2, dimethylamino monoborane (C
2h
6and CuCl BN)
22H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 200m by 1.0L specific surface
2/ g, pore volume is 1.00, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 120 DEG C of dryings, obtains described catalyst.The Ni content analyzing this catalyst through ICP-MS is 12.00g/L, B content 4.00g/L, Cu content 5.00g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.93% as calculated, and selective is 84.82%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 5]
The preparation of catalyst: by containing 8.50gNi, containing 3.20gAs with containing the Ni (CO) of 2.90gCu
4, arsenic acid (H
3asO
40.5H
2and Cu (OAc) O)
2h
2the abundant mixed dissolution of O, in ethanol, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.Ni content through this catalyst of icp analysis is 8.50g/L, As content 3.20g/L, Cu content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.23% as calculated, and selective is 85.32%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 6]
The preparation of catalyst: by containing 8.50gFe, containing 3.20gAs with containing the ferrocene (Fe (C of 2.90gAg
5h
5)
2), AsCl
38H
2o and silver ammino solution ([Ag (NH
3)
2] OH) and fully mixed dissolution be in the nitric acid of 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.Fe content through this catalyst of icp analysis is 8.50g/L, As content 3.20g/L, Ag content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.09% as calculated, and selective is 85.44%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 7]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gTe with containing the Co of 2.90gAg
2(CO)
8, (NH
4)
2teO
4with trifluoroacetic acid silver (AgC
2f
3o
2) fully mixed dissolution be in the acetic acid of 10wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.Co content through this catalyst of icp analysis is 8.50g/L, Te content 3.20g/L, Ag content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.55% as calculated, and selective is 85.34%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 8]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gTe with containing the Co (NO of 2.90gAu
3)
26H
2o, TeO
2with gold chloride (HAuCl
4) fully mixed dissolution be in the hydrochloric acid of 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.Co content through this catalyst of icp analysis is 8.50g/L, Te content 3.20g/L, Au content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 3.0MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1:10, after sustained response 3.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 51.66% as calculated, and selective is 80.24%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 9]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gTe with containing the Co (OAc) of 2.90gMg
24H
2o, H
6teO
6and MgSO
4abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.Co content through this catalyst of icp analysis is 8.50g/L, Te content 3.20g/L, Mg content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 10.0MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and 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.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 62.03% as calculated, and selective is 84.88%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 10]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB with containing the CoCl of 2.90gCa
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2and Ca (NO O)
3)
2abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Ca content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.42% as calculated, and selective is 85.13%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 11]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB with containing the CoCl of 2.90gBe
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2and BeCl O)
2abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Be content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.53% as calculated, and selective is 85.22%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 12]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB with containing the CoCl of 2.90gBa
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o) and the abundant mixed dissolution of BaO be in the hydrochloric acid of 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Ba content 2.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 61.41% as calculated, and selective is 85.39%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 13]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB, containing 2.00gAu with containing the CoCl of 0.90gSr
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o), NH
4auCl
42H
2o and Sr (OAc)
20.5H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Au content 2.00g/L, Sr content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 63.17% as calculated, and selective is 86.90%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
The present embodiment compares can find out with embodiment 1, embodiment 2, and the activity and selectivity that IB metal A u alkaline-earth metal Sr is improving ethylidene diacetate catalyst has good synergy.
[embodiment 14]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB, containing 2.00gCu with containing the CoCl of 0.90gSr
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o), cupric tartrate (C
4h
4o
6cuXH
2and Sr (OAc) O)
20.5H
2the abundant mixed dissolution of O is in the hydrochloric acid of 8wt% in concentration, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Cu content 2.00g/L, Sr content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 62.92% as calculated, and selective is 86.95%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 15]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gB, containing 1.20gAu, containing 0.80gCu with containing the CoCl of 0.90gSr
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o), NH
4auCl
42H
2o, cupric tartrate (C
4h
4o
6cuXH
2and Sr (OAc) O)
20.5H
2the abundant mixed dissolution of O is in the hydrochloric acid of 8wt% in concentration, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 3.20g/L, Au content 1.20g/L, Cu content 0.80g/L, Sr content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 65.06% as calculated, and selective is 89.51%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
The present embodiment compares can find out with embodiment 13, embodiment 14, and other active component of IB metal A u and Cu and the present invention has good synergy at the activity and selectivity improving ethylidene diacetate catalyst.
[embodiment 16]
The preparation of catalyst: by containing 8.50gCo, containing 3.20gTe, containing 1.20gAu, containing 0.80gCu with containing the CoCl of 0.90gSr
26H
2o, (NH
4)
2teO
4, NH
4auCl
42H
2o, cupric tartrate (C
4h
4o
6cuXH
2and Sr (OAc) O)
20.5H
2the abundant mixed dissolution of O is in the hydrochloric acid of 8wt% in concentration, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.Co content through this catalyst of icp analysis is 8.50g/L, Te content 3.20g/L, Au content 1.20g/L, Cu content 0.80g/L, Sr content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 64.97% as calculated, and selective is 90.02%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 17]
The preparation of catalyst: by containing 8.50gCo, containing 1.52gB, containing 1.68gTe, containing 1.20gAu, containing 0.80gCu with containing the CoCl of 0.90gSr
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o), (NH
4)
2teO
4, NH
4auCl
42H
2o, cupric tartrate (C
4h
4o
6cuXH
2and Sr (OAc) O)
20.5H
2the abundant mixed dissolution of O is in the hydrochloric acid of 8wt% in concentration, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 1.52g/L, Te content 1.68g/L, Au content 1.20g/L, Cu content 0.80g/L, Sr content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 66.87% as calculated, and selective is 91.04%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
The present embodiment can be found out compared with embodiment 15, embodiment 16, in metalloid, in B, Te and the present invention, other active component works in coordination with the selective and yield of favourable raising ethylidene diacetate, describes between Co, B, Te, Au, Cu and Sr active component and there is well synergy.
[embodiment 18]
The preparation of catalyst: by containing 8.50gCo, containing 1.52gB, containing 1.68gTe, containing 1.20gAu, containing 0.80gCu with containing the CoCl of 0.90gBe
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o), (NH
4)
2teO
4, NH
4auCl
42H
2o, cupric tartrate (C
4h
4o
6cuXH
2and BeCl O)
2abundant mixed dissolution is in the hydrochloric acid of 8wt% in concentration, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 1.52g/L, Te content 1.68g/L, Au content 1.20g/L, Cu content 0.80g/L, Be content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 66.73% as calculated, and selective is 91.29%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 19]
The preparation of catalyst: by containing 8.50gCo, containing 1.52gB, containing 1.68gTe, containing 1.20gAu, containing 0.80gCu, containing 0.50gSr with containing the CoCl of 0.40gBe
26H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2o), (NH
4)
2teO
4, NH
4auCl
42H
2o, cupric tartrate (C
4h
4o
6cuXH
2o), Sr (OAc)
20.5H
2o and BeCl
2abundant mixed dissolution is in the hydrochloric acid of 8wt% in concentration, obtains maceration extract 400ml, is 165m by 1.0L specific surface
2/ g, pore volume is 0.95, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h in 100 DEG C of dryings, obtains described catalyst.The Co content analyzing this catalyst through ICP-MS is 8.50g/L, B content 1.52g/L, Te content 1.68g/L, Au content 1.20g/L, Cu content 0.80g/L, Sr content 0.50g/L, Be content 0.90g/L.
The synthesis of ethylidene diacetate: 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol methyl acetate are added in 500ml titanium material reactor, first discharge in still with argon gas and be pressurized to 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 6.8MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of ethylidene diacetate is 67.50% as calculated, and selective is 91.84%, for convenience of explanation and compare, by the yield of the preparation condition of catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
The present embodiment can be found out compared with embodiment 17, embodiment 18, in alkaline-earth metal, in Sr, Be and the present invention, other active component works in coordination with the selective and yield of favourable raising ethylidene diacetate, describes between Co, B, Te, Au, Cu, Sr and Be active component and there is well synergy.
Table 1
Table 2 (continued)
Table 2 (Continued)
Claims (10)
1. prepare the catalyst that ethylidene diacetate is used, described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprise chosen from Fe series elements at least one, be selected from metalloid element at least one and be selected from least one metallic element in IB and alkaline-earth metal.
2. catalyst according to claim 1, is characterized in that at least one in described iron series element chosen from Fe, cobalt and nickel.
3. catalyst according to claim 1, is characterized in that described metalloid element is selected from least one in boron, arsenic and tellurium.
4. catalyst according to claim 1, is characterized in that described IB metal is selected from least one in copper, silver and gold.
5. catalyst according to claim 1, is characterized in that described alkaline-earth metal is selected from least one in beryllium, magnesium, calcium, strontium and barium.
6. catalyst according to claim 1, it is characterized in that the content of iron series element in catalyst is 3.00 ~ 15.00g/L, the content of metalloid element is 0.10 ~ 5.00g/L.
7. catalyst according to claim 1, at least one content that it is characterized in that being selected from described in catalyst metal in IB and alkaline-earth metal is 0.50 ~ 8.00g/L.
8. the preparation method of the catalyst described in claim 1, comprises the steps:
1., by the composition of catalyst, the solution of the compound of metal in the compound of the compound of iron series element, metalloid element, IB and alkaline-earth metal is mixed with carrier;
2., dry.
9. the synthetic method of ethylidene diacetate, with methyl acetate, carbon monoxide and hydrogen for raw material, is solvent with acetic acid, and according to any one of claim 1 ~ 7, catalyst and co-catalyst iodide synthesize ethylidene diacetate under existing.
10. synthetic method according to claim 9, is characterized in that the temperature of reacting is 130 ~ 200 DEG C.
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Citations (5)
| 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 |
| US5354886A (en) * | 1990-10-05 | 1994-10-11 | Korea Research Institute Of Chemical Technology | Catalysts on inorganic carriers for producing ethylidene diacetate |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
| CN103934000A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method thereof |
-
2014
- 2014-09-17 CN CN201410474679.8A patent/CN105478137B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5354886A (en) * | 1990-10-05 | 1994-10-11 | Korea Research Institute Of Chemical Technology | Catalysts on inorganic carriers for producing ethylidene diacetate |
| CN103934000A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method thereof |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
Non-Patent Citations (1)
| Title |
|---|
| 杨运信 等: "新型醋酸乙烯醋催化剂研制", 《金山油化纤》 * |
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