CN105478116A - Catalyst for synthesizing ethylidene diacetate - Google Patents
Catalyst for synthesizing ethylidene diacetate Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing 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 rhodium, alkaline-earth metal and at least one metal element selected from VIB and VA, 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 the catalyst for the synthesis of ethylidene diacetate, the synthetic method of ethylidene diacetate method for preparing catalyst and 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 catalyst for the synthesis of ethylidene diacetate, 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: for the synthesis of the catalyst of ethylidene diacetate, and described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprises rhodium, alkaline-earth metal and is selected from least one metallic element in VIB and VA.Preferred described active component comprises rhodium, alkaline-earth metal, at least one metallic element that is selected from least one metallic element in VIB and is selected from VA simultaneously.Now there is synergy improving in the selective and yield of EDDA between the metallic element of VIB and the metallic element of VA.
In technique scheme, at least one of described alkaline-earth metal preferably in beryllium, magnesium, calcium, strontium and barium.
In technique scheme, at least one of described vib metal preferably in chromium, molybdenum and tungsten.
In technique scheme, at least one of described VA metal preferably in antimony and bismuth.
In technique scheme, as most preferred technical scheme, described active component comprises rhodium, alkaline-earth metal, chromium element and antimony element simultaneously; Such as, when described active component is made up of rhodium, magnesium, strontium, chromium and antimony element.
In technique scheme, in described catalyst, the content of rhodium is preferably 3.00 ~ 15.00g/L, is more preferably 5.0 ~ 10.0g/L; In described catalyst, the content of alkaline-earth metal is preferably 0.10 ~ 5.00g/L, is more preferably 0.50 ~ 3.00g/L; At least one content being selected from metal in VIB and VA 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. the solution pressing metallic compound in the compound of composition by rhodium of catalyst, the compound of alkaline-earth metal, VIB and VA mixes with carrier;
2. dry.
In technique scheme, at least one of compound preferably in rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate of step 1. described rhodium.At least one of compound preferably in alkaline earth oxide, alkaline earth metal chloride, alkaline earth nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate of step 1. described alkaline-earth metal.At least one of compound preferably in chromic acetate, chromic nitrate, chromium chloride, molybdenum pentachloride and sodium tungstate of step 1. described vib metal.Step is at least one of compound preferably in basic bismuth carbonate, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride of metal in described VA 1..Step 2. described baking temperature is 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 at least one metallic element that the active component of catalyst comprises certain amount rhodium, alkaline-earth metal and is selected from VIB and VA, be conducive to improving the activity of catalyst and stability, thus improve the yield of ethylidene diacetate and selective.
Experimental result shows, ethylidene diacetate yield prepared by the present invention reaches 60.85%, selectively reach 86.72%, achieve good technique effect, especially when in catalyst, active component comprises rhodium, alkaline-earth metal simultaneously, is selected from least one metallic element in VIB and is selected from least one metallic element in VA, 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 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gCr
33H
2o, MgCl
2and CrCl
36H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Cr content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.85% as calculated, and selective is 86.72%, 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 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gSb
33H
2o, MgCl
2and Cl
3the abundant mixed dissolution of Sb, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Sb content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.71% as calculated, and selective is 86.93%, 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 6.50gRh and the RhCl containing 1.70gMg be contained
33H
2o and MgCl
2abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured.
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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 51.41% as calculated, and selective is 73.27%, 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 Rh, Mg active constituent catalyst containing Rh, Mg and Cr active component, catalyst performance simultaneously containing Rh, Mg and Sb active component, the selective and yield of ethylidene diacetate all wants height.
[embodiment 3]
The preparation of catalyst: by containing 5.00gRh, containing 0.50gBe with containing the Rh (OAc) of 1.00gCr
3, BeSO
44H
2o and Cr (OAc)
36H
2the abundant mixed dissolution of O is in the acetic acid of 10wt% in concentration, obtains 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 Rh content of this catalyst is 5.00g/L, Be content 0.50g/L after measured, Cr 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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 59.82% as calculated, and selective is 86.83%, 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 10.00gRh, containing 3.00gCa with containing the Rh (NO of 5.00gCr
3)
3, Ca (NO
3)
24H
2o and Cr (NO
3)
39H
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 Rh content of this catalyst is 10.00g/L, Ca content 3.00g/L after measured, Cr 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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.18% as calculated, and selective is 86.23%, 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 6.50gRh, containing 1.70gSr with containing the RhCl of 3.40gMo
33H
2o, Sr (OA
c)
20.5H
2o and MoCl
5abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Sr content 1.70g/L after measured, Mo content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.42% as calculated, and selective is 86.53%, 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 6.50gRh, containing 1.70gBa with containing the Rh (SO of 3.40gW
4)
3, BaO and ammonium tungstate ((NH
4)
10w
12o
414H
2o) fully mixed dissolution is in pure water, and obtaining maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Ba content 1.70g/L after measured, W content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.57% as calculated, and selective is 86.87%, 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 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gBi
33H
2o, MgCl
2with basic bismuth carbonate ((BiO)
2cO
30.5H
2o) fully mixed dissolution is in pure water, and obtaining maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Bi content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.52% as calculated, and selective is 86.34%, 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 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gBi
33H
2o, MgCl
2and Bi
2(SO
4)
3abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Bi content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.44% as calculated, and selective is 86.22%, 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 9]
The preparation of catalyst: by containing 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gBi
33H
2o, MgCl
2and Bi
2o
3abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Bi content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.13% as calculated, and selective is 86.54%, 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 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gBi
33H
2o, MgCl
2and BiCl
3abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Bi content 3.40g/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 53.89% as calculated, and selective is 78.04%, 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.
[embodiment 11]
The preparation of catalyst: by containing 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gSb
33H
2o, MgCl
2and Sb
2o
3abundant mixed dissolution is in the aqueous solution of nitric acid of 8wt% in concentration, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Sb content 3.40g/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 60.91% as calculated, and selective is 85.94%, 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 6.50gRh, containing 1.70gMg with containing the RhCl of 3.40gSb
33H
2o, MgCl
2and Cl
3the abundant mixed dissolution of Sb, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 1.70g/L after measured, Sb content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.38% as calculated, and selective is 86.49%, 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 6.50gRh, containing 1.70gSr with containing the RhCl of 3.40gCr
33H
2o, SrCl
26H
2o and CrCl
36H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Sr content 1.70g/L after measured, Cr content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 60.42% as calculated, and selective is 86.28%, 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 14]
The preparation of catalyst: by containing 6.50gRh, containing 0.73gMg, containing 0.97gSr with containing the RhCl of 3.40gCr
33H
2o, MgCl
2, SrCl
26H
2o and CrCl
36H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 0.73g/L after measured, Sr content 0.97g/L, Cr content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 61.85% as calculated, and selective is 87.83%, 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 1, embodiment 13, in alkaline-earth metal, in Sr, Mg and the present invention, other active component works in coordination with the selective and yield of favourable raising ethylidene diacetate, describes between Rh, Sr, Mg and Cr tetra-kinds of active components and there is well synergy.
[embodiment 15]
The preparation of catalyst: by containing 6.50gRh, containing 0.73gMg, containing 0.97gSr with containing the RhCl of 3.40gSb
33H
2o, MgCl
2, SrCl
26H
2o and Cl
3the abundant mixed dissolution of Sb, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 0.73g/L after measured, Sr content 0.97g/L, Sb content 3.40g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 61.80% as calculated, and selective is 87.86%, 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 16]
The preparation of catalyst: by containing 6.50gRh, containing 0.73gMg, containing 0.97gSr, containing 1.07gCr with containing the RhCl of 2.33gSb
33H
2o, MgCl
2, SrCl
26H
2o, CrCl
36H
2o and Cl
3the abundant mixed dissolution of Sb, in pure water, obtains maceration extract 400ml, is 175m by 1.0L specific surface
2/ g, pore volume is 0.96, 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 Rh content of this catalyst is 6.50g/L, Mg content 0.73g/L after measured, Sr content 0.97g/L, Cr content 1.07g/L, Sb content 2.33g/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 6.5MPa, improve mixing speed to 1200rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 165 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 63.79% as calculated, and selective is 88.45%, 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 14, embodiment 15, in vib metal, in Cr, VA metal, in Sb and the present invention, other active component works in coordination with the selective and yield of favourable raising ethylidene diacetate, describes between Rh, Sr, Mg, Cr and Sb five kinds of active components and there is well synergy.
Table 1
Table 2
Claims (10)
1., for the synthesis of the catalyst of ethylidene diacetate, described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprises rhodium, alkaline-earth metal and is selected from least one metallic element in VIB and VA.
2. 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.
3. catalyst according to claim 1, is characterized in that described vib metal is selected from least one in chromium, molybdenum and tungsten.
4. catalyst according to claim 1, is characterized in that described VA metal is selected from least one in antimony and bismuth.
5. catalyst according to claim 1, it is characterized in that the content of rhodium in catalyst is: 3.00 ~ 15.00g/L, the content of alkaline-earth metal is: 0.10 ~ 5.00g/L.
6. catalyst according to claim 1, at least one content that it is characterized in that being selected from described in catalyst metal in VIB and VA is 0.5 ~ 8.0g/L.
7., by the preparation method of catalyst according to claim 1, comprise the steps:
1. the solution pressing metallic compound in the compound of composition by rhodium of catalyst, the compound of alkaline-earth metal, VIB and VA mixes with carrier;
2. dry.
8. the production method of catalyst according to claim 7, is characterized in that the compound of step 1. described rhodium is selected from least one in rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate.
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 ~ 6, 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0035860A2 (en) * | 1980-03-06 | 1981-09-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing ethylidene diacetate and/or acetaldehyde |
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing 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 |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| EP0035860A2 (en) * | 1980-03-06 | 1981-09-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing ethylidene diacetate and/or acetaldehyde |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
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