CN105289668A - Ethylidene diacetate catalyst and preparation method thereof - Google Patents
Ethylidene diacetate catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ethylidene diacetate catalyst and a preparation method thereof and mainly solves the problems in the prior art that an ethylidene diacetate catalyst is relatively low in activity and selectivity. The ethylidene diacetate catalyst comprises a main catalyst and a promoter, wherein the main catalyst comprises a carrier and an active component which is a rhodium compound; the promoter is an iodide; the carrier is silicon dioxide which is modified by a fluorochemical and coated with a coating; the coating consists of a modified metallic element and a silicon dioxide binder by which the modified metallic element is bonded onto the surface of the carrier; the content of the fluorine element is 0.50-5.00 g/L; the content of the modified metallic element is 0.010-1.00 g/L; the modified metallic element is selected from at least one of IIA metallic elements. By the adoption of the technical scheme, the problem is better solved, and the ethylidene diacetate catalyst can be used for industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the synthetic method of ethylidene diacetate catalyst, preparation method and ethylidene diacetate.
Background technology
Vinyl acetate (VAc) is one of maximum 50 kinds of industrial chemicals of world wide production, by autohemagglutination or with other monomer copolymerization, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE) or the derivative such as copolymer resins (EVA), vinyl acetate-chloride copolymer (EVC) can be generated.These derivatives are widely used in cementing agent, coating, ink, leather processing, fiber process, emulsifying agent, the aspect such as water-solubility membrane and soil conditioner of adhesive, building coating, paper or fabric.
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 not high problem of ethylidene diacetate yield, and provide a kind of new ethylidene diacetate catalyst, 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 preparation methods of the described catalyst of one of above-mentioned technical problem.
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: ethylidene diacetate catalyst, and described catalyst comprises major catalyst and co-catalyst, and described major catalyst comprises carrier, active component; Described active component adopts the compound of rhodium; Described co-catalyst is iodide; Described carrier is for containing cated silica with fluorochemical its surface modified; Described coating forms by modified metal element and by the silica binder that described modified metal element is bonded in described carrier surface; Described fluorine-containing constituent content is 0.50 ~ 5.00g/L; Modified metal constituent content is 0.010 ~ 1.00g/L; Described modified metal element is selected from least one in IIA metallic element.
The compound of rhodium described in technique scheme is preferably RhCl
3.Described iodide are preferably iodomethane.At least one in the preferred ammonium fluosilicate of described fluorine-containing compound, ammonium fluoride, hydrofluoric acid and sodium fluoride.At least one of described IIA metallic element preferably in Mg, Ca, Sr and Ba.More preferably described IIA metallic element comprises Sr and Ba simultaneously.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: major catalyst preparation method described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
1. fluorine-containing compound is mixed with aqueous impregnation silica, drying obtains described catalyst carrier precursor I;
2. the hydroxide of described modified metal element or oxide and Ludox are mixed to get coating liquid;
3. above-mentioned coating liquid is coated to precursor carrier I surface, dry, roasting obtains described catalyst carrier II;
4. the composition of catalyst is pressed by RhCl
3solution mixes with described catalyst carrier II;
5. standing, dry, roasting, obtains described major catalyst.
The preparation key of catalyst of the present invention is the preparation of major catalyst, after obtaining major catalyst, to contact can obtain catalyst of the present invention by making major catalyst with described co-catalyst.The mode that major catalyst contacts with co-catalyst is not particularly limited, and is also not particularly limited the opportunity of contact making both.Both such as can be made before catalyst of the present invention is used for chemical reaction contact to form described catalyst, and in the reaction system that both can also be made to apply at catalyst of the present invention, contact makes catalyst in-situ preparation.
The present inventor finds, in technique scheme, activity component impregnation is used at the same time ammonium fluosilicate, ammonium fluoride, containing Sr with no matter be selective containing the catalyst that obtains on the compound modified carrier of Ba or EDDA yield all reaches best.
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, Reactive Synthesis ethylidene diacetate under catalyst according to any one of the technical scheme of one of above-mentioned technical problem exists.
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 0.10 ~ 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 catalyst carrier uses fluorine-containing compound and IIA metallic element to carry out modified, is conducive to improving the activity of major catalyst and stability, thus improves the yield of ethylidene diacetate and selective.
Experimental result shows, the ethylidene diacetate yield prepared by the present invention reaches 62.16%, selectively reaches 84.03%, achieves good technique effect.Especially in catalyst carrier modifying process, use ammonium fluosilicate, ammonium fluoride simultaneously, containing Sr and work in coordination with containing Ba time, achieve more outstanding technique effect.Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain described catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.57g/L, containing Mg0.47g/L for carrier.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 60.55% as calculated, selective is 84.39%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, 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].
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is the spherical SiO of 5.6mm by 1.0L diameter
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 51.27% as calculated, selective is 79.86%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[comparative example 2]
For the comparative example of [embodiment 1].
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Then after Muffle furnace 500 DEG C of roastings, catalyst carrier II is obtained.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
Carrier by analysis, fluorine-containing 1.57g/L.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 55.63% as calculated, selective is 80.24%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[comparative example 3]
For the comparative example of [embodiment 1].
The preparation of catalyst carrier II: be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 1.0g and concentration, coating liquid is sprayed at the spherical SiO that 1.0L diameter is 5.6mm uniformly
2carrier mixes, and 100 DEG C of dryings, obtain catalyst carrier II after Muffle furnace 500 DEG C of roastings.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, is warming up to 500 DEG C of roasting 5h, obtains major catalyst in N2 atmosphere.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
Carrier by analysis, containing Mg0.47g/L.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 55.83% as calculated, selective is 81.53%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, 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, the catalyst carrier that the present invention adopts, use the carrier of Performance Ratio without any modification of the fluorine-containing and metal-modified rear catalyst of IIA, than only with fluorine-containing compound modified carrier, more excellent than the performance of the catalyst only made with the metal-modified carrier of IIA simultaneously, selective and the yield of ethylidene diacetate all wants high, this describes between fluorine-containing compound and IIA metal be present in good synergy as can be seen from the data of embodiment 1, comparative example 1 ~ 3.
[embodiment 2]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluoride aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.58g/L, containing Mg0.48g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 60.82% as calculated, selective is 84.21%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 3]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the hydrofluoric acid aqueous solution 0.8L of 5.00g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 10.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 2.4g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, is warming up to 500 DEG C of roasting 5h, obtains major catalyst in N2 atmosphere.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 4.90g/L, containing Mg0.97g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 61.24% as calculated, selective is 83.97%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 4]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the sodium fluoride aqueous solution 0.8L of 0.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 1.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 0.1g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 0.59g/L, containing Mg0.04g/L for carrier.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 60.63% as calculated, selective is 84.66%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 5]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the lime powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.57g/L, containing Ca0.59g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 61.89% as calculated, selective is 83.88%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 6]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the strontium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.58g/L, containing Sr0.70g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 61.19% as calculated, selective is 84.15%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 7]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the barium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.58g/L, containing Ba0.79g/L for carrier.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 62.04% as calculated, selective is 84.22%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 8]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluoride aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the barium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.57g/L, containing Ba0.78g/L for carrier.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 62.16% as calculated, selective is 84.03%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 9]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the barium hydroxide powder of 0.5g, 0.5g strontium hydroxide powder and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain catalyst carrier II after Muffle furnace 500 DEG C of roastings.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.58g/L, containing Ba0.39g/L, containing Sr0.35g/L for carrier.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 63.27% as calculated, selective is 84.87%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 9 and embodiment 6 and embodiment 7, in the selective and yield improving EDDA, Ba and Sr has synergy.
[embodiment 10]
The preparation of catalyst carrier II: be the spherical SiO of 5.6mm by the ammonium fluosilicate containing 1.00g fluorine and the aqueous solution 0.8L of ammonium fluoride containing 0.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the barium hydroxide powder of 1.0g and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain the carrier II being coated with modified metal element after Muffle furnace 500 DEG C of roastings.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.58g/L, containing Ba0.78g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 63.14% as calculated, selective is 85.01%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 8 and embodiment 7, in the selective and yield improving EDDA, ammonium fluosilicate and ammonium fluoride have synergy.
[embodiment 11]
The preparation of catalyst carrier II: be the spherical SiO of 5.6mm by the ammonium fluosilicate containing 1.00g fluorine and the aqueous solution 0.8L of ammonium fluoride containing 0.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the barium hydroxide powder of 0.5g, 0.5g strontium hydroxide powder and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain catalyst carrier II after Muffle furnace 500 DEG C of roastings.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 8.0MPa, improve mixing speed to 1500rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 170 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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.
By analysis, fluorine-containing 1.58g/L, containing Ba0.39g/L, containing Sr0.36g/L for carrier.The Rh content of this catalyst is 6.67g/L.The yield of ethylidene diacetate is 67.02% as calculated, selective is 87.93%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, in the selective and yield improving EDDA, ammonium fluosilicate, ammonium fluoride and Ba, Sr have synergy.
[embodiment 12]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 1500rpm, 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.
By analysis, fluorine-containing 1.57g/L, containing Mg0.47g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 51.12% as calculated, selective is 71.24%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
[embodiment 13]
The preparation of catalyst carrier II: will be the spherical SiO of 5.6mm containing the ammonium fluosilicate aqueous solution 0.8L of 1.60g fluorine and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% Ludox 4.0g is fully mixed to get coating liquid by the magnesium hydroxide powder of 1.0g and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after Muffle furnace 500 DEG C of roastings, obtain catalyst carrier II.
The preparation of major catalyst: by the RhCl containing 6.80gRh
33H
2o is dissolved in pure water, obtains maceration extract 500ml, is immersed in by catalyst carrier II described in 1.0L in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain major catalyst.
The synthesis of ethylidene diacetate: 0.5mol acetic acid, 0.02mol major catalyst, 0.02mol iodomethane and 0.15mol 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 1500rpm, agitating heating is warming up to reaction temperature simultaneously, controlling reaction temperature is 200 DEG C, 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.
By analysis, fluorine-containing 1.57g/L, containing Mg0.47g/L for carrier.The Rh content of this catalyst is 6.68g/L.The yield of ethylidene diacetate is 62.54% as calculated, selective is 83.47%, for convenience of explanation and compare, by the yield of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, ethylidene diacetate with selectively list in table 1 and table 2 respectively.
Table 1 (continued)
Table 1 (Continued)
Table 2 (continued)
Table 2 (Continued)
Claims (10)
1. ethylidene diacetate catalyst, described catalyst major catalyst and co-catalyst, major catalyst comprises carrier, active component; Described active component adopts the compound of rhodium; Described co-catalyst is iodide; Described carrier is for containing cated silica with fluorochemical its surface modified; Described coating forms by modified metal element and by the silica binder that described modified metal element is bonded in described carrier surface; Described fluorine-containing constituent content is 0.50 ~ 5.00g/L; Modified metal constituent content is 0.010 ~ 1.00g/L; Described modified metal element is selected from least one in IIA metallic element.
2. catalyst according to claim 1, is characterized in that the compound of described rhodium is RhCl
3.
3. catalyst according to claim 1, is characterized in that described iodide are iodomethane.
4. catalyst according to claim 1, is characterized in that described fluorine-containing compound is selected from least one in ammonium fluosilicate, ammonium fluoride, hydrofluoric acid and sodium fluoride.
5. catalyst according to claim 1, is characterized in that described IIA metallic element is selected from least one in Mg, Ca, Sr and Ba.
6., by the preparation method of major catalyst according to claim 1, comprise the steps:
1. fluorine-containing compound is mixed with aqueous impregnation silica, drying obtains described catalyst carrier precursor I;
2. the hydroxide of described modified metal element or oxide and Ludox are mixed to get coating liquid;
3. above-mentioned coating liquid is coated to precursor carrier I surface, dry, roasting obtains described catalyst carrier II;
4. the composition of catalyst is pressed by RhCl
3mix with described catalyst carrier II;
5. standing, dry, roasting, obtains described major catalyst.
7. the synthetic method of ethylidene diacetate, with methyl acetate, carbon monoxide and hydrogen for raw material, take acetic acid as solvent, under Claims 1 to 5 catalyst described in any one exists, carry out Reactive Synthesis ethylidene diacetate.
8. synthetic method according to claim 7, is characterized in that the temperature of reacting is 130 ~ 200 DEG C.
9. synthetic method according to claim 7, is characterized in that the pressure reacted is 3.0 ~ 10.0MPa.
10. synthetic method according to claim 7, is characterized in that carbon monoxide and hydrogen volume ratio are 0.10 ~ 10.0.
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|---|---|---|---|---|
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| JPH04225838A (en) * | 1990-10-05 | 1992-08-14 | Korea Res Inst Chem Technol | Solid catalyst for ethylidene diacetate and its manufacture and manufacture of ethylidene dialetate by contnuous proces utilzing the same |
| CN101124043A (en) * | 2004-12-20 | 2008-02-13 | 国际人造丝公司 | Modified support materials for catalysts |
| 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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|---|---|---|---|---|
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| JPH04225838A (en) * | 1990-10-05 | 1992-08-14 | Korea Res Inst Chem Technol | Solid catalyst for ethylidene diacetate and its manufacture and manufacture of ethylidene dialetate by contnuous proces utilzing the same |
| CN101124043A (en) * | 2004-12-20 | 2008-02-13 | 国际人造丝公司 | Modified support materials for catalysts |
| 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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