CN105478113B - Produce the catalyst used in ethylidene diacetate - Google Patents
Produce the catalyst used in ethylidene diacetate Download PDFInfo
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Abstract
The present invention relates to the catalyst used in production ethylidene diacetate, mainly solve the problems, such as that ethylidene diacetate catalyst activity and selectivity is relatively low in the prior art, by using ethylidene diacetate catalyst, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes at least one selected from platinum cluster metal, the technical solution selected from metalloid element at least one and selected from least one of IIB and lanthanide element metallic element, the technical problem is preferably resolved, available in the industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the catalyst used in production ethylidene diacetate, the catalyst system used in ethylidene diacetate is produced
The synthetic method of Preparation Method and ethylidene diacetate.
Background technology
Vinyl acetate, i.e. vinyl acetate (vinyl acetate, abbreviation VAC or VAM), are water white transparency at room temperature
Inflammable liquid, the ether fragrance with sweet tea.It is one of Organic Chemicals that yield is larger in the world, and it is poly- to be widely used in production
Vinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal resin etc.
A series of chemical industry and fiber product, are widely used in all trades and professions.
Ethene vapor phase method and acetylene in gas phase method technique are used inside and outside the producing country of vinyl acetate, belongs to petrochemical process
Route, from after rising C1 chemistry, in the 1980s, U.S. Ha Erkang (Halcon) companies and British Petroleum (BP) company are successively
It is proposed is prepared new process-carbonyl process synthesizing vinyl acetate of vinyl acetate by methanol and synthesis gas.The technique does not depend on oil
Work raw material, but by methyl acetate and the carbonylation of synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then pass through
Cross thermal cracking production vinyl acetate and acetic acid.The novel part of whole technique is the hydroformylation reaction of methyl acetate, is catalyzed
Agent radium chloride is simultaneously modified with beta-picoline and iodomethane, and carbon monoxide intercalation reaction is the key point of whole technology.
It is (entitled via US4,429,150 by the preparation method of methyl acetate synthesis ethylidene diacetate：
Manufacture of ethylidene diacetate) it is disclosed, i.e., with methyl acetate or methyl ether, carbon monoxide and hydrogen
For raw material, catalyst is using the double acetic acid Asias second of synthesis in the presence of VIII halide or acetate and phosphorous polar solvent
Ester.US5,354,886 is (entitled：Catalysts on inorganic carriers for producing
Ethylidene diacetate) mention RhCl3Or rhodium compound is supported on diatomite, titanium oxide, magnesia, aluminium oxide
With loaded catalyst is made on zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, under polar solvent conditions,
The reaction synthesis ethylidene diacetate under above-mentioned catalyst.There are double vinegar during ethylidene diacetate is prepared in the above method
The problem of sour ethyl yield is low and selective not high.
The content of the invention
The problem of the first technical problem to be solved by the present invention is that ethylidene diacetate yield is low and selectivity is low, there is provided
A kind of catalyst produced used in ethylidene diacetate, the catalyst have ethylidene diacetate high income to ethylidene diacetate
The characteristics of high selectivity.
The second technical problem to be solved by the present invention is the preparation side using one of the above-mentioned technical problem catalyst
Method.
The third technical problem to be solved by the present invention is double acetic acid using one of the above-mentioned technical problem catalyst
The synthetic method of ethyl.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Produce ethylidene diacetate institute
Catalyst, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes being selected from platinum cluster metal
At least one, at least one and selected from least one of IIB and lanthanide element metal member selected from metalloid element
Element.It is preferred that the active component is at the same time including platinum cluster metallic element, metalloid element, selected from least one of IIB metals member
Element and selected from least one of lanthanide series metal metallic element.At this time the metallic element of the metallic element of IIB and lanthanide series metal it
Between improve EDDA selectivity and yield in terms of have synergistic effect.
In above-mentioned technical proposal, the platinum cluster metallic element preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium.
In above-mentioned technical proposal, the metalloid element preferably is selected from least one of boron, arsenic and tellurium.
In above-mentioned technical proposal, as most preferred technical solution, the active component metalloid element is more preferably boron
With tellurium metalloid.
In above-mentioned technical proposal, the IIB metals preferably are selected from least one of zinc, cadmium and mercury.
In above-mentioned technical proposal, the lanthanide series metal preferably is selected from least one of lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
In above-mentioned technical proposal, as most preferred technical solution, the active component at the same time including platinum cluster metallic element,
Metalloid element, IIB metals and lanthanide series metal；Such as the active component includes rhodium, boron, zinc (or cadmium) and cerium, or including
Rhodium, boron (or tellurium), zinc, cadmium and cerium, either including rhodium, boron, tellurium, zinc, cadmium and cerium (or lutetium) or including rhodium, boron, tellurium, zinc,
Cadmium, cerium and lutetium.
In above-mentioned technical proposal, the content of platinum cluster metallic element is preferably 3.00~15.00g/L in the catalyst, more
Preferably 5.00~10.00g/L；The content of metalloid element is preferably 0.10~5.00g/L in the catalyst, more preferably
1.00~4.00g/L；In the catalyst in IIB and lanthanide series at least one content of metal be preferably 0.50~
8.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the catalyst is preferably 50~300m2/ g, more
Preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case, includes the following steps：
1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of metalloid element, IIB metals and lanthanum
It is that the solution of the compound of metal is mixed with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. platinum cluster metal preferably is selected from radium chloride, two ligand of rhodium acetate, three
Phenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, four ammonia palladium of dichloro, palladium, ammonium chloropalladite, excessively ruthenic chloride, amine, two in ruthenic acid four
At least one of platinum chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid.Step is 1. described accurate golden
The compound for belonging to element preferably is selected from boric acid, ammonium pentaborate, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, titanium dioxide
At least one of tellurium and telluric acid.Step 1. the IIB metallic compounds preferably be selected from zinc gluconate, zinc citrate, zinc acetate,
At least one of cadmium acetate, cadmium nitrate, caddy and mercuric sulfate.1. the lanthanide metals compound preferably is selected from vinegar to step
Sour lanthanum, lanthanum chloride, lanthanum nitrate, cerous acetate, cerium chloride, cerous nitrate, praseodymium acetate, praseodymium chloride, acetic acid neodymium, samarium trichloride, ytterbium chloride and
At least one of lutecium chloride.2. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of ethylidene diacetate, with
Methyl acetate, carbon monoxide and hydrogen are raw material, using acetic acid as solvent, are reacted in the presence of catalyst and co-catalyst iodide
Generate ethylidene diacetate.The preferred iodomethane of iodide.
The key of the present invention is the selection of catalyst, and skilled person will know how definite suitable according to being actually needed
Reaction temperature, the reaction time, the proportioning of reaction pressure and material.But the temperature reacted in above-mentioned technical proposal 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.Carbon monoxide with
The molar ratio of hydrogen is preferably 0.1~10.0.
Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the conversion ratio of methyl acetate and the yield and selectivity of ethylidene diacetate：
Compared with prior art, key of the invention is that the active component of catalyst includes a certain amount of platinum cluster metal member
Element, metalloid element and selected from least one of IIB and lanthanide metals metallic element, are conducive to improve major catalyst
Activity and stability, so as to improve the yield and selectivity of ethylidene diacetate.
Test result indicates that the ethylidene diacetate yield prepared by the present invention selectively reaches up to 61.53%
86.49%, achieve active component in preferable technique effect, especially catalyst while include platinum cluster metal, metalloid member
Element, selected from least one of IIB metallic elements and selected from least one of lanthanide series metal metallic element when, achieve more
Prominent technique effect, can be used in the synthesis of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of catalyst：By Rh containing 6.30g, the RhCl containing 2.90gB and containing 3.00gZn3·3H2O, ammonium pentaborate
((NH4)B5O8·8H2) and zinc gluconate (C O12H22O14Zn3·3H2O) it is sufficiently mixed and is dissolved in pure water, obtains maceration extract
400ml, than surface is 165m by 1.0L2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B
Content 2.90g/L, Zn content 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.53%, and selectivity is 86.49%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 2】
The preparation of catalyst：By Rh containing 6.30g, the RhCl containing 2.90gB and containing 3.00gCe3·3H2O, ammonium pentaborate
((NH4)B5O8·8H2) and Ce (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L ratios
Surface is 165m2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation in above-mentioned maceration extract, stand 2h in
100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content 2.90g/L,
Ce contents 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.73%, and selectivity is 86.26%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By Rh containing 6.30g and the RhCl containing 2.90gB3·3H2O and ammonium pentaborate ((NH4)B5O8·
8H2O) it is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume 0.95, directly
Footpath is the spherical SiO of 5.6mm2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Rh contents that ICP-MS analyzes the catalyst are 6.30g/L, B content 2.90g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 52.54%, and selectivity is 75.37%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using at the same time containing Rh, B and Zn work
Property component while catalyst performance ratio containing Rh, B and Ce active component will be more containing only the performance of Rh, B activity component catalyst
Excellent, the selectivity and yield of ethylidene diacetate will be high.
【Embodiment 3】
The preparation of catalyst：By the triphenylphosphine chlorine rhodium of Rh containing 5.00g, B containing 1.00g and the Zn containing 1.00g
(C54H45ClP3Rh), boric acid (H3BO3) and zinc citrate Zn3(C6H5O7)2·2H2It is 10wt% that O, which is sufficiently mixed and is dissolved in concentration,
Acetic acid in, obtain maceration extract 400ml, than surface be 150m by 1.0L2/ g, pore volume 0.90, a diameter of 5.6mm's is spherical
Al2O3Carrier impregnation stands 2h in 80 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is analyzed through ICP-MS
The Rh contents of agent are 5.00g/L, B content 1.00g/L, Zn content 1.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 57.47%, and selectivity is 85.62%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 4】
The preparation of catalyst：By the two ligand (Rh of rhodium acetate containing 10.00gRh, containing the 4.00gAs and Cd containing 5.00g2
(OAc)4), arsenic acid (H3AsO4·0.5H2) and Cd (OAc) O2·2H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract
400ml, than surface is 200m by 1.0L2/ g, pore volume 1.00, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 120 DEG C of dryings, obtains the catalyst.Rh contents through the icp analysis catalyst are 10.00g/L, As
Content 4.00g/L, Cd content 5.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 62.24%, and selectivity is 85.59%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 5】
The preparation of catalyst：By Rh containing 6.30g, the Rh (NO containing the 2.90gTe and Cd containing 3.00g3)3, ammonium tellurate
((NH4)2TeO4) and Cd (NO3)2·4H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.Rh contents through the icp analysis catalyst are 6.30g/L, Te contents 2.90g/L, Cd content
3.00g/L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.45%, and selectivity is 86.25%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 6】
The preparation of catalyst：By the PdCl containing 6.30gPd, containing 2.90gTe and containing 3.00gCd2、TeO2And CdCl2It is fully mixed
Close and be dissolved in the hydrochloric acid that concentration is 8wt%, obtain maceration extract 400ml, than surface be 165m by 1.0L2/ g, pore volume 0.95,
The spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.
Pd contents through the icp analysis catalyst are 6.30g/L, Te contents 2.90g/L, Cd content 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.51%, and selectivity is 86.38%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 7】
The preparation of catalyst：By the four ammonia palladium (Pd (NH of dichloro containing 6.30gPd, containing 2.90gTe and containing 3.00gHg3)4Cl2·H2O)、H6TeO6And HgSO4It is sufficiently mixed and is dissolved in the salt that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L
It is 165m than surface2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.Pd contents through the icp analysis catalyst are 6.30g/L, Te content 2.90g/L,
Hg contents 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.30%, and selectivity is 86.35%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 8】
The preparation of catalyst：By the Pd (OAc) containing 6.30gPd, B containing 2.90g and containing 3.00gSm2, ammonium pentaborate ((NH4)
B5O8·8H2) and SmCl O3·6H2O, which is sufficiently mixed, to be dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract 400ml, will
1.0L is 165m than surface2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is quiet in above-mentioned maceration extract
2h is put in 100 DEG C of dryings, obtains the catalyst.The Pd contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content
2.90g/L, Sm content 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 3.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 130 DEG C, and the molar ratio of carbon monoxide and hydrogen is 1：After 10, sustained response 3.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 51.78%, and selectivity is 79.73%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 9】
The preparation of catalyst：By the RuCl containing 6.30gRu, B containing 2.90g and the La containing 3.00g3·XH2O, ammonium pentaborate
((NH4)B5O8·8H2) and LaCl O3·7H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared surface
For 165m2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C in above-mentioned maceration extract
It is dry, obtain the catalyst.The Ru contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content 2.90g/L, La content
3.00g/L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 10.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 200 DEG C, and the molar ratio of carbon monoxide and hydrogen is 10：After 1, sustained response 10.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 62.85%, and selectivity is 84.61%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 10】
The preparation of catalyst：By the ammonium chloroplatinite ((NH containing 6.30gPt, containing 2.90gB and containing 3.00gPr4)2PtCl4)、
Ammonium pentaborate ((NH4)B5O8·8H2) and Cl O3Pr·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, will
1.0L is 165m than surface2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is quiet in above-mentioned maceration extract
2h is put in 100 DEG C of dryings, obtains the catalyst.The Pt contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content
2.90g/L, Pr content 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.42%, and selectivity is 86.29%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 11】
The preparation of catalyst：By the OsCl containing 6.30gOs, containing 2.90gB and containing 3.00gNd3·3H2O, ammonium pentaborate
((NH4)B5O8·8H2) and Nd (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L ratios
Surface is 165m2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation in above-mentioned maceration extract, stand 2h in
100 DEG C of dryings, obtain the catalyst.The Os contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content 2.90g/L,
Nd contents 3.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.21%, and selectivity is 86.23%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 12】
The preparation of catalyst：By the IrCl containing 6.30gIr, containing 2.90gB and containing 3.00gYb3·XH2O, ammonium pentaborate
((NH4)B5O8·8H2) and YbCl O3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared surface
For 165m2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C in above-mentioned maceration extract
It is dry, obtain the catalyst.The Ir contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content 2.90g/L, Yb content
3.00g/L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.19%, and selectivity is 86.54%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 13】
The preparation of catalyst：By the RhCl containing 6.30gRh, containing 2.90gB and containing 3.00gLu3·3H2O, ammonium pentaborate
((NH4)B5O8·8H2) and LuCl O3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared surface
For 165m2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C in above-mentioned maceration extract
It is dry, obtain the catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content 2.90g/L, Lu content
3.00g/L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 61.28%, and selectivity is 86.33%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 14】
The preparation of catalyst：By Rh containing 6.30g, the RhCl containing 2.90gB, containing 1.45gZn and containing 1.55gCe3·3H2O、
Ammonium pentaborate ((NH4)B5O8·8H2O), zinc gluconate (C12H22O14Zn3·3H2) and Ce (OAc) O3·5H2O is sufficiently mixed molten
Solution obtains maceration extract 400ml in pure water, than surface is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm's is spherical
SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.This is analyzed through ICP-MS to urge
The Rh contents of agent are 6.30g/L, B content 2.90g/L, Zn content 1.45g/L, Ce content 1.55g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 63.03%, and selectivity is 87.92%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment is compared with embodiment 1, embodiment 2 as can be seen that IIB metals Zn and lanthanide series metal Ce is improving double vinegar
The activity and selectivity of sour ethyl catalyst has preferable synergistic effect.
【Embodiment 15】
The preparation of catalyst：By Rh containing 6.30g, the RhCl containing 2.90gB, containing 1.45gCd and containing 1.55gCe3·3H2O、
Ammonium pentaborate ((NH4)B5O8·8H2O)、Cd(NO3)2·4H2O and Ce (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, is obtained
Than surface it is 165m by 1.0L to maceration extract 400ml2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are
6.30g/L, B content 2.90g/L, Cd content 1.45g/L, Ce content 1.55g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 62.94%, and selectivity is 88.04%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 16】
The preparation of catalyst：By Rh containing 6.30g, containing 2.90gB, containing 0.78gZn, containing 0.67gCd and containing 1.55gCe's
RhCl3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), zinc gluconate (C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O
With Ce (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g, hole
Hold for 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B content 2.90g/L, Zn content 0.78g/L, Cd
Content 0.67g/L, Ce content 1.55g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 64.96%, and selectivity is 89.15%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment is compared with embodiment 14, embodiment 15 as can be seen that IIB metal Zn and Cd is other living with the present invention
Property component there is preferable synergistic effect in the activity and selectivity for improving ethylidene diacetate catalyst.
【Embodiment 17】
The preparation of catalyst：By Rh containing 6.30g, containing 2.90gTe, containing 0.78gZn, containing 0.67gCd and containing 1.55gCe's
RhCl3·3H2O, ammonium tellurate ((NH4)2TeO4), zinc gluconate (C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O and Ce
(OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume are
0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.Rh contents through the icp analysis catalyst are 6.30g/L, Te contents 2.90g/L, Zn content 0.78g/L, Cd content
0.67g/L, Ce content 1.55g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 64.93%, and selectivity is 89.20%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 18】
The preparation of catalyst：To contain 6.30g Rh, containing 1.34gB, containing 1.56gTe, containing 0.78gZn, containing 0.67gCd and contain
1.55gCe RhCl3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), ammonium tellurate ((NH4)2TeO4), zinc gluconate
(C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O and Ce (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, is impregnated
Liquid 400ml, than surface is 165m by 1.0L2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is in above-mentioned leaching
In stain liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are 6.30g/
L, B content 1.34g/L, Te content 1.56g/L, Zn content 0.78g/L, Cd content 0.67g/L, Ce content 1.55g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 66.13%, and selectivity is 90.81%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment compared with embodiment 16, embodiment 17 as can be seen that in metalloid B, Te with it is of the invention in it is other
The favourable selectivity and yield for improving ethylidene diacetate of active component collaboration, illustrates Rh, B, Te, Zn, Cd and Ce activearm
/ presence acts synergistically well.
【Embodiment 19】
The preparation of catalyst：To contain 6.30g Rh, containing 1.34gB, containing 1.56gTe, containing 0.78gZn, containing 0.67gCd and contain
1.55gLu RhCl3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), ammonium tellurate ((NH4)2TeO4), zinc gluconate
(C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O and LuCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract
400ml, than surface is 165m by 1.0L2/ g, pore volume 0.95, the spherical SiO of a diameter of 5.6mm2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is analyzed through ICP-MS are 6.30g/L, B
Content 1.34g/L, Te content 1.56g/L, Zn content 0.78g/L, Cd content 0.67g/L, Lu content 1.55g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 66.34%, and selectivity is 90.71%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 20】
The preparation of catalyst：To contain 6.30g Rh, containing 1.34gB, containing 1.56gTe, containing 0.78gZn, containing 0.67gCd, contain
The 0.70gCe and RhCl containing 0.85gLu3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), ammonium tellurate ((NH4)2TeO4), Portugal
Grape saccharic acid zinc (C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O、Ce(OAc)3·5H2O and LuCl3·6H2O is sufficiently mixed molten
Solution obtains maceration extract 400ml in pure water, than surface is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm's is spherical
SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.This is analyzed through ICP-MS to urge
The Rh contents of agent are 6.30g/L, B content 1.34g/L, Te content 1.56g/L, Zn content 0.78g/L, Cd content 0.67g/L,
Ce contents 0.70g/L, Lu content 0.85g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reaction kettles, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 175 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reaction mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 67.79%, and selectivity is 91.68%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment can be seen that Ce, Lu and its in the present invention in lanthanide series metal compared with embodiment 18, embodiment 19
The favourable selectivity and yield for improving ethylidene diacetate of its active component collaboration, illustrates that Rh, B, Te, Zn, Cd, Ce and Lu live
Property component between exist well synergistic effect.
Table 1
Table 2 (continued)
2 (Continued) of table
Claims (7)
1. producing the catalyst used in ethylidene diacetate, the catalyst uses SiO2、Al2O3Or its mixture is carrier,
Active component includes at least one selected from platinum cluster metal, selected from metalloid element at least one and selected from IIB and group of the lanthanides gold
Belong at least one of element metallic element, the content of the platinum cluster metal is 3.00~15.00g/L, and metalloid element contains
Measure as 0.10~5.00g/L, it is described selected from least one of IIB metals and lanthanide series metal content be 0.50~8.00g/L.
2. catalyst according to claim 1, it is characterised in that the platinum cluster metal is in platinum, palladium, osmium, iridium, ruthenium and rhodium
At least one.
3. catalyst according to claim 1, it is characterised in that the metalloid element in boron, arsenic and tellurium at least one
Kind.
4. catalyst according to claim 1, it is characterised in that the IIB metals are selected from least one of zinc, cadmium and mercury.
5. catalyst according to claim 1, it is characterised in that the lanthanide element is selected from lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium
At least one of with lutetium.
6. the preparation method of the catalyst described in claim 1, includes the following steps：
It is 1. by the composition of catalyst that the compound of platinum cluster metallic element, the compound of metalloid element, IIB metals and group of the lanthanides is golden
The solution of the compound of category is mixed with carrier；
2. dry.
7. the synthetic method of ethylidene diacetate, using methyl acetate, carbon monoxide and hydrogen as raw material, using acetic acid as solvent,
Ethylidene diacetate is synthesized in the presence of catalyst any one of Claims 1 to 5 and co-catalyst iodide.
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Citations (5)
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|---|---|---|---|---|
| EP0035860A2 (en) * | 1980-03-06 | 1981-09-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing ethylidene diacetate and/or acetaldehyde |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| 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 |
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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 |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| EP0035860A2 (en) * | 1980-03-06 | 1981-09-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing ethylidene diacetate and/or acetaldehyde |
| 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 |
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