CN105478116B - For synthesizing the catalyst of ethylidene diacetate - Google Patents
For synthesizing the catalyst of ethylidene diacetate Download PDFInfo
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Abstract
The present invention relates to the catalyst for synthesizing ethylidene diacetate, mainly solves the problems, such as that ethylidene diacetate catalyst activity and selectivity is relatively low in the prior art, and by using ethylidene diacetate catalyst, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline-earth metal and the technical solution selected from least one of VIB and VA 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 for synthesizing ethylidene diacetate, ethylidene diacetate method for preparing catalyst and
The synthetic method of 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 for being used to synthesize 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：For synthesizing double acetic acid Asias second
The catalyst of ester, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline-earth metal
With selected from least one of VIB and VA metallic element.It is preferred that the active component is at the same time including rhodium, alkaline-earth metal, selected from VIB
At least one of metallic element and selected from least one of VA metallic elements.The metal of the metallic element of VIB and VA at this time
There is synergistic effect in terms of EDDA selectivity and yield is improved between element.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, the vib metal preferably is selected from least one of chromium, molybdenum and tungsten.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, as most preferred technical solution, the active component at the same time including rhodium, alkaline-earth metal,
Chromium and antimony element；Such as the active component rhodium, magnesium, strontium, chromium and antimony element when being made of.
In above-mentioned technical proposal, the content of rhodium is preferably 3.00~15.00g/L in the catalyst, more preferably 5.0~
10.0g/L；The content of alkaline-earth metal is preferably 0.10~5.00g/L in the catalyst, more preferably 0.50~3.00g/L；
In the catalyst selected from VIB and VA 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 catalyst composition by the compound of rhodium, the compound of alkaline-earth metal, VIB and VA metallic compound it is molten
Liquid is mixed with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. rhodium preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate
At least one of.The compound of the step 1. alkaline-earth metal preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkali
At least one of earth metal nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate.The change of the step 1. vib metal
Compound preferably is selected from least one of chromic acetate, chromic nitrate, chromium chloride, molybdenum pentachloride and sodium tungstate.Step 1. gold in the VA
The compound of category preferably is selected from basic bismuth carbonate, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride at least
It is a kind of.2. the drying temperature is 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 rhodium, alkaline earth gold
Belong to and selected from least one of VIB and VA metallic element, be conducive to improve the activity and stability of catalyst, 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 60.85%
86.72%, achieve active component in preferable technique effect, especially catalyst while include rhodium, alkaline-earth metal, be selected from
At least one of VIB metallic elements and during selected from least one of VA metallic elements, achieve more prominent technology effect
Fruit, 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 the RhCl of Rh containing 6.50g, Mg containing 1.70g and the Cr containing 3.40g3·3H2O、MgCl2With
CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, pore volume are
0.96, 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.The Rh contents of the catalyst are 6.50g/L, Mg contents 1.70g/L, Cr content 3.40g/L after measured.
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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.85%, and selectivity is 86.72%, 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 the RhCl of Rh containing 6.50g, Mg containing 1.70g and the Sb containing 3.40g3·3H2O、MgCl2With
Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, pore volume 0.96, 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 for measuring the catalyst are 6.50g/L, Mg contents 1.70g/L, Sb content 3.40g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.71%, and selectivity is 86.93%, 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 the RhCl of Rh containing the 6.50g and Mg containing 1.70g3·3H2O and MgCl2It is sufficiently mixed dissolving
In pure water, maceration extract 400ml is obtained, than surface is 175m by 1.0L2/ g, pore volume 0.96, 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.The catalyst after measured
Rh contents are 6.50g/L, Mg contents 1.70g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 51.41%, and selectivity is 73.27%, 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, Mg and Cr work
Property component while catalyst performance ratio containing Rh, Mg and Sb active component will be more containing only the performance of Rh, Mg active constituent catalyst
Excellent, the selectivity and yield of ethylidene diacetate will be high.
【Embodiment 3】
The preparation of catalyst：By the Rh (OAc) of Rh containing 5.00g, Be containing 0.50g and the Cr containing 1.00g3、BeSO4·4H2O
With Cr (OAc)3·6H2O, which is sufficiently mixed, to be dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract 400ml, 1.0L is compared table
Face is 150m2/ g, pore volume 0.90, the spherical Al of a diameter of 5.6mm2O3Carrier impregnation stands 2h in 80 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Rh contents of the catalyst are 5.00g/L after measured, Be contents 0.50g/L, Cr 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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 59.82%, and selectivity is 86.83%, 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 Rh (NO of Rh containing 10.00g, Ca containing 3.00g and the Cr containing 5.00g3)3、Ca(NO3)2·
4H2O and Cr (NO3)3·9H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 200m by 1.0L2/ g,
Pore volume is 1.00, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 120 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Rh contents of the catalyst are 10.00g/L, Ca contents 3.00g/L, Cr content 5.00g/L after measured.
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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.18%, 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 5】
The preparation of catalyst：By the RhCl of Rh containing 6.50g, Sr containing 1.70g and the Mo containing 3.40g3·3H2O、Sr
(OAC)2·0.5H2O and MoCl5It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 175m by 1.0L2/
G, pore volume 0.96, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains in above-mentioned maceration extract
To the catalyst.The Rh contents of the catalyst are 6.50g/L, Sr contents 1.70g/L, Mo content 3.40g/L after measured.
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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.42%, and selectivity is 86.53%, 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 Rh (SO of Rh containing 6.50g, Ba containing 1.70g and the W containing 3.40g4)3, BaO and ammonium tungstate
((NH4)10W12O41·4H2O) it is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 175m by 1.0L2/ g,
Pore volume is 0.96, the spherical SiO of a diameter of 5.6mm2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Rh contents of the catalyst are 6.50g/L, Ba content 1.70g/L, W content 3.40g/L after measured.
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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.57%, and selectivity is 86.87%, 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 RhCl of Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g3·3H2O、MgCl2With
Basic bismuth carbonate ((BiO)2CO3·0.5H2O) it is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, 1.0L is compared into surface
For 175m2/ g, pore volume 0.96, 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 of the catalyst are 6.50g/L after measured, Mg contents 1.70g/L, Bi content
3.40g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.52%, and selectivity is 86.34%, 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 RhCl of Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g3·3H2O、MgCl2With
Bi2(SO4)3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into surface
For 175m2/ g, pore volume 0.96, 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 of the catalyst are 6.50g/L after measured, Mg contents 1.70g/L, Bi content
3.40g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.44%, and selectivity is 86.22%, 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 RhCl of Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g3·3H2O、MgCl2With
Bi2O3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
175m2/ g, pore volume 0.96, 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.The Rh contents of the catalyst are 6.50g/L, Mg contents 1.70g/L, Bi content 3.40g/ after measured
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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.13%, 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 10】
The preparation of catalyst：By the RhCl of Rh containing 6.50g, Mg containing 1.70g and the Bi containing 3.40g3·3H2O、MgCl2With
BiCl3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
175m2/ g, pore volume 0.96, 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.The Rh contents of the catalyst are 6.50g/L, Mg contents 1.70g/L, Bi content 3.40g/ after measured
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 53.89%, and selectivity is 78.04%, 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 11】
The preparation of catalyst：By Rh containing 6.50g, Mg containing 1.70g and RhCl containing 3.40gSb3·3H2O、MgCl2With
Sb2O3It is sufficiently mixed and is dissolved in the aqueous solution of nitric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
175m2/ g, pore volume 0.96, 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.The Rh contents of the catalyst are 6.50g/L, Mg contents 1.70g/L, Sb content 3.40g/ after measured
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 60.91%, and selectivity is 85.94%, 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 Rh containing 6.50g, Mg containing 1.70g and RhCl containing 3.40gSb3·3H2O、MgCl2With
Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, pore volume 0.96, 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 for measuring the catalyst are 6.50g/L, Mg contents 1.70g/L, Sb content 3.40g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.38%, 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 13】
The preparation of catalyst：By Rh containing 6.50g, the RhCl containing the 1.70gSr and Cr containing 3.40g3·3H2O、SrCl2·
6H2O and CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 175m by 1.0L2/ g, hole
Hold for 0.96, 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 of the catalyst are 6.50g/L, Sr contents 1.70g/L, Cr content 3.40g/L after measured.
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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 60.42%, and selectivity is 86.28%, 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 6.50g, Mg containing 0.73g, the RhCl containing the 0.97gSr and Cr containing 3.40g3·
3H2O、MgCl2、SrCl2·6H2O and CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L
It is 175m than surface2/ g, pore volume 0.96, 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.The Rh contents of the catalyst are 6.50g/L after measured, Mg contents 0.73g/L, and Sr contains
Measure 0.97g/L, Cr contents 3.40g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 61.85%, and selectivity is 87.83%, 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 Sr, Mg and its in the present invention in alkaline-earth metal compared with embodiment 1, embodiment 13
The favourable selectivity and yield for improving ethylidene diacetate of its active component collaboration, illustrates tetra- kinds of activearms of Rh, Sr, Mg and Cr
/ presence acts synergistically well.
【Embodiment 15】
The preparation of catalyst：By Rh containing 6.50g, Mg containing 0.73g, the RhCl containing the 0.97gSr and Sb containing 3.40g3·
3H2O、MgCl2、SrCl2·6H2O and Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared surface
For 175m2/ g, pore volume 0.96, 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 of the catalyst are 6.50g/L after measured, Mg contents 0.73g/L, Sr content
0.97g/L, Sb content 3.40g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 61.80%, and selectivity is 87.86%, 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：6.50g Rh, Mg containing 0.73g will be contained, containing 0.97gSr, Cr containing 1.07g and containing 2.33gSb
RhCl3·3H2O、MgCl2、SrCl2·6H2O、CrCl3·6H2O and Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, is impregnated
Liquid 400ml, than surface is 175m by 1.0L2/ g, pore volume 0.96, 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 of the catalyst are 6.50g/L after measured, and Mg contains
Measure 0.73g/L, Sr contents 0.97g/L, Cr content 1.07g/L, Sb content 2.33g/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 6.5MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 165 DEG C, and the molar ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 7.0h, 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 63.79%, and selectivity is 88.45%, 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 14, embodiment 15 as can be seen that in vib metal in Cr, VA metal Sb and this
The favourable selectivity and yield for improving ethylidene diacetates of other active components collaboration in invention, illustrate Rh, Sr, Mg, Cr and
There is synergistic effect well between five kinds of active components of Sb.
Table 1
Table 2
Claims (10)
1. the catalyst for synthesizing ethylidene diacetate, the catalyst use SiO2、Al2O3Or its mixture is carrier,
Active component includes rhodium, alkaline-earth metal, selected from least one of VIB metallic elements and selected from least one of VA metals member
Element；The content of rhodium is in catalyst：3.00~15.00g/L, the content of alkaline-earth metal are：0.10~5.00g/L；It is described to be selected from
At least one content of metal is 0.5~8.0g/L in VIB and VA；Load surface area per unit volume is 50~300m2/ g, pore volume for 0.80~
1.20。
2. catalyst according to claim 1, it is characterised in that the alkaline-earth metal in beryllium, magnesium, calcium, strontium and barium extremely
Few one kind.
3. catalyst according to claim 1, it is characterised in that the vib metal is selected from least one of chromium, molybdenum and tungsten.
4. catalyst according to claim 1, it is characterised in that the VA metals are selected from least one of antimony and bismuth.
5. catalyst according to claim 1, it is characterised in that the content of rhodium is in catalyst：5.0~10.0g/L, alkaline earth
The content of metal is：0.50~3.00g/L.
6. catalyst according to claim 1, it is characterised in that described in catalyst in VIB and VA metal at least one
Kind content is 1.00~5.00g/L.
7. as the preparation method of the catalyst described in claim 1, include the following steps：
1. by catalyst composition by the solution of metallic compound in the compound of rhodium, the compound of alkaline-earth metal, VIB and VA with
Carrier mixes；
2. dry.
8. the production method of catalyst according to claim 7, it is characterized in that the compound of the step 1. rhodium is selected from acetic acid
At least one of rhodium, rhodium nitrate, radium chloride and rhodium sulfate.
9. 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 claim 1~6 and co-catalyst iodide.
10. synthetic method according to claim 9, it is characterized in that the temperature of reaction is 130~200 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0035860A2 (en) * | 1980-03-06 | 1981-09-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing ethylidene diacetate and/or acetaldehyde |
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
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2014
- 2014-09-17 CN CN201410474705.7A patent/CN105478116B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| EP0035860A2 (en) * | 1980-03-06 | 1981-09-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing ethylidene diacetate and/or acetaldehyde |
| CN103553913A (en) * | 2013-10-28 | 2014-02-05 | 中国石油化工股份有限公司 | Synthetic method of ethylidene diacetate |
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