CN109053439A - A method of asymmetric oxalate is synthesized by transesterification path - Google Patents
A method of asymmetric oxalate is synthesized by transesterification path Download PDFInfo
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Abstract
A method of asymmetric oxalate is synthesized by transesterification path, is related to a kind of method for synthesizing asymmetric oxalate, the present invention is using the higher alcohols such as symmetrical oxalate and ethyl alcohol, propyl alcohol, butanol, amylalcohol as reaction raw materials, the method for one-step synthesis method asymmetry oxalate.For the catalyst used for mesoporous-microporous compound multi-functional basic catalyst, it is advantageous that mesoporous can significantly improve mass transfer effect, and micropore significantly improves carrier specific surface area, improves the dispersion degree in activated centre.Using 15%BaO-4%MgO-2%La2O3/ Cs-meso- β is catalyst, in feed ethanol and dimethyl oxalate with molar ratio 2:1, air speed 6h‑1, 80 DEG C of reaction temperature, when reacting under normal pressure, product methyl ethyl oxalate is selectively stablized 85% or so, and steady state operation 1000h, catalytic activity and selectivity of product are basically unchanged.Entire response path has synthesis path short, and selectivity of product is high, and catalyst preparation is simple, and efficient pollution-free stablizes the characteristics of non-inactivation.
Description
Technical field
The present invention relates to a kind of methods for synthesizing asymmetric oxalate, are synthesized not more particularly to one kind by transesterification path
The method of symmetrical oxalate.
Background technique
Oxalate (Dialkyloxalates can be abbreviated as DRO) is widely used in field of fine chemical such as: for manufacturing
The intermediate of ethylene glycol, oxalic acid, oxamides and some drugs and dyestuff is important basic chemical industry raw material.Dimethyl oxalate knot
Structure formula is CH3OOCCOOCH3, as important chemical industry and medical material, it is commonly used for synthesizing vitamin B13, hydrogen is added to prepare second
Alkyd methyl esters, ethylene glycol, can also act on ammonia can be generated oxamides etc..Diethy-aceto oxalate structural formula is C2H5OOCCOOC2H5,
It is a kind of colourless oil liquid under room temperature, there is aromatic odor, can be miscible with the common solvents such as ethyl alcohol, ether, water facile hydrolysis is met, it is low
Important industrial chemicals ethylene glycol can be made in pressure plus hydrogen.Methyl ethyl oxalate structural formula is CH3OOCCOOC2H5, due to its molecule knot
There is methyl and ethyl simultaneously in structure, so its characteristic for having dimethyl oxalate, diethy-aceto oxalate concurrently, it is certain special to can be used as
Organic synthesis reagent, extractant, adhesive, plasticizer and a variety of medicine intermediates, simultaneously can be used for the molten of extraordinary fragrance
Agent.
Consulting literatures are it is found that oxalate is mainly the following synthetic method at present:
(1) alcoholic acid esterification method: the industrialized preparing process that diethy-aceto oxalate generallys use at present is esterification process, with oxalic acid and second
Alcohol is raw material, uses inorganic acid (such as concentrated sulfuric acid) or strong-acid ion exchange resin for catalyst, utilizes chloroform, benzene and significantly
Excessive ethyl alcohol takes away the water generated in the crystallization water and reaction of oxalic acid to make reaction balance move to right, and improves conversion ratio, yield
Up to 80% ~ 90%.Reaction time is short, and product postprocessing is simple.But alcoholic acid esterification method energy consumption is high, a large amount of soda acids of consumption, produces work
Skill is at high cost, and has very big pollution to environment, it is difficult to meet the needs of modern chemical industry development and wanting for environmental protection
It asks.
(2) carbon monoxide liquid phase coupling method: Fenton is when studying platinum group metal liquid-phase catalysis carbonylation, discovery
In oxidizing atmosphere, a kind of molysite is added in the reaction system or mantoquita is aoxidized as oxidant, carbon monoxide and methanol
Coupling reaction generates oxalate, in its further research work, they compared different molysite or mantoquita acid adding or alkali with
PdCl2Catalyst system activity, discovery CO pressure increase, the selectivity of oxalate and ethyl acetate can be improved, with
PdCl2/CuCl/CuCl2For catalyst system, reaction obtains liquid product medium-height grass acid esters selectivity up to 68.9%, and carbonic ester is selective
28.7%.There are severe reaction conditions for liquid phase coupling method, need to carry out under high pressure, high production cost, equipment corrosion and catalyst stream
The problems such as mistake.
(3) carbon monoxide gas phase coupling method:
Under the action of catalyst for carbon monoxide, normal pressure and methyl nitrite coupling reaction generate dimethyl oxalate and one to the first step
Nitrogen oxide, reaction equation are as follows:
2C2H5ONO+2CO→(COOC2H5)2+2NO
Second step is coupling reaction, and the nitric oxide of generation enters packed tower after separating with product, there under room temperature with methanol
It is reacted with oxygen and generates methyl nitrite, reaction equation are as follows:
2NO+2CH3OH+1/2O2→2CH3ONO+H2O
The methyl nitrite of generation returns to coupling process and is recycled.Net reaction are as follows:
2CO+1/2O2+2CH3OH→(COOCH3)2+H2O
Carbon monoxide normal pressure gas-phase catalytic coupling synthesis of oxalate, reaction item abundant, at low cost, pollution-free with raw material sources
The advantages that part is mild, product purity is high, production serialization, is environmental-friendly Green Chemistry new process.By carbon monoxide and Asia
Nitrate catalyzes and synthesizes symmetrical oxalate, opens the new way of C1 chemical production oxalic acid symmetrical ester.It is closed via this C1 route
At oxalate higher cost, but on long terms especially for China's oil resource shortage, and the resource knot of rich coal resources
Structure, this coal chemical industry synthesis of oxalate route have important strategic importance.
The synthetic method of asymmetry oxalate is there are no document report at present, we propose a kind of one-step synthesis method not at this
The response path of symmetrical oxalate.The reaction of the one-step synthesis asymmetry oxalate has synthesis path short, and selectivity of product is high,
Catalyst preparation is simple, and efficient pollution-free stablizes the characteristics of non-inactivation.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for synthesizing asymmetric oxalate by transesterification path, and the present invention is with right
The higher alcohols such as oxalate and ethyl alcohol, propyl alcohol, butanol, amylalcohol are referred to as reaction raw materials, the method for one-step synthesis method asymmetry oxalate.
The catalyst used is mesoporous-microporous compound multi-functional basic catalyst, it is advantageous that mesoporous can significantly improve mass transfer effect
Fruit, synthesis path is short, and selectivity of product is high.
The purpose of the present invention is what is be achieved through the following technical solutions:
A method of asymmetric oxalate being synthesized by transesterification path, the method reaction route equation is as follows:
(COOR)2+R'OH→ROH+ROOCCOOR'…………………………………………....(1)；
Raw material is respectively symmetrical oxalate and R ' OH, and wherein R ' OH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol；The catalysis present invention
The catalyst of single step reaction is with mesoporous and microcellular structure compound basic catalyst；With mesoporous and microcellular structure compound
Basic catalyst general formula be X/Z, wherein Z be different topology structure carrier, including topological structure be MOR, FAU, MFI, FER,
BEA molecular sieve and routine SiO2、Al2O3、ZrO2, one or more of carriers such as MgO and ZnO oxide；X be Li,
The oxide of one or more kinds of metals in Na, K, Ca, Cr, Fe, Al, La.
A kind of method that asymmetric oxalate is synthesized by transesterification path, the Z molecular sieve carrier, Hydrogen point
Son sieve passes through ion exchange, and Bronsted acid is poisoned by metal ion, so that it is not had Bronsted acid；With alkali metal from
For the BEA molecular sieve carrier (M-BEA, M can be Li, Na, K, Ca, Cr, Fe, Al, La) that son poisons, the preparation method is as follows: will
The H-BEA molecular sieve of certain mass, is placed in deionized water, the metal-nitrate solutions of 1M is added thereto respectively, at 90 DEG C
Exchange 2 h.It is dried overnight after filtration washing in 120 DEG C, Li-BEA, Na- BEA, K- can be obtained in 600 DEG C of 6 h of roasting
BEA,Ca-BEA,Cr- BEA,Fe- BEA,Al -BEA,La-BEA；Other molecular sieves and support preparation method are similar, are labeled as
M-Z, wherein M includes Li, Na, K, Ca, Cr, Fe, Al, La.
A kind of method that asymmetric oxalate is synthesized by transesterification path, it is described that there is mesoporous and microcellular structure to carry
The preparation method of Jie's micro porous molecular sieve carrier: the loading type alkali metal oxide catalyst of body certain mass M-Z carrier is added
Enter into certain density acid solution, is then stirred at reflux 6 h at 100 DEG C of oil bath, filtration washing, 120 DEG C of 12 h of drying,
M-Z-DAl carrier after obtaining dealuminzation；It is then added in certain density alkaline solution, handles 30 in 60 DEG C of water-baths
Min, filtration washing, 120 DEG C of 12 h of drying obtain Jie's micropore M-Z-DAl-DSi carrier；It is put into Muffle furnace and is protected in 550 DEG C
5 h are held, are denoted as: M-meso-Z.
A kind of method that asymmetric oxalate is synthesized by transesterification path, the system of given an account of micro porous molecular sieve carrier
Preparation Method, the molecular sieve of different topology structure include the one or more of EMT, MOR, MWW, FAU, MFI, FER, BEA；The acid
Property solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；The alkaline solution includes NaOH, Na2CO3
Deng one or more, preferably NaOH；The alkaline solution concentration is 0.05mol/L-2.0mol/L.
A kind of method that asymmetric oxalate is synthesized by transesterification path, the one-step synthesis asymmetry oxalate
Path, continuous fixed bed reaction or continuous beat the various alcohols of liquid charging stock and dimethyl oxalate under normal pressure to 10MPa reaction pressure, with pump
Molar ratio is 2:1 charging, and in above-mentioned catalyst existence condition, reaction synthesizes asymmetric oxalate, air speed 0.1- in next step
100 h-1, under conditions of 40-160 DEG C of reaction temperature, catalyst is multi-functional compound basic catalyst, and catalyst amount is raw material
The 0.5-3wt% of quality.
A kind of method synthesizing asymmetric oxalate by transesterification path, the continuous fixed bed reaction or continuous preparation is not
During symmetrical oxalate, optimum condition is alcohols (R ' OH is the higher alcohols such as ethyl alcohol, propyl alcohol, butanol): dimethyl oxalate rubs
You are ratio=2:1, air speed 2-8 h-1, 40-110 DEG C of reaction temperature.
A kind of method that asymmetric oxalate is synthesized by transesterification path, the one-step synthesis asymmetry oxalate
Path, continuous fixed bed reaction or continuous its still reaction pressure 0.1-10MPa, alcohols and dimethyl oxalate molar ratio are 2:1, are being catalyzed
It is reacted under agent existence condition and prepares asymmetric oxalate, closed 25-135 DEG C in reaction kettle, react 0.5-10 h, catalyst is alkali
Property catalyst, catalyst amount be material quality 0.1-8wt %.
A kind of method synthesizing asymmetric oxalate by transesterification path, the still reaction, it is not right to prepare
During claiming oxalate, optimum condition is alcohols (R ' OH can be ethyl alcohol, propyl alcohol, butanol higher alcohols): dimethyl oxalate mole
Than=2:1,50-100 DEG C of reaction temperature.
Detailed description of the invention
Fig. 1 is influence of the differential responses temperature to feed stock conversion and selectivity of product.
Reaction condition as shown in the figure: the molar ratio of ethyl alcohol and dimethyl oxalate is 2:1,6 h of air speed-1, it reacts under normal pressure,
15%BaO-4%MgO-2%La2O3/ Cs-meso- β makees catalyst, 10 g of catalyst quality.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention uses high-performance solid catalyst, realizes that (R can be methyl, ethyl, propyl for symmetrical oxalate and various alcohols
Equal alkyl, R ' OH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol) method of one-step synthesis asymmetry oxalate, the response path is such as
Shown in lower:
(COOR)2+R’OH→ROH+ROOCCOOR’…………………………………………....(1)
The path is using multi-functional compound basic matterial as catalyst, and by symmetrical oxalate and various alcohols, (R ' OH can be ethyl alcohol, third
The higher alcohols such as alcohol, butanol) it is one step high selectivity asymmetry oxalate of reaction raw materials, solid basic catalyst is fairly insoluble
In reaction raw materials and product, reaction process is not present any pollutant, entire response path green, energy-saving and environmental protection, efficient.Gu
Body catalyst is isolated by filtration, reuse, and catalyst be reused many times after be still able to maintain higher activity.
Catalyst of the present invention is with mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst
Agent, general formula X/Z, it is MOR, FAU, MFI, FER, BEA points that wherein Z, which is the carrier of different topology structure, including topological structure,
Son sieve and routine SiO2、Al2O3、ZrO2, one or more of carriers such as MgO and ZnO oxide；X be Li, Na, K,
The oxide of one or more kinds of metals in Ca, Cr, Fe, Al, La.
The BEA molecular sieve carrier (M-BEA, M can be Li, Na, K, Ca, Cr, Fe, Al, La) poisoned with alkali metal ion is
The metal of 1M is added the preparation method is as follows: the H-BEA molecular sieve of certain mass is placed in deionized water in example thereto respectively
Nitrate solution, in 90 DEG C of 2 h of exchange.It is dried overnight after filtration washing in 120 DEG C, Li- can be obtained in 600 DEG C of 6 h of roasting
BEA,Na-BEA,K-BEA,Ca-BEA,Cr-BEA,Fe-BEA,Al-BEA,La-BEA.Other molecular sieves and support preparation method
It is similar, it is labeled as M-Z, wherein M includes Li, Na, K, Ca, Cr, Fe, Al, La etc..
1. the preparation of Jie's micro porous molecular sieve carrier: certain mass M-Z carrier is added in certain density acid solution,
Then 6 h, filtration washing, 120 DEG C of 12 h of drying, the M-Z-DAl carrier after obtaining dealuminzation are stirred at reflux at 100 DEG C of oil bath.So
After be added in certain density alkaline solution, 30 min, filtration washing are handled in 60 DEG C of water-baths, 120 DEG C of 12 h of drying are obtained
To Jie's micropore M-Z-DAl-DSi carrier.It is put into Muffle furnace in 550 DEG C of holding 5h, is denoted as: M-meso-Z.
The molecular sieve of heretofore described different topology structure includes one kind of EMT, MOR, MWW, FAU, MFI, FER, BEA
Or it is a variety of；The acid solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；The alkaline solution packet
Include NaOH, Na2CO3Deng one or more, preferably NaOH；The alkaline solution concentration is 0.05mol/L-2.0mol/L.
2. the preparation of composite catalyst: taking metal X mass is the X metal nitrate and chlorine of M-meso-Z mass 0.1-50%
The mixed solution of salt dissolving is impregnated into the M-meso-Z carrier duct after roasting several times in ultrasound environments；110 after dipping
Dry 12h, 550 DEG C of roasting 5h obtain the catalyst X/M-meso-Z with composite pore structural at DEG C.
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural.
The present invention with symmetrical oxalate and various alcohols (R'OH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol) for raw material,
The catalyst existence condition of above-mentioned preparation synthesizes asymmetric oxalate in next step, and reactor can be fixed bed reactors, fluidisation
Bed reactor or tank reactor.
Continuous fixed bed reaction or continuous specific embodiment of the present invention are as follows: under normal pressure to 10MPa reaction pressure, beat liquid with pump
The various alcohols of raw material and dimethyl oxalate molar ratio are 2:1 charging, and in above-mentioned catalyst existence condition, reaction is synthesized not in next step
Symmetrical oxalate, air speed are 0.1-100 h-1, under conditions of 40-160 DEG C of reaction temperature, protected in the catalyst present invention
Various multi-functional compound basic catalysts, catalyst amount are the 0.5-3wt% of material quality.
During preparing asymmetric oxalate with fixed bed reaction, optimum condition is that (R ' OH can be second to various alcohols
The higher alcohols such as alcohol, propyl alcohol, butanol): dimethyl oxalate molar ratio=2:1, air speed 2-8 h-1, 40-110 DEG C of reaction temperature.
Still reaction specific embodiment of the present invention are as follows: reaction pressure 0.1-10MPa, various alcohols and dimethyl oxalate rub
You react prepare asymmetric oxalate in the presence of a catalyst than being 2:1, closed 25-135 DEG C in reaction kettle, reaction
0.5-10 h, catalyst are the various basic catalysts protected in the present invention, and catalyst amount is the 0.1-8wt of material quality
%。
During preparing asymmetric oxalate with still reaction, optimum condition be various alcohols (R ' OH can be ethyl alcohol,
The higher alcohols such as propyl alcohol, butanol): dimethyl oxalate molar ratio=2:1,50-100 DEG C of reaction temperature.
Catalyst of the present invention is multi-functional compound basic catalyst, it is advantageous that mesoporous can significantly improve
Mass transfer effect, and micropore significantly improves carrier specific surface area, improves the dispersion degree in activated centre.In continuous fixed bed reaction or continuous,
Long-lasting catalytic reacts non-inactivation, and at a lower temperature, product asymmetry oxalate reaches more highly selective, catalyst preparation
Simply, no pollution to the environment, energy conservation and environmental protection.In still reaction, post catalyst reaction can be again by simple processing
Recycling, and catalyst be reused many times after be still able to maintain higher activity.
Embodiment 1
In fixed bed reactors, influence of the different catalysts to feed stock conversion and selectivity of product is probed into.Respectively by 10 g
Variety classes catalyst is filled into fixed bed reactors, and feed ethanol and dimethyl oxalate molar ratio 2:1 are added a certain amount of
Isosorbide-5-Nitrae-dioxane makees solvent, and mixed liquor is pumped into reactor after preheater heats using constant flow pump, air speed 6
h-1, 80 DEG C of reaction temperature, react under normal pressure, stablize 500 h, sampling carries out chromatography calculating, feed stock conversion, production after stablizing
Object yield is as shown in table 1.
。
As can be seen from Table 1, with 15%BaO-4%MgO-2%La2O3When/Cs-meso- β is catalyst, the catalysis effect of reaction
Fruit is best, and dimethyl oxalate conversion ratio is up to 68%, and the molar selectivity of product mesoxalic acid methyl ethyl ester is up to 85%.
Embodiment 2
In fixed bed reactors, influence of the differential responses temperature to feed stock conversion and selectivity of product is probed into.In fixed bed
15%BaO-4%MgO-2%La is packed into reaction tube2O310 g of/Cs-meso- beta catalyst, feed ethanol and dimethyl oxalate mole
Than 2:1, a certain amount of Isosorbide-5-Nitrae-dioxane is added and makees solvent, mixed liquor is pumped after preheater heats using constant flow pump
Enter in reactor, air speed is 6 h-1, react under normal pressure, it is as shown in the table for reaction temperature, and stablizes 500 h, samples and carries out after stablizing
Chromatography calculates, and feed stock conversion, product yield are as shown in table 2.
。
From table 2 it can be seen that the conversion ratio of reactant dimethyl oxalate gradually increases with the raising of reaction temperature, produce
The selectivity of object methyl ethyl oxalate gradually decreases.When temperature reaches 80 DEG C, the yield of methyl ethyl oxalate reaches peak.
Embodiment 3
In fixed bed reactors, influence of the different alcohols to feed stock conversion and selectivity of product is probed into.In fixed bed reaction
15%BaO-4%MgO-2%La is packed into pipe2O310 g of/Cs-meso- beta catalyst, feed ethanol and dimethyl oxalate molar ratio 2:
1, a certain amount of Isosorbide-5-Nitrae-dioxane is added and makees solvent, mixed liquor is pumped into instead after preheater heats using constant flow pump
It answers in device, air speed is 6 h-1, 80 DEG C of reaction temperature, react under normal pressure, stablize 500 h, sampling carries out chromatography meter after stablizing
It calculates, feed stock conversion, product yield are as shown in table 3.
。
As can be seen from Table 3, asymmetric oxalate, reaction result phase are synthesized using different alcohols as reaction raw materials
Difference is larger, and as R group becomes complicated, the yield of asymmetric oxalate is gradually decreased.The reason is that as R group becomes multiple
Miscellaneous, the steric hindrance of ROH becomes larger, and R group is difficult to close to dimethyl oxalate and is replaced.
Embodiment 4
In fixed bed reactors, influence of the differential responses air speed to feed stock conversion and selectivity of product is probed into.In fixed bed
Middle loading 15%BaO-4%MgO-2%La2O310 g of/Cs-meso- beta catalyst, feed ethanol and dimethyl oxalate molar ratio 2:1,
A certain amount of Isosorbide-5-Nitrae-dioxane is added and makees solvent, mixed liquor is pumped into reaction after preheater heats, using constant flow pump
In device, it is as shown in the table for differential responses air speed, 80 DEG C of reaction temperature, reacts under normal pressure, and stablize 500 h, samples and carries out after stablizing
Chromatography calculates, and feed stock conversion, selectivity of product are as shown in table 4.
。
From table 4, it can be seen that with the increase of air speed, reaction-ure conversion-age is gradually reduced, when air speed reaches 6h-1When, grass
The yield highest of sour methyl ethyl ester.
Embodiment 5
By 2000 g15%BaO-4%MgO-2%La2O3It is 10 cm that/Cs-meso- beta catalyst, which is packed into internal diameter, is highly 200 cm
Stainless steel fixed bed reactors in, reactor void volume part is filled with quartz sand., feed ethanol rubs with dimethyl oxalate
You than 2:1, a certain amount of Isosorbide-5-Nitrae-dioxane is added and makees solvent, mixed liquor after preheater heats, using constant flow pump by its
It is pumped into reactor, air speed 6h-1, 80 DEG C of reaction temperature, react under normal pressure, product methyl ethyl oxalate is selectively stablized on 85% left side
The right side, 1000 h of steady state operation, catalytic activity and selectivity of product are basically unchanged.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (9)
1. a kind of method for synthesizing asymmetric oxalate by transesterification path, which is characterized in that the method reaction route equation
Formula is as follows:
(COOR)2+R'OH→ROH+ROOCCOOR'…………………………………………....(1)；
Raw material is respectively symmetrical oxalate and R ' OH, and wherein R ' OH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol；The catalysis present invention
The catalyst of single step reaction is with mesoporous and microcellular structure compound basic catalyst；With mesoporous and microcellular structure compound
Basic catalyst general formula be X/Z, wherein Z be different topology structure carrier, including topological structure be MOR, FAU, MFI, FER,
BEA molecular sieve and routine SiO2、Al2O3、ZrO2, one or more of carriers such as MgO and ZnO oxide；X be Li,
The oxide of one or more kinds of metals in Na, K, Ca, Cr, Fe, Al, La.
2. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 1, which is characterized in that institute
Z molecular sieve carrier is stated, hydrogen type molecular sieve passes through ion exchange, Bronsted acid is poisoned by metal ion, does not have it
Bronsted is acid；Poisoned with alkali metal ion BEA molecular sieve carrier (M-BEA, M can for Li, Na, K, Ca, Cr, Fe, Al,
La for), the preparation method is as follows: the H-BEA molecular sieve of certain mass to be placed in deionized water, 1M be added thereto respectively
Metal-nitrate solutions, in 90 DEG C of 2 h of exchange.
3. be dried overnight after filtration washing in 120 DEG C, 600 DEG C of 6 h of roasting, can be obtained Li-BEA, Na- BEA, K-BEA,
Ca-BEA,Cr- BEA,Fe- BEA,Al -BEA,La-BEA；Other molecular sieves and support preparation method are similar, are labeled as M-Z,
Wherein M includes Li, Na, K, Ca, Cr, Fe, Al, La.
4. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 1, which is characterized in that institute
It states with mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, the preparation side of Jie's micro porous molecular sieve carrier
Method: certain mass M-Z carrier is added in certain density acid solution, is then stirred at reflux 6 h, mistake at 100 DEG C of oil bath
Filter washing, 120 DEG C of 12 h of drying, the M-Z-DAl carrier after obtaining dealuminzation；It is then added in certain density alkaline solution,
30 min, filtration washing are handled in 60 DEG C of water-baths, 120 DEG C of 12 h of drying obtain Jie's micropore M-Z-DAl-DSi carrier；It puts
Enter in Muffle furnace in 550 DEG C of 5 h of holding, is denoted as: M-meso-Z.
5. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 3, which is characterized in that institute
Give an account of the preparation method of micro porous molecular sieve carrier, the molecular sieve of different topology structure include EMT, MOR, MWW, FAU, MFI, FER,
BEA's is one or more；The acid solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；It is described
Alkaline solution includes NaOH, Na2CO3Deng one or more, preferably NaOH；The alkaline solution concentration is 0.05mol/L-
2.0mol/L。
6. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 1, which is characterized in that institute
One-step synthesis asymmetry oxalate path is stated, continuous fixed bed reaction or continuous beats liquid original under normal pressure to 10MPa reaction pressure, with pump
Various alcohols and dimethyl oxalate molar ratio are expected for 2:1 charging, and in above-mentioned catalyst existence condition, reaction synthesis is not right in next step
Claim oxalate, air speed is 0.1-100 h-1, under conditions of 40-160 DEG C of reaction temperature, catalyst is that multi-functional compound alkalinity is urged
Agent, catalyst amount are the 0.5-3wt% of material quality.
7. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 5, which is characterized in that institute
During stating the asymmetric oxalate of continuous fixed bed reaction or continuous preparation, optimum condition is that (R ' OH is ethyl alcohol, propyl alcohol, butanol to alcohols
Equal higher alcohols): dimethyl oxalate molar ratio=2:1, air speed 2-8 h-1, 40-110 DEG C of reaction temperature.
8. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 6, which is characterized in that institute
State one-step synthesis asymmetry oxalate path, continuous fixed bed reaction or continuous its still reaction pressure 0.1-10MPa, alcohols and oxalic acid two
Methyl esters molar ratio is 2:1, in the presence of a catalyst the asymmetric oxalate of reaction preparation, closed 25-135 DEG C in reaction kettle,
0.5-10 h is reacted, catalyst is basic catalyst, and catalyst amount is the 0.1-8wt % of material quality.
9. a kind of method for synthesizing asymmetric oxalate by transesterification path according to claim 7, which is characterized in that institute
Still reaction is stated, during preparing asymmetric oxalate, optimum condition is that (R ' OH can be ethyl alcohol, propyl alcohol, butanol height to alcohols
Carbon alcohol): dimethyl oxalate molar ratio=2:1,50-100 DEG C of reaction temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279762A (en) * | 2020-11-11 | 2021-01-29 | 新疆至臻化工工程研究中心有限公司 | Technological method for synthesizing ethyl methyl oxalate through heterogeneous catalysis ester exchange |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712564A (en) * | 2010-01-20 | 2012-10-03 | 宇部兴产株式会社 | Process for production of diaryl oxalate |
| CN107473968A (en) * | 2017-07-20 | 2017-12-15 | 沈阳化工大学 | A kind of method of ester-interchange method methyl ethyl carbonate |
-
2018
- 2018-07-03 CN CN201810718517.2A patent/CN109053439A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712564A (en) * | 2010-01-20 | 2012-10-03 | 宇部兴产株式会社 | Process for production of diaryl oxalate |
| CN107473968A (en) * | 2017-07-20 | 2017-12-15 | 沈阳化工大学 | A kind of method of ester-interchange method methyl ethyl carbonate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279762A (en) * | 2020-11-11 | 2021-01-29 | 新疆至臻化工工程研究中心有限公司 | Technological method for synthesizing ethyl methyl oxalate through heterogeneous catalysis ester exchange |
| CN112279762B (en) * | 2020-11-11 | 2023-08-11 | 新疆至臻化工工程研究中心有限公司 | Process method for synthesizing methyl ethyl oxalate by heterogeneous catalysis transesterification |
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Application publication date: 20181221 |