CN108911975A - By the method for dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis - Google Patents
By the method for dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis Download PDFInfo
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Abstract
By the method for dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, the method for being related to synthesizing symmetrical oxalate, using the higher alcohols such as dimethyl oxalate and ethyl alcohol, propyl alcohol, butanol, amylalcohol as reaction raw materials, the method for the symmetrical oxalate of one-step synthesis method.For the catalyst used for mesoporous-microporous compound multi-functional basic catalyst, it is advantageous that mesoporous significantly improve mass-transfer efficiency, and micropore significantly improves carrier specific surface area, improves the dispersion degree in activated centre.Use 10%MgO-5%Al2O3-8%Fe2O3/Na-meso-Y for catalyst, in feed ethanol and dimethyl oxalate with molar ratio 20:1, air speed is 2 h-1, and 100 DEG C of reaction temperature, when reacting under normal pressure, product diethy-aceto oxalate is selectively stablized 82% or so, and 1000 h of steady state operation, catalytic activity and selectivity of product are basically unchanged.The characteristics of entire response path has synthesis path short, and process flow is simple, and feed stock conversion and selectivity of product are high, catalyst stabilization non-inactivation.
Description
Technical field
The present invention relates to a kind of methods for synthesizing symmetrical oxalate, more particularly to one kind by dimethyl oxalate and alcohols one
The method that step synthesizes symmetrical oxalate.
Background technique
Oxalate（Dialkyloxalates can be abbreviated as DRO）It 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.Its mesoxalic acid diethyl
The purposes of ester is the most extensive, and important industrial chemicals ethylene glycol can be made in diethy-aceto oxalate low-voltage hydrogenation.Diethy-aceto oxalate
（Diethyl oxalate can be abbreviated as DEO）Also known as diethyl oxalate, molecular formula are：C6H10O4.Fusing point is -40.6
DEG C, boiling point is 185.7 DEG C, density 1.0785.Be a kind of colourless oil liquid under room temperature, there is aromatic odor, can with ethyl alcohol,
The common solvents such as ether are miscible, meet water facile hydrolysis.
Diethy-aceto oxalate is important Organic Chemicals, can produce the objects such as ethylene glycol as important chemical intermediate
Matter, and can be reacted with many heterocyclic compounds such as aliphatic ester；Diethy-aceto oxalate the moisture absorption and is slowly decomposed into air
Oxalic acid and ethyl alcohol act on ammonia and generate amide compound, are ethyl pyruvate with condensation of acetone.Diethy-aceto oxalate is in terms of medicine
It can be used to synthesize the thymine as intermediate, further manufacture the drugs such as, phenobarbital bright at karr and penicillin；Organic
Synthesis aspect, diethy-aceto oxalate can be used for manufacturing the organic substances such as plastics promotor, dyestuff, cellulose esters；In the industrial production,
Diethy-aceto oxalate can be used as production of the solvent for television picture tube cathode spray solution, and can be used as the auxiliary agent of textile industry
And lubricant of low temperature resistant high pressure etc..
Consulting literatures are it is found that oxalate is mainly the following synthetic method at present：
（One）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, using inorganic acid（Such as concentrated sulfuric acid）Or strong-acid ion exchange resin is 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.
（Two）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.
（Three）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：
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 is：
2NO+2CH3OH+1/2O2→2CH3ONO+H2O
The methyl nitrite of generation returns to coupling process and is recycled.Net reaction is:
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.
Currently, industrially substantially reduced using methanol-methyl nitrite-through carbonylation dimethyl oxalate method production cost,
Dimethyl oxalate cost is lower than 4000 yuan/ton, therefore preparing other oxalic acid esters by dimethyl oxalate has significant economy attached
It is value added.We propose a kind of response path of symmetrical oxalate of one-step synthesis method at this.The symmetrical oxalate of the one-step synthesis it is anti-
There should be synthesis path short, process flow is simple, and feed stock conversion and selectivity of product are high, the spy of catalyst stabilization non-inactivation
Point.
Summary of the invention
The purpose of the present invention is to provide a kind of method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis,.
The purpose of the present invention is what is be achieved through the following technical solutions：
By the method for dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, the method includes one-step synthesis method oxalic acid is symmetrical
Ester reaction route equation is as follows：
(COOCH3)2+2ROH→2CH3OH+ROOCCOOR……………………………………..(1)
Raw material is respectively dimethyl oxalate and ROH, and wherein ROH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol；
The catalyst for being catalyzed single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；Catalyst Formula
For X/Z, wherein Z is the carrier of different topology structure, including topological structure is MOR, FAU, MFI, FER, BEA molecular sieve and often
Advise SiO2、Al2O3、ZrO2, one or more of MgO and ZnO carrier oxide；X is Li, Na, K, Ca, Cr, Fe, Al, La
The oxide of middle one or more metal.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, the Z molecular sieve carrier, hydrogen
Type molecular sieve passes through ion exchange, and Bronsted acid is poisoned by metal ion, so that it is not had Bronsted acid；With alkali gold
Belong to the FAU molecular sieve carrier that ion poisons（M- FAU, M can be Li, Na, K, Ca, Cr, Fe, Al, La）For, preparation method is such as
Under：It is placed in the H-FAU molecular sieve of certain mass in deionized water, the metal-nitrate solutions of 1M are added thereto respectively,
90 DEG C of 2 h of exchange；Be dried overnight after filtration washing in 120 DEG C, 600 DEG C of 6 h of roasting, can be obtained Li- FAU, Na- FAU,
K-FAU,Ca-EMT,Cr- FAU,Fe- FAU,Al - FAU,La-FAU；Other molecular sieves and support preparation method are similar, mark
It is denoted as M-Z, wherein M includes Li, Na, K, Ca, Cr, Fe, Al, La.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, it is described that there is mesoporous and micropore knot
The loading type alkali metal oxide catalyst of structure carrier, the preparation method of Jie's micro porous molecular sieve carrier：By certain mass M-Z carrier
It is added in certain density acid solution, 6 h, filtration washing, 120 DEG C of dryings 8 is then stirred at reflux at 100 DEG C of oil bath
H, the 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 8 h of drying obtain Jie's micropore M-Z-DAl-DSi carrier；It is put into Muffle furnace and is kept in 550 DEG C
6 h, are denoted as：M-meso-Z.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, given an account of micro porous molecular sieve carrier
Preparation method, the molecular sieve of different topology structure includes the one or more of EMT, MOR, MWW, FAU, MFI, FER, BEA；Acid
Property solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；Alkaline solution includes NaOH, Na2CO3Deng
It is one or more, preferably NaOH；Alkaline solution concentration is 0.05mol/L-2.0mol/L.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, the reaction are fixed bed atmospheric pressure
To 10MPa reaction pressure, the various alcohols of liquid charging stock are beaten with pump and dimethyl oxalate molar ratio is 20:1 charging, is urged above-mentioned
Reaction synthesizes symmetrical oxalate to agent existence condition in next step, and air speed is 0.1-100 h-1,60-200 DEG C of reaction temperature of item
Under part, catalyst is multi-functional compound basic catalyst, and catalyst amount is the 0.1-3wt% of material quality, the symmetrical oxalic acid of product
Ester yield is not less than 80%.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, the continuous fixed bed reaction or continuous system
During standby symmetrical oxalate, optimum condition is various alcohols（ROH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol）：Oxalic acid two
Methyl esters molar ratio=20:1, air speed 0.5-5 h-1, 70-140 DEG C of reaction temperature.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, the continuous fixed bed reaction or continuous are anti-
Pressure 0.1-10MPa is answered, various alcohols and dimethyl oxalate molar ratio are 20:1, reaction preparation pair in the presence of a catalyst
Claim oxalate, closed 25-150 DEG C in reaction kettle, reacts 0.5-10 h, catalyst is the various base catalysis protected in the present invention
Agent, catalyst amount are the 0.1-10 wt % of material quality.
The method by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, it is described to prepare symmetrical oxalate
Optimum condition is each alcohols in the process（ROH is the higher alcohols such as ethyl alcohol, propyl alcohol, butanol）：Dimethyl oxalate molar ratio=20:1, instead
Answer 90-140 DEG C of 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 in figure：The molar ratio of ethyl alcohol and dimethyl oxalate is 20:1,2 h of air speed-1, react under normal pressure, 10%
MgO-5% Al2O3-8%Fe2O3/ Na-meso-Y 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 dimethyl oxalate and various alcohols（ROH can be ethyl alcohol, propyl alcohol, fourth
The higher alcohols such as alcohol）The method of the symmetrical oxalate of one-step synthesis, the response path are as follows：
(COOCH3)2+2ROH→2CH3OH+ROOCCOOR……………………………………..(1)
The path is using multi-functional compound basic matterial as catalyst, by dimethyl oxalate and various alcohols（ROH can be ethyl alcohol, third
The higher alcohols such as alcohol, butanol）For the one symmetrical oxalate of step high selectivity of reaction raw materials, solid basic catalyst is completely insoluble in
Reaction raw materials and product, the unique by-product of reaction process are asymmetric oxalate.By reactive distillation, Methanol product is gradually removed
The selectivity of reaction system, target product oxalic acid symmetrical ester can be close to 100%.Solid catalyst is isolated by filtration, and repetition makes
With.Therefore, entire response path green, energy-saving and environmental protection, efficiently.
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 FAU molecular sieve carrier poisoned with alkali metal ion（M-FAU, M can be Li, Na, K, Ca, Cr, Fe, Al, La）For
Example, preparation method are as follows：It is placed in the H-FAU molecular sieve of certain mass in deionized water, the metal of 1M is added 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
FAU,Na-FAU,K-FAU,Ca-EMT,Cr-FAU,Fe-FAU,Al-FAU,La-FAU.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 dry 8h, the M-Z-DAl carrier after obtaining dealuminzation are stirred at reflux at 100 DEG C of oil bath.Then
It is added in certain density alkaline solution, 30 min, filtration washing is handled in 60 DEG C of water-baths, 120 DEG C of dry 8h are situated between
Micropore M-Z-DAl-DSi carrier.It is put into Muffle furnace in 550 DEG C of holding 6h, 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 10h, 550 DEG C of 3 h of roasting 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 is with dimethyl oxalate and various alcohols（ROH, R can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol）For raw material,
Symmetrical oxalate is synthesized in next step in the catalyst existence condition of above-mentioned preparation, 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 is：Under normal pressure to 10MPa reaction pressure, liquid is beaten with pump
The various alcohols of raw material and dimethyl oxalate molar ratio are 20:1 charging, in the reaction synthesis pair in next step of above-mentioned catalyst existence condition
Claim oxalate, air speed is 0.1-100 h-1, under conditions of 60-200 DEG C of reaction temperature, catalyst be protected in the present invention it is each
The multi-functional compound basic catalyst of kind, catalyst amount are the 0.1-3wt% of material quality, and the symmetrical oxalate yield of product is not low
In 80%.
During preparing symmetrical oxalate with fixed bed reaction, optimum condition is various alcohols（ROH can for ethyl alcohol,
The higher alcohols such as propyl alcohol, butanol）：Dimethyl oxalate molar ratio=20:1, air speed 0.5-5 h-1, 70-140 DEG C of reaction temperature.
Still reaction specific embodiment of the present invention is：Reaction pressure 0.1-10MPa, various alcohols and dimethyl oxalate rub
You are than being 20:1, it reacts prepare symmetrical oxalate in the presence of a catalyst, closed 25-150 DEG C in reaction kettle, react 0.5-
10 h, catalyst are the various basic catalysts protected in the present invention, and catalyst amount is the 0.1-10 wt % of material quality.
During preparing symmetrical oxalate with still reaction, optimum condition is various alcohols（ROH can be ethyl alcohol, third
The higher alcohols such as alcohol, butanol）：Dimethyl oxalate molar ratio=20:1,90-140 DEG C of reaction temperature.
Catalyst of the present invention is multi-functional compound basic catalyst, it is advantageous that mesoporous 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, catalysis
Non-inactivation is reacted in agent for a long time, and the symmetrical oxalate selectivity of product is high, and catalyst preparation is simple, no pollution to the environment, energy-saving ring
It protects.
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, using constant flow pump by ethyl alcohol and dimethyl oxalate respectively with molar ratio
20:1 ratio is pumped into reactor, and air speed is 2 h-1, 100 DEG C of reaction temperature, react under normal pressure, stablize 500 h, after stablizing
Sampling carries out chromatography calculating, and feed stock conversion, product yield are as shown in table 1.
Influence of the 1 variety classes catalyst of table to feed stock conversion, selectivity of product
As can be seen from Table 1, with 10%MgO-5%-Al2O3-8%Fe2O3When/Na-meso-Y is catalyst, the catalytic effect of reaction
Most preferably, dimethyl oxalate conversion ratio is up to 98%, and the molar selectivity of product medium-height grass diethyl phthalate is up to 83%.
Embodiment 2
In fixed bed reactors, influence of the different material molar ratio to feed stock conversion and selectivity of product is probed into.In fixation
10%MgO-5% Al is packed into bed reaction tube2O3-8%Fe2O310 g of/Na-meso-Y catalyst, using constant flow pump by ethyl alcohol and grass
Dimethyl phthalate is respectively with molar ratio 10:1,12:1,14:1,16:1,20:1,24:1 ratio is pumped into reactor, air speed 2
h-1, it 100 DEG C of reaction temperature, reacts under normal pressure, stablizes 500 h, sampling carries out chromatography calculating after stablizing, feed stock conversion,
Product yield is as shown in table 2.
Influence of the 2 different material molar ratio of table to feed stock conversion, selectivity of product
As can be seen from Table 2, with 10%MgO-5% Al2O3-8%Fe2O3/ Na-meso-Y is catalyst
When, with gradually increasing for alcohol ester molar ratio, the selectivity of reaction-ure conversion-age and diethy-aceto oxalate is all increased.When
The molar ratio of ethyl alcohol and dimethyl oxalate is greater than 20:When 1, raw material dimethyl oxalate conversion ratio and product diethy-aceto oxalate selectivity
It is approximate constant.
Embodiment 3
In fixed bed reactors, influence of the differential responses temperature to feed stock conversion and selectivity of product is probed into.In fixed bed
10%MgO-5% Al is packed into reaction tube2O3-8%Fe2O310 g of/Na-meso-Y catalyst, using constant flow pump by various alcohols with
Dimethyl oxalate is with molar ratio 20:1 ratio is pumped into reactor, and air speed is 2 h-1, react under normal pressure, reaction temperature such as table
It is shown, and stablize 500 h, sampling carries out chromatography calculating after stablizing, and feed stock conversion, product yield are as shown in table 3.
Influence of the 3 differential responses temperature of table to feed stock conversion, selectivity of product
From table 3 it can be seen that with the raising of reaction temperature, the conversion ratio and product diethy-aceto oxalate of reactant dimethyl oxalate
Selectivity increase, but when temperature be higher than 100 DEG C after, continue increase temperature, reaction-ure conversion-age and product yield are several
It is constant.
Embodiment 4
In fixed bed reactors, influence of the different alcohols to feed stock conversion and product yield is probed into.In fixed bed reaction pipe
Middle loading 10%MgO-5% Al2O3-8%Fe2O310 g of/Na-meso-Y catalyst, using constant flow pump by various alcohols and oxalic acid two
Methyl esters is with molar ratio 20:1 ratio is pumped into reactor, and air speed is 2 h-1, 100 DEG C of reaction temperature, react under normal pressure, stablize
500 h, sampling carries out chromatography calculating after stablizing, and feed stock conversion, product yield are as shown in table 4.
Influence of the different alcohols of table 4 to feed stock conversion, selectivity of product
As can be seen from Table 4, symmetrical oxalate is synthesized using different alcohols as reaction raw materials, reaction result difference is larger, with R
Group becomes complicated, and the yield of symmetrical oxalate gradually decreases.The reason is that as R group complicates, the space bit resistive of ROH
Greatly, R group is difficult to close to dimethyl oxalate and is replaced.
Embodiment 5
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 10%MgO-5% Al2O3-8%Fe2O310 g of/Na-meso-Y catalyst, using constant flow pump by each ethyl alcohol and oxalic acid diformazan
Ester is with molar ratio 20:1 ratio is pumped into reactor, and it is as shown in the table for differential responses air speed, and 100 DEG C of reaction temperature, under normal pressure
Reaction, and stablize 500 h, sampling carries out chromatography calculating after stablizing, and feed stock conversion, selectivity of product are as shown in table 5.
Influence of 5 reaction velocity of table to feed stock conversion, selectivity of product
As can be seen from Table 5, as the molar selectivity of the increase reaction-ure conversion-age of air speed and diethy-aceto oxalate is basically unchanged,
When air speed is greater than 2 h-1When, the two decline is obvious.
Embodiment 6
By 2000 g10%MgO-5% Al2O3-8%Fe2O3It is 10 cm that/Na-meso-Y catalyst, which is packed into internal diameter, is highly 200
In the stainless steel fixed bed reactors of cm, reactor void volume part is filled with quartz sand., using constant flow pump by ethyl alcohol and grass
Dimethyl phthalate is with molar ratio 20:1 ratio is pumped into reactor, and air speed is 2 h-1, it 100 DEG C of reaction temperature, reacts under normal pressure,
Product diethy-aceto oxalate is selectively stablized 82% or so, and 1000 h of steady state operation, catalytic activity and selectivity of product are substantially not
Become.
Embodiment 7
In three-necked flask, ethyl alcohol and dimethyl oxalate molar ratio 10:1, catalyst 10%MgO-5% Al2O3-8%Fe2O3/Na-
Meso-Y additional amount is 2 wt% of total mass of raw material, and 78 DEG C of reaction temperature, the methanol of generation is separated and collected by water segregator.
After reacting 5 h, mixture carries out chromatography, only ethyl alcohol and diethy-aceto oxalate, absolutely not other by-products in there-necked flask.
After product is filtered to remove solid catalyst while hot, after 60 DEG C of vacuum rotary steam 20min of clear liquid, the high-purity diethy-aceto oxalate of white is obtained
Solid.It filters rear catalyst and reuses 100 circulations or more, catalytic activity still maintains constant.
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 (8)
1. by the method for dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, which is characterized in that the method includes a steps
Method synthesis of oxalic acid symmetrical ester reaction route equation is as follows：
(COOCH3)2+2ROH→2CH3OH+ROOCCOOR……………………………………..(1)
Raw material is respectively dimethyl oxalate and ROH, and wherein ROH can be the higher alcohols such as ethyl alcohol, propyl alcohol, butanol；
The catalyst for being catalyzed single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；Catalyst Formula
For X/Z, wherein Z is the carrier of different topology structure, including topological structure is MOR, FAU, MFI, FER, BEA molecular sieve and often
Advise SiO2、Al2O3、ZrO2, one or more of MgO and ZnO carrier oxide；X is Li, Na, K, Ca, Cr, Fe, Al, La
The oxide of middle one or more metal.
2. the method according to claim 1 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
In the Z molecular sieve carrier, hydrogen type molecular sieve passes through ion exchange, and Bronsted acid is poisoned by metal ion, makes it not
With Bronsted acidity；The FAU molecular sieve carrier poisoned with alkali metal ion（M- FAU, M can for Li, Na, K, Ca, Cr,
Fe,Al,La）For, preparation method is as follows：The H-FAU molecular sieve of certain mass is placed in deionized water, respectively thereto
The metal-nitrate solutions of 1M are added, in 90 DEG C of 2 h of exchange；It is dried overnight after filtration washing in 120 DEG C, 600 DEG C of roastings 6
Li- FAU, Na- FAU, K-FAU, Ca-EMT, Cr- FAU, Fe- FAU, Al-FAU, La-FAU can be obtained in h；Other points
Son sieve and support preparation method are similar, are labeled as M-Z, wherein M includes Li, Na, K, Ca, Cr, Fe, Al, La.
3. the method according to claim 1 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
In described with mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, the system of Jie's micro porous molecular sieve carrier
Preparation Method：Certain mass M-Z carrier is added in certain density acid solution, is then stirred at reflux 6 at 100 DEG C of oil bath
H, filtration washing, 120 DEG C of 8 h of drying, the M-Z-DAl carrier after obtaining dealuminzation；It is then added to certain density alkaline solution
In, 30 min, filtration washing are handled in 60 DEG C of water-baths, 120 DEG C of 8 h of drying obtain Jie's micropore M-Z-DAl-DSi carrier；
It is put into Muffle furnace in 550 DEG C of 6 h of holding, is denoted as：M-meso-Z.
4. the method according to claim 1 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
In, the preparation method of given an account 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；Acid solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；
Alkaline solution includes NaOH, Na2CO3Deng one or more, preferably NaOH；Alkaline solution concentration is 0.05mol/L-2.0mol/
L。
5. the method according to claim 1 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
In the reaction is to beat the various alcohols of liquid charging stock under fixed bed atmospheric pressure to 10MPa reaction pressure with pump and dimethyl oxalate rubs
You are than being 20:1 charging, in above-mentioned catalyst existence condition, reaction synthesizes symmetrical oxalate, air speed 0.1-100 in next step
H-1, under conditions of 60-200 DEG C of reaction temperature, catalyst is multi-functional compound basic catalyst, and catalyst amount is raw material matter
The 0.1-3wt% of amount, the symmetrical oxalate yield of product are not less than 80%.
6. the method according to claim 1 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
During the continuous fixed bed reaction or continuous prepares symmetrical oxalate, optimum condition is various alcohols（ROH can be ethyl alcohol, third
The higher alcohols such as alcohol, butanol）：Dimethyl oxalate molar ratio=20:1, air speed 0.5-5 h-1, 70-140 DEG C of reaction temperature.
7. the method according to claim 6 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
In the continuous fixed bed reaction or continuous reaction pressure 0.1-10MPa, various alcohols and dimethyl oxalate molar ratio are 20:1, it is urging
It is reacted under agent existence condition and prepares symmetrical oxalate, closed 25-150 DEG C in reaction kettle, react 0.5-10 h, catalyst is this
The various basic catalysts protected in invention, catalyst amount are the 0.1-10 wt % of material quality.
8. the method according to claim 1 by dimethyl oxalate and the symmetrical oxalate of alcohols one-step synthesis, feature exist
In described to prepare optimum condition during symmetrical oxalate be each alcohols（ROH is the higher alcohols such as ethyl alcohol, propyl alcohol, butanol）：Grass
Dimethyl phthalate molar ratio=20:1,90-140 DEG C of reaction temperature.
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| CN110511138A (en) * | 2019-09-24 | 2019-11-29 | 河北广润化工有限公司 | A kind of production technology of symmetrical oxalate |
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| 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 |
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2018
- 2018-07-03 CN CN201810719131.3A patent/CN108911975A/en active Pending
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| 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 |
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| CN110511138A (en) * | 2019-09-24 | 2019-11-29 | 河北广润化工有限公司 | A kind of production technology of symmetrical oxalate |
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