CN102649728A - Method for producing oxalate through gas-phase reaction of carbon monoxide - Google Patents
Method for producing oxalate through gas-phase reaction of carbon monoxide Download PDFInfo
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- CN102649728A CN102649728A CN201110045120XA CN201110045120A CN102649728A CN 102649728 A CN102649728 A CN 102649728A CN 201110045120X A CN201110045120X A CN 201110045120XA CN 201110045120 A CN201110045120 A CN 201110045120A CN 102649728 A CN102649728 A CN 102649728A
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Abstract
The invention relates to a method for producing oxalate through gas-phase reaction of carbon monoxide, and mainly solves the technical problem in the prior art that the target product is low in selectivity. The method adopts a mixed gas containing both nitrous acid ester and carbon monoxide as the raw material, and comprises the step that the raw material is in contact with a precious metal catalyst to produce oxalate under the conditions that the reaction temperature is 100-180 DEG C, the hourly space velocity is 500-10,000 hours <-1> and the reaction pressure is -0.08-1.5MPa, wherein the precious metal catalyst selects palladium as the active component, at least one of gallium or germanium as the additive and at least one of aluminum oxide, silicon oxide or molecular sieve as the carrier. By adopting the technical scheme, the problem is better solved and the method provided by the invention can be used for industrial increase production of oxalate.
Description
Technical field
The present invention relates to a kind of method of producing barkite, particularly about method by CO and methyl nitrite or ethyl nitrite coupling production dimethyl oxalate or oxalic acid diethyl ester by the CO gas-phase reaction.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various midbody.Get into 21 century, barkite receives international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare crucial industrial chemicals terepthaloyl moietie, and terepthaloyl moietie mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import terepthaloyl moietie every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and the production technique cost is high, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking an operational path that cost is low, environment is good always.The sixties in last century; The D.F.Fenton of U.S. Associated Oil Company finds; Carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative coupling method synthesis of oxalate and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer is prone to run off in the reaction process.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
Along with carbon monoxide oxidative coupling legal system in the world is equipped with the research and development of barkite Technology, domestic many research institutions have also carried out research work to this field.According to the china natural resources characteristic distributions, be the feedstock production organic oxygen-containing compound with the carbon monoxide, for the pressure of alleviating petroleum products, rationally utilize coal and natural gas source to have crucial strategic importance.At present; Become important research project in domestic one-carbon chemical and the organic chemical industry field by carbon monoxide oxidative coupling method synthesis of oxalate; Successively there are how tame research institution and research institutions to be devoted to catalyzer development, process exploitation and the engineering amplification work in this field, and obtained bigger progress.
Although above-mentioned numerous research institution has obtained than much progress technically, technology itself still remains further to be improved and development, especially improves reaction preference how, and aspects such as raising activity of such catalysts all need further research and break through.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopts vapor phase process, and CO is under the participation of ethyl nitrite; Under the catalysis of bimetal loaded catalyst, coupling generates the oxalic acid diethyl ester bullion, reacts to be self-enclosed working cycle; CO gas with get into coupler reactor from the ethyl nitrite of regeneration reactor through mixing preheating, reaction back gas obtains water white oxalic acid diethyl ester lime set through condensation separation; The non-condensable gas that contains NO gets into regeneration reactor, in regeneration reactor, returns coupler reactor and uses continuously with ethanol, the recycling of oxygen reaction generation ethyl nitrite, and this invention is on the basis of lab scale research in early stage; With the industrial production is that background is carried out, and the continuous operation examination is amplified in mould examination and the pilot scale accomplished under the industrial operation condition, and the linked reaction temperature is low; Product concentration improves; Present method is more energy-conservation, and is pollution-free, high efficiency.But per pass conversion that should technology CO is 20～60%, and the purpose selectivity of product all remains further to be improved about 96%.
Document CN 95116136.9 discloses the catalyzer of the synthetic usefulness of a kind of barkite, selects for use Zr to make auxiliary agent, develops novel Pd-Zr/Al with pickling process
2O
3Catalyzer.This catalyzer is to adopt fixed-bed reactor as carbon monoxide and the reaction of nitrous acid ester synthesis of oxalic ester by gaseous catalysis.But the yield of its barkite of catalyzer that is adopted in this patent is lower, and the impurity of virgin gas is had relatively high expectations, and the selectivity of product barkite is 95%, and the per pass conversion of nitrous acid ester is up to 64%, all remains further to be improved.
Summary of the invention
Technical problem to be solved by this invention is the low problem of barkite selectivity that in the past exists in the document, and a kind of new method of producing barkite by the CO gas-phase reaction is provided.This method has the high advantage of barkite selectivity.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method of being produced barkite by the CO gas-phase reaction; With the mixed gas that contains nitrous acid ester and CO is raw material, and 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is under the condition of-0.08～1.5MPa, and raw material contacts with noble metal catalyst, and reaction generates barkite; Wherein, noble metal catalyst comprises carrier, active ingredient and auxiliary agent, and by weight percentage, noble metal catalyst comprises following component:
A) being selected from palladium is active ingredient, is 0.003～1.5% of catalyst weight in the simple substance consumption;
B) being selected from least a in gallium or the germanium is auxiliary agent, is 0.005～9% of catalyst weight in the simple substance consumption;
C) 89～99.5% carrier;
Wherein carrier is selected from Al
2O
3, silicon oxide or molecular sieve at least a.
In the technique scheme, the precious metal catalyst agent carrier is preferably selected from Al
2O
3, its specific surface preferable range is 2～100 meters squared per gram.The precious metal catalyst agent carrier more preferably is selected from α-Al
2O
3, its specific surface more preferably scope is 2～80 meters squared per gram.The palladium active ingredient of noble metal catalyst is that the preferable range of catalyst weight is 0.1～1% in the simple substance consumption.At least a auxiliary agent in gallium or the germanium is that the preferable range of catalyst weight is 0.01～5% in the simple substance consumption.
The reaction conditions preferable range of reactor drum is in the technique scheme: 110～160 ℃ of temperature of reaction, volume space velocity are 1000～6000 hours-1, and reaction pressure is-0.02～1.0MPa; Reaction conditions more preferably scope is: 110～150 ℃ of temperature of reaction, volume space velocity are 2000～5000 hours
-1, reaction pressure is-0.01～0.5MPa.Contain in the mixed gas feed of nitrous acid ester and CO, the mol ratio of CO and nitrous acid ester is 0.5～5: 1; The preferable range of the mol ratio of CO and nitrous acid ester is 1.0～2: 1.Nitrous acid ester is selected from methyl nitrite, ethyl nitrite or its mixture, preferably from methyl nitrite.
The Preparation of catalysts process of the inventive method is following:
A) soluble salt with palladium and gallium or germanium is mixed with steeping fluid by metering, and transferring the pH value of steeping fluid is 0.8～9;
B) carrier is soaked in steeping fluid;
C) after the drying, roasting under air or nitrogen atmosphere.
Detailed process is: according to the charge capacity of catalyst activity metal component and auxiliary agent, select for use halogenide, nitrate salt, acetate or the oxalate of gallium or germanium and palladium metal and water to be mixed with hybrid infusion solution.In order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, generally also need add on a small quantity with metal salt anion acid accordingly, making pH value of aqueous solution is between 0.8～9.Be immersed in carrier in the steeping fluid for preparing then, to guarantee that dipping fluid power uniform loading is on carrier.After abundant absorbing load, take out carrier, dry naturally in dropping a hint, after 120 ℃ of dryings, pass through roasting, just can make the catalyzer of the inventive method.
As everyone knows, in CO coupling producing oxalic ester reaction process, the selectivity of barkite height is closely related with the character of catalyzer; Especially the selection of the character of carrier and auxiliary agent all has remarkable influence to the selectivity of barkite; The present inventor is surprised to find, and adopts technical scheme of the present invention, and the specific surface through the control catalyst carrier is in 2～100 meters squared per gram scopes; And selecting at least a in gallium or the germanium be auxiliary agent, and prepared catalyzer is at reaction process medium-height grass acid esters selectivity height.
Adopting technical scheme of the present invention, is raw material with the mixed gas that contains nitrous acid ester and CO, is active ingredient to be selected from palladium, be selected from gallium or the germanium at least a for auxiliary agent with comprise that is selected from an Al
2O
3, silicon oxide or at least a of molecular sieve be 110～160 ℃ for the carrier noble metal catalyzer is a catalyzer in temperature of reaction, volume space velocity is 1000～6000 hours
-1, reaction pressure is under the condition of-0.02～1.0MPa, and raw material contacts with catalyzer, and nitrous acid ester and CO reaction generates barkite in the raw material, and the selectivity of barkite can obtain better technical effect greater than 99%.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Take by weighing 100 gram α-Al
2O
3Carrier is pressed 0.1wt%Pd+0.3wt%Ga/ α-Al
2O
3Content prepares catalyzer; Its step is following: select Palladous nitrate and gallium nitrate for use; According to the charge capacity preparation steeping fluid of Pd and gallium,, in steeping fluid, add a small amount of nitric acid in order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide compound is heavy fixed; Making the PH=0.8 of steeping fluid, is the α-Al of 8 meters squared per gram with specific surface area
2O
3Carrier is put into the mixed impregnant liquor for preparing and is soaked for some time, takes out then to be placed in the air and dries, drying, roasting under air, nitrogen or argon gas atmosphere, just processes Pd-Ga/ α-Al
2O
3Catalyst A, catalyst A before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then, wherein, the mol ratio of CO and methyl nitrite is 1.2: 1, is 130 ℃ in temperature of reaction, the reaction volume air speed is 2000 hours
-1, reaction pressure is-condition of 0.08MPa under, raw material contacts with catalyzer, reacts, its reaction result is: CO per pass conversion 78.4%, the selectivity of dimethyl oxalate are 99.2%.
[embodiment 2]
Take by weighing 100 gram α-Al
2O
3Carrier is pressed 0.3wt%Pd+0.8wt%Ga/ α-Al
2O
3Content prepares catalyzer; Its step is following: select Palladous nitrate and gallium nitrate for use; According to the charge capacity preparation steeping fluid of Pd and gallium,, in steeping fluid, add a small amount of nitric acid in order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide compound is heavy fixed; Making the PH=6 of steeping fluid, is the α-Al of 5 meters squared per gram with specific surface area
2O
3Carrier is put into the mixed impregnant liquor for preparing and is soaked for some time, takes out then to be placed in the air and dries, drying, roasting under air, nitrogen or argon gas atmosphere, just processes Pd-Ga/ α-Al
2O
3Catalyst B, catalysis B before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then, wherein, the mol ratio of CO and methyl nitrite is 1.5: 1, is 110 ℃ in temperature of reaction, the reaction volume air speed is 800 hours
-1, reaction pressure is-condition of 0.05MPa under, raw material contacts with catalyzer, reacts, its reaction result is: CO per pass conversion 63.2%, the selectivity of dimethyl oxalate are 99.7%.
[embodiment 3]
Take by weighing 100 gram α-Al
2O
3Carrier is pressed 0.8wt%Pd+2.5wt%Ga/ α-Al
2O
3Content prepares catalyzer; Its step is following: select Palladous chloride and gallium nitrate for use; According to the charge capacity preparation steeping fluid of Pd and gallium,, in steeping fluid, add a small amount of nitric acid in order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide compound is heavy fixed; Making the PH=3 of steeping fluid, is the α-Al of 30 meters squared per gram with specific surface area
2O
3Carrier is put into the mixed impregnant liquor for preparing and is soaked for some time, takes out then to be placed in the air and dries, drying, roasting under air, nitrogen or argon gas atmosphere, just processes Pd-Ga/ α-Al
2O
3Catalyzer C, catalyzer C before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then, wherein, the mol ratio of CO and methyl nitrite is 2: 1,140 ℃ of temperature of reaction, the reaction volume air speed is 3000 hours
-1, reaction pressure is-condition of 0.02MPa under, raw material contacts with catalyzer, reacts, its reaction result is: CO per pass conversion 45.2%, the selectivity of dimethyl oxalate are 99.1%.
[embodiment 4]
Take by weighing 80 gram silica supports, prepare catalyzer by the 0.3wt%Pd+3wt%Ge/ silica content, its step is following: select Palladous nitrate and nitric acid germanium for use; Charge capacity preparation steeping fluid according to Pd and germanium; In order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide compound is heavy fixed, in steeping fluid, add a small amount of nitric acid, make the PH=2 of steeping fluid; With specific surface area is that the silica support of 100 meters squared per gram is put into the mixed impregnant liquor for preparing and soaked for some time; Take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process Pd-Ge/ silicon oxide catalyst D, catalyzer D before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then; Wherein, The mol ratio of CO and methyl nitrite is 4: 1, and 160 ℃ of temperature of reaction, the reaction volume air speed is 6000 hours
-1, reaction pressure is under the condition of 0.02MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 22.2%, the selectivity of dimethyl oxalate are 98.3%.
[embodiment 5]
Take by weighing 100 gram α-Al
2O
3Carrier is pressed 0.2wt%Pd+1wt%Ge/ α-Al
2O
3Content prepares catalyzer; Its step is following: select Palladous nitrate and nitric acid germanium for use; According to the charge capacity preparation steeping fluid of Pd and germanium,, in steeping fluid, add a small amount of nitric acid in order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide compound is heavy fixed; Making the PH=4 of steeping fluid, is the α-Al of 30 meters squared per gram with specific surface area
2O
3Carrier is put into the mixed impregnant liquor for preparing and is soaked for some time, takes out then to be placed in the air and dries, drying, roasting under air, nitrogen or argon gas atmosphere, just processes Pd-Ge/ α-Al
2O
3Catalyzer E, catalyzer E before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then, wherein, the mol ratio of CO and methyl nitrite is 1.3: 1,170 ℃ of temperature of reaction, the reaction volume air speed is 8000 hours
-1, reaction pressure is under the condition of 0.5MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 74.6%, the selectivity of dimethyl oxalate are 97.3%.
[embodiment 6]
Taking by weighing 100 gram silica alumina ratios is that 100 ZSM-5 molecular sieve is a carrier, prepares catalyzer by 0.2wt%Pd+0.1wt%Ga/ZSM-5 content, and its step is following: select Palladous chloride and gallium nitrate for use; Charge capacity preparation steeping fluid according to Pd and gallium; In order to prevent that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide compound is heavy fixed, in steeping fluid, add a small amount of nitric acid, make the PH=2 of steeping fluid; With specific surface area is that the ZSM-5 molecular sieve carrier of 100 meters squared per gram is put into the mixed impregnant liquor for preparing and soaked for some time; Take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process Pd-Ga/ZSM-5 sieve catalyst F, catalyzer F before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then; Wherein, The mol ratio of CO and methyl nitrite is 1.5: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.2MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 63.8%, the selectivity of dimethyl oxalate are 99.5%.
[embodiment 7]
Step and condition according to embodiment 1 make 0.3wt%Pd+0.6wt%Ga/ α-Al
2O
3Catalyzer G, catalyzer G before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then, wherein, the mol ratio of CO and methyl nitrite is 1.3: 1,120 ℃ of temperature of reaction, the reaction volume air speed is 1500 hours
-1, reaction pressure is under the condition of 0.1MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 73.9%, the selectivity of dimethyl oxalate are 99.8%.
[embodiment 8]
Step and condition according to embodiment 1 make 0.5wt%Pd+1.8wt%Ga/ α-Al
2O
3Catalyzer H, catalyzer H before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite then, wherein, the mol ratio of CO and methyl nitrite is 0.6: 1,120 ℃ of temperature of reaction, the reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.03MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 96.2%, the selectivity of dimethyl oxalate are 99.1%.
[embodiment 9]
Step and condition according to embodiment 1 make 0.3wt%Pd+0.6wt%Ge/ α-Al
2O
3Catalyst I, catalyst I before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours, be raw material with CO and methyl nitrite, wherein, the mol ratio of CO and methyl nitrite is 0.9: 1,120 ℃ of temperature of reaction, the reaction volume air speed is 2500 hours
-1, reaction pressure is under the condition of 0.3MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 93.1%, the selectivity of dimethyl oxalate are 99.4%.
[embodiment 10]
Step and condition according to embodiment 1 make 0.2wt%Pd+0.3wt%Ge/ silicon oxide catalyst J; Catalyzer J before use all through 300 ℃ of excess temperatures with hydrogen reducing 4 hours; With CO and ethyl nitrite is raw material, and wherein, the mol ratio of CO and ethyl nitrite is 1.3: 1; 130 ℃ of temperature of reaction, the reaction volume air speed is 4000 hours
-1, reaction pressure is under the condition of 0.05MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 72.8%, the selectivity of oxalic acid diethyl ester are 99.4%.
[comparative example 1]
Adopt the catalyzer of the embodiment 6 among the document CN02146105.8.According to embodiment 1 same reaction conditions and reaction raw materials, react, its reaction result is: CO per pass conversion 74.1%, the selectivity of dimethyl oxalate are 95.7%.
[comparative example 2]
Adopt the catalyzer of the embodiment 5 among the document CN02146105.8.According to embodiment 1 same reaction conditions and reaction raw materials, react, its reaction result is: CO per pass conversion 73.1%, the selectivity of dimethyl oxalate are 96.1%.
Claims (9)
1. a method of producing barkite by the CO gas-phase reaction is a raw material with the mixed gas that contains nitrous acid ester and CO, and 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is under the condition of-0.08～1.5MPa, and raw material contacts with noble metal catalyst, and reaction generates barkite; Wherein, noble metal catalyst comprises carrier, active ingredient and auxiliary agent, and by weight percentage, noble metal catalyst comprises following component:
A) being selected from palladium is active ingredient, is 0.003～1.5% of catalyst weight in the simple substance consumption;
B) being selected from gallium or germanium is auxiliary agent, is 0.005～9% of catalyst weight in the simple substance consumption;
C) 89～99.5% carrier;
Wherein carrier is selected from Al
2O
3, silicon oxide or molecular sieve at least a.
2. according to the said method of producing barkite of claim 1, it is characterized in that the precious metal catalyst agent carrier is selected from Al by the CO gas-phase reaction
2O
3, its specific surface is 2～100 meters squared per gram.
3. according to the said method of producing barkite of claim 2, it is characterized in that the precious metal catalyst agent carrier is selected from α-Al by the CO gas-phase reaction
2O
3, its specific surface is 2～80 meters squared per gram.
4. according to the said method of producing barkite by the CO gas-phase reaction of claim 1, it is characterized in that the noble metal catalyst active ingredient is a palladium, is 0.1～1% of catalyst weight in the simple substance consumption.
5. according to the said method of producing barkite by the CO gas-phase reaction of claim 1, it is characterized in that the precious metal catalyst agent aid is at least a in gallium or the germanium, is 0.01～5% of catalyst weight in the simple substance consumption.
6. according to the said method of producing barkite by the CO gas-phase reaction of claim 1, the temperature of reaction that it is characterized in that reactor drum is 110～160 ℃, and volume space velocity is 1000～6000 hours
-1, reaction pressure is-0.02～1.0MPa.
7. according to the said method of producing barkite by the CO gas-phase reaction of claim 1, it is characterized in that containing in the mixed gas feed of nitrous acid ester and CO, the mol ratio of CO and nitrous acid ester is 0.5～5: 1.
8. according to the said method of producing barkite by the CO gas-phase reaction of claim 7, it is characterized in that containing in the mixed gas feed of nitrous acid ester and CO, the mol ratio of CO and nitrous acid ester is 1.0～2: 1.
9. according to the said method of producing barkite of claim 1, it is characterized in that nitrous acid ester is selected from methyl nitrite, ethyl nitrite or its mixture by the CO gas-phase reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962060A (en) * | 2012-11-22 | 2013-03-13 | 北京北大先锋科技有限公司 | Catalyst for synthetizing dimethyl oxalate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6056937A (en) * | 1983-09-08 | 1985-04-02 | Ube Ind Ltd | Production of oxalic acid diester |
| CN1055492A (en) * | 1990-04-10 | 1991-10-23 | 浙江大学 | Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide |
| CN1100089A (en) * | 1993-04-29 | 1995-03-15 | 拜尔公司 | Process for preparing dialkyl carbonates |
-
2011
- 2011-02-25 CN CN201110045120.XA patent/CN102649728B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6056937A (en) * | 1983-09-08 | 1985-04-02 | Ube Ind Ltd | Production of oxalic acid diester |
| CN1055492A (en) * | 1990-04-10 | 1991-10-23 | 浙江大学 | Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide |
| CN1100089A (en) * | 1993-04-29 | 1995-03-15 | 拜尔公司 | Process for preparing dialkyl carbonates |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962060A (en) * | 2012-11-22 | 2013-03-13 | 北京北大先锋科技有限公司 | Catalyst for synthetizing dimethyl oxalate and preparation method thereof |
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