CN102219677A - Method for producing oxalate by coupling carbon monoxide(CO) - Google Patents
Method for producing oxalate by coupling carbon monoxide(CO) Download PDFInfo
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- CN102219677A CN102219677A CN2010101469009A CN201010146900A CN102219677A CN 102219677 A CN102219677 A CN 102219677A CN 2010101469009 A CN2010101469009 A CN 2010101469009A CN 201010146900 A CN201010146900 A CN 201010146900A CN 102219677 A CN102219677 A CN 102219677A
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Abstract
The invention relates to a method for producing oxalate by coupling CO, and mainly aims to solve the technical problem of low selectivity of target products in the prior art. The method comprises the following steps of: a, introducing a raw material mixture containing nitrite and CO into a raw material purifier, removing water and alcohol at the temperature of between 30 DEG C below zero and 10 DEG C to obtain effluent I; and b, introducing the purified effluent I into a coupling reactor, and contacting a palladium-contained catalyst at the reaction temperature of between 100 and 160 DEG C and the reaction space velocity of between 500 and 6,000 hour<-1> under the reaction pressure of between -0.09 and 1.5 MPa to obtain reaction effluent containing oxalate, wherein the raw material purifier used in the step a is a crystallizer or a cooler. The technical scheme solves the technical problem of low selectivity of the target products; and the method can be applied to the industrial production of increasing the yield of the oxalate.
Description
Technical field
The present invention relates to a kind of method, particularly about the method for CO and methyl nitrite or ethyl nitrite coupling production dimethyl oxalate or oxalic acid diethyl ester by the CO preparing oxalate by coupling 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 intermediate.Enter 21 century, barkite is subjected to 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 acid 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 ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol 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, production technique cost height, 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 easily runs off in the reaction process.By 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 0.5MP, 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, by carbon monoxide oxidative coupling method synthesis of oxalate to become important research project in domestic one-carbon chemical and the organic chemical industry field, 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 technically than much progress, 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, adopt vapor phase process, CO is under the participation of ethyl nitrite, under the catalysis of bimetal loaded catalyst, coupling generates the oxalic acid diethyl ester crude product, reaction is self-enclosed working cycle, CO gas enters coupler reactor with ethyl nitrite from regeneration reactor through mixing preheating, reaction back gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, the non-condensable gas that contains NO enters regeneration reactor, in regeneration reactor and ethanol, the recirculation of oxygen reaction generation ethyl nitrite is returned coupler reactor and is used continuously, and the present invention is on the basis of lab scale research in early stage, is that background is carried out with the industrial production, the continuous operation examination is amplified in mould examination and the pilot scale finished under the industrial operation condition, the linked reaction temperature is low, and product concentration improves, and present method is more energy-conservation, pollution-free, high efficiency.But the per pass conversion of this 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 fat 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 unstripped 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 that the barkite selectivity that in the past exists in the document is low, and the problem that the nitrous acid ester utilization ratio is low provides a kind of new method by the CO preparing oxalate by coupling reaction.This method has barkite selectivity height, the advantage that the nitrous acid ester utilization ratio is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method by the CO preparing oxalate by coupling reaction may further comprise the steps:
A) contain the raw mix of nitrous acid ester and CO, at first incoming stock cleaner removes water and alcohol under temperature-30～10 ℃ condition, obtain effluent I;
B) the effluent I after purifying enters coupler reactor 100～160 ℃ of temperature of reaction, and reaction pressure is-0.09～1.5MPa, and reaction velocity is 500～6000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain barkite;
Wherein the raw material cleaner is crystallizer or water cooler in the step a).
Raw material cleaner service temperature is preferably-20～5 ℃ in the technique scheme, the operational condition of coupler reactor is preferably: the mol ratio of CO and nitrous acid ester be 1～3: 1, temperature of reaction is 100～150 ℃, and reaction pressure is-0.05～1.0MPa, and reaction velocity is 1000～5000 hours
-1
In the technique scheme palladium-containing catalyst with at least a in silicon oxide, aluminum oxide or the molecular sieve be carrier, preferred aluminum oxide is a carrier, molecular screening is from ZSM-5, mordenite, MCM-22 or beta-molecular sieve.Active ingredient is a palladium metal, is benchmark with the carrier, and the weight content of palladium is 0.05～5%, and the preferred weight content range is 0.1～3%, and nitrous acid ester is selected from methyl nitrite or ethyl nitrite.
As everyone knows, nitrous acid ester is that chemical property is active, meets acid, illumination and is heated and easily decomposes, and product is carbon monoxide, carbonic acid gas and oxynitride.Studies show that, be equipped with in the process of barkite in carbon monoxide oxidative coupling legal system, the content of water and alcohol needs control in the raw material alkyl nitrous acid ester gas mixture, otherwise can the activity of subsequent catalyst be impacted, conventional treatment technology is to remove water and alcohol by siccative, but the alkyl nitrous acid ester is being when removing moisture content in the conventional drying agent, also takes place easily to decompose and causes the loss of alkyl nitrous acid ester.The present invention adopts crystallizer or water cooler technology, allow the nitrous acid ester material that contains alcohol and water by crystallizer or water cooler, divide dried uply and pure at low temperatures, not only avoid the heat or the catalytic decomposition of alkyl nitrous acid ester, can keep the requirement of subsequent reactions simultaneously water-content.
Adopt technical scheme of the present invention, aluminum oxide with supported palladium is a catalyzer, with the vehicle weight is benchmark, the weight content of palladium metal is 0.1～3%, is that 1～3: 1 mixture is a raw material with the mol ratio of CO and methyl nitrite, the at first incoming stock cleaner of this raw mix, under temperature-20～5 ℃ condition, remove water and alcohol, it is 100～150 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, and reaction pressure is-0.05～1.0MPa, and reaction velocity is 1000～5000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain dimethyl oxalate, wherein, the CO per pass conversion is the highest can be greater than 71%, the selectivity of barkite is the highest can to have obtained better technical effect greater than 99%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
With CO and methyl nitrite is raw material, wherein, the mol ratio of CO and methyl nitrite is 1.2: 1, is catalyzer with palladium load aluminum oxide, is benchmark with the vehicle weight, the weight content of palladium metal is 1.5%, CO and methyl nitrite raw material at first enter crystallizer, remove water and alcohol under temperature-20 ℃ condition, and it is 120 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, reaction pressure is-0.05MPa that reaction velocity is 1000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain dimethyl oxalate, its reaction result is: CO per pass conversion 62.3%, the selectivity of dimethyl oxalate are 98.2%.
[embodiment 2]
With CO and methyl nitrite is raw material, wherein, the mol ratio of CO and methyl nitrite is 1.5: 1, is catalyzer with palladium load aluminum oxide, is benchmark with the vehicle weight, the weight content of palladium metal is 0.5%, CO and methyl nitrite raw material at first enter crystallizer, remove water and alcohol under temperature-10 ℃ condition, and it is 130 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, reaction pressure is 0.05MPa, and reaction velocity is 2000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain dimethyl oxalate, its reaction result is: CO per pass conversion 55.4%, the selectivity of dimethyl oxalate are 97.9%.
[embodiment 3]
With CO and ethyl nitrite is raw material, wherein, the mol ratio of CO and ethyl nitrite is 1: 1, is catalyzer (the Si/Al mol ratio is 550: 1) with palladium load ZSM-5 molecular sieve, is benchmark with the vehicle weight, the weight content of palladium metal is 0.8%, CO and ethyl nitrite raw material at first enter water cooler, remove water and alcohol under temperature-8 ℃ condition, and it is 140 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, reaction pressure is 0.1MPa, and reaction velocity is 3000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain oxalic acid diethyl ester, its reaction result is: CO per pass conversion 66.4%, the selectivity of oxalic acid diethyl ester are 99.1%.
[embodiment 4]
With CO and ethyl nitrite is raw material, wherein, the mol ratio of CO and ethyl nitrite is 1.6: 1, is catalyzer with palladium load aluminum oxide, is benchmark with the vehicle weight, the weight content of palladium metal is 0.2%, CO and ethyl nitrite raw material at first enter crystallizer, remove water and alcohol under temperature-2 ℃ condition, and it is 155 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, reaction pressure is 0.5MPa, and reaction velocity is 4000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain oxalic acid diethyl ester, its reaction result is: CO per pass conversion 45.4%, the selectivity of oxalic acid diethyl ester are 98.3%.
[embodiment 5]
With CO and methyl nitrite is raw material, wherein, the mol ratio of CO and methyl nitrite is 2: 1, is catalyzer with palladium load αYang Hualv, with the vehicle weight is benchmark, the weight content of palladium metal is 0.2%, and catalyzer also contains 0.2% iron, and CO and methyl nitrite raw material at first enter crystallizer, under 0 ℃ of condition of temperature, remove water and alcohol, it is 140 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, and reaction pressure is 0.8MPa, and reaction velocity is 3000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain dimethyl oxalate, its reaction result is: CO per pass conversion 44.4%, the selectivity of dimethyl oxalate are 99.3%.
[embodiment 6]
With CO and ethyl nitrite is raw material, wherein, the mol ratio of CO and ethyl nitrite is 3: 1, is catalyzer with palladium load αYang Hualv, with the vehicle weight is benchmark, the weight content of palladium metal is 2%, and catalyzer also contains 0.1% potassium, and CO and ethyl nitrite raw material at first enter crystallizer, under temperature-5 ℃ condition, remove water and alcohol, it is 115 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, and reaction pressure is 0.1MPa, and reaction velocity is 1000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain oxalic acid diethyl ester, its reaction result is: CO per pass conversion 25.2%, the selectivity of oxalic acid diethyl ester are 97.9%.
[embodiment 7]
With CO and methyl nitrite is raw material, wherein, the mol ratio of CO and methyl nitrite is 1.2: 1, is catalyzer with palladium load αYang Hualv, is benchmark with the vehicle weight, the weight content of palladium metal is 0.4%, CO and methyl nitrite raw material at first enter crystallizer, remove water and alcohol under temperature-10 ℃ condition, and it is 130 ℃ in temperature of reaction that the effluent I that obtains enters coupler reactor, reaction pressure is 0.2MPa, and reaction velocity is 2000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain dimethyl oxalate, its reaction result is: CO per pass conversion 78.4%, the selectivity of dimethyl oxalate are 99.3%.
[comparative example 1]
According to embodiment 7 identical catalyzer, condition and reaction raw materials, just only adopting the 5A molecular sieve is siccative, and its reaction result is as follows: CO per pass conversion 60.3%, the selectivity of dimethyl oxalate are 86.8%.
[comparative example 2]
According to embodiment 7 identical catalyzer, condition and reaction raw materials, just only adopting the ZSM-5 molecular sieve is siccative, and its reaction result is as follows: CO per pass conversion 58.1%, the selectivity of dimethyl oxalate are 82.5%.
Claims (6)
1. method by the CO preparing oxalate by coupling reaction may further comprise the steps:
A) contain the raw mix of nitrous acid ester and CO, at first incoming stock cleaner removes water and alcohol under temperature-30～10 ℃ condition, obtain effluent I;
B) the effluent I after purifying enters coupler reactor 100～160 ℃ of temperature of reaction, and reaction pressure is-0.09～1.5MPa, and reaction velocity is 500～6000 hours
-1Condition under contact with palladium-containing catalyst, generate the reaction effluent contain barkite;
Wherein the raw material cleaner is crystallizer or water cooler in the step a).
2. according to the described method of claim 1 by the CO preparing oxalate by coupling reaction, it is characterized in that purification of raw materials device service temperature is-20～5 ℃, 100～150 ℃ of the temperature of reaction of coupler reactor, reaction pressure are-0.05～1.0MPa, and reaction velocity is 1000～5000 hours
-1
3. according to the described method of claim 1 by the CO preparing oxalate by coupling reaction, it is characterized in that palladium-containing catalyst is a carrier with at least a in silicon oxide, aluminum oxide or the molecular sieve, active ingredient is a palladium metal, is benchmark with the carrier, and the weight percentage of palladium is 0.01～5%.
4. according to the described method by the CO preparing oxalate by coupling reaction of claim 3, it is characterized in that palladium-containing catalyst is a carrier with the aluminum oxide, is benchmark with the carrier, and the weight percentage of palladium is 0.1～3%.
5. according to the described method of claim 1, it is characterized in that nitrous acid ester is selected from methyl nitrite or ethyl nitrite by the CO preparing oxalate by coupling reaction.
6. according to the described method of claim 1, it is characterized in that the mol ratio of CO and nitrous acid ester is 1～3: 1 in the raw material by the CO preparing oxalate by coupling reaction.
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| CN2010101469009A CN102219677A (en) | 2010-04-15 | 2010-04-15 | Method for producing oxalate by coupling carbon monoxide(CO) |
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| CN2010101469009A CN102219677A (en) | 2010-04-15 | 2010-04-15 | Method for producing oxalate by coupling carbon monoxide(CO) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922939A (en) * | 2014-04-18 | 2014-07-16 | 华陆工程科技有限责任公司 | Process for carrying out low-temperature dehydration on feed gas used in the industrial production of ethylene glycol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN1054765A (en) * | 1990-03-14 | 1991-09-25 | 中国科学院福建物质结构研究所 | Continuous process for synthesis of oxalic ester by gaseous catalysis |
| CN101475472A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO in gaseous phase |
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2010
- 2010-04-15 CN CN2010101469009A patent/CN102219677A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN1054765A (en) * | 1990-03-14 | 1991-09-25 | 中国科学院福建物质结构研究所 | Continuous process for synthesis of oxalic ester by gaseous catalysis |
| CN101475472A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO in gaseous phase |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922939A (en) * | 2014-04-18 | 2014-07-16 | 华陆工程科技有限责任公司 | Process for carrying out low-temperature dehydration on feed gas used in the industrial production of ethylene glycol |
| CN103922939B (en) * | 2014-04-18 | 2016-08-17 | 华陆工程科技有限责任公司 | The technique that unstripped gas in ethylene glycol industrial production is carried out low temperature dewatering |
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Application publication date: 20111019 |