CN102649739B - Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling - Google Patents
Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling Download PDFInfo
- Publication number
- CN102649739B CN102649739B CN201110046378.1A CN201110046378A CN102649739B CN 102649739 B CN102649739 B CN 102649739B CN 201110046378 A CN201110046378 A CN 201110046378A CN 102649739 B CN102649739 B CN 102649739B
- Authority
- CN
- China
- Prior art keywords
- reaction
- heat exchange
- gas
- reactor
- exchange block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method of synthesizing oxalic ester by CO (carbon monoxide) gaseous phase coupling, which mainly solves the technical problems that in a reaction process of synthesizing the oxalic ester by the CO gas coupling, the temperature is difficult to control and the selectivity of the oxalic ester is low. According to the invention, the technical scheme adopted is that a mixed gas of nitrous acid ester and CO is taken as raw material, and the raw material is in contact with precious metal catalysts in multi-region heat exchange tube reactors to generate effluences including the oxalic ester through reaction under the conditions that the reaction temperature is 100-180 DEG C, the volume space velocity is 500-10,000 h<-1>, the reaction pressure is negative 0.08-1.5 MPa, and the molar ratio of CO to the nitrous acid ester is (1-5):1. According to the invention, the problem is better solved, and the method can be used in the industrial production of synthesizing the oxalic ester by the CO gaseous phase coupling.
Description
Technical field
The present invention relates to a kind of method of CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester, particularly, about adopting multi-region heat exchanging pipe reactor to realize the reaction of CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester, be practically applicable in CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester reaction process.
Background technology
Barkite is important Organic Chemicals, in a large number for fine chemistry industry, produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.Enter 21 century, barkite is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, barkite ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example, carry out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize pharmaceutically as the chest acyl alkali of hormone.In addition, barkite low-voltage hydrogenation can be prepared very important 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 within 2007 years, import volume is nearly 4,800,000 tons.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and production technique cost is high, and energy consumption is large, seriously polluted, and prepared using is unreasonable.For many years, people are finding 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, alcohol and 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.
For Oxidation of Carbon Monoxide coupling method synthesis of oxalate, from development course, divide and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is harsher, and reaction is under high pressure carried out, liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.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 technique of Yu Buxingchan company exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
Along with Oxidation of Carbon Monoxide coupling method in the world, prepare the research and development of barkite Technology, domestic many research institutions have also carried out research work to this field.According to china natural resources characteristic distributions, the carbon monoxide of take is prepared organic oxygen-containing compound as raw material, for alleviate petroleum products pressure, rationally utilize coal and natural gas source to there is very important strategic importance.At present, by Oxidation of Carbon Monoxide coupling method synthesis of oxalate, become important research topic in domestic one-carbon chemical and organic chemical industry field, successively You Duojia research institution and research institutions are devoted to catalyst preparation, process exploitation and the engineering amplification work in this field, and have obtained greater advance.
Although above-mentioned numerous research institution, has obtained technically compared with much progress, technology itself still needs to be further improved and develops, and especially how, improves reaction preference, and the aspects such as activity that improve catalyzer 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 supported catalyst, coupling oxalic diethyl ester crude product, reaction is self-closing circulating process, CO gas enters coupler reactor with the ethyl nitrite from regeneration reactor through mixing preheating, after reaction, gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, non-condensable gas containing 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, this invention is on the basis of lab scale research in early stage, the industrial production of take is carried out as background, continuous operation examination is amplified in the mould examination and the pilot scale that have completed under industrial operation condition, linked reaction temperature is low, product concentration improves, present method is more energy-conservation, pollution-free, high efficiency.But the per pass conversion of this technology CO is 20～60%, and object selectivity of product, in 96% left and right, all needs further to be improved.
Document CN 95116136.9 discloses the catalyzer of the synthetic use of a kind of barkite, selects Zr to make auxiliary agent, by pickling process, develops novel Pd-Zr/Al
2o
3catalyzer.It is to adopt fixed-bed reactor that this catalyzer reacts with nitrous acid ester synthesis of oxalic ester by gaseous catalysis as carbon monoxide.But the yield of its barkite of catalyzer adopting in this patent is lower, and the impurity of unstripped gas is had relatively high expectations, the selectivity of product barkite is only 95%.
The subject matter that the related technology of above-mentioned document exists is that barkite selectivity of product is low.
Summary of the invention
Technical problem to be solved by this invention is for CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester reaction process in previous literature technology, temperature is controlled difficulty, the technical problem that barkite selectivity is low, provides a kind of method of new CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester.The method of this CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester is for CO (carbon monoxide converter) gas coupling producing oxalic ester process, and temperature is controlled evenly, has advantages of that barkite selectivity 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 of CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester, the mixed gas that contains nitrous acid ester and CO of take is raw material, and 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 condition, raw material contacts with the noble metal catalyst in multi-region heat exchanging pipe reactor, reaction generates the effluent containing barkite, wherein multi-region heat exchanging pipe reactor is substantially by feed(raw material)inlet (1), porous gas sparger (2), gas distribution chamber (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11), form with product outlet (12), it is characterized in that catalyst bed (7) is sequentially divided into the first heat exchange block (22) according to the mobile direction of reaction gas, the second heat exchange block (19) and the 3rd heat exchange block (16), the first heat exchange block (22) is connected with first district's heat transferring medium entrance (21) with first district's heat transferring medium outlet (23), the second heat exchange block (19) is connected with Second Region heat transferring medium outlet (20) with Second Region heat transferring medium entrance (8), is connected with the 3rd heat exchange block (16) Yu tri-district's heat transferring medium entrance (15) He tri-district's heat transferring medium outlets (17).
In technique scheme, porous gas sparger (2) is positioned at gas distribution chamber (24), and is connected with feed(raw material)inlet (1), and porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12).Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outer is heat transferring medium.Between the first heat exchange block (22) and the second heat exchange block (19), by the first subregion dividing plate (6), separate, between the second heat exchange block (19) and the 3rd heat exchange block (16), by the second subregion dividing plate (9), separate.The first subregion dividing plate (6) is lower apart from reactor upper tubesheet (4) is 1/8～1/3 of reactor length; Second subregion dividing plate (9) distance the first subregion dividing plate (6) is lower is 1/8～1/3 of reactor length.
In technique scheme, to be preferably temperature of reaction be 100～160 ℃ to reaction conditions, and volume space velocity is 500～5000 hours
-1, reaction pressure is-0.05～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1.Noble metal catalyst active constituent is preferably selected from least one in platinum or palladium, and carrier is preferably selected from least one in aluminum oxide or silicon oxide.
As everyone knows, CO is strong exothermal reaction with reacting of nitrous acid ester gas phase coupling producing oxalic ester, reaction kinetics research shows, temperature of reaction uniform very remarkable on the impact of object selectivity of product, especially in reactor feed gas, the decomposition loss of nitrous acid ester and temperature of reaction cognation are very strong, and the decomposition loss of the higher sub-acid esters of temperature of reaction is just higher.We know, for conventional fixed-bed reactor, because catalyzed reaction is carried out on catalyzer and not according to front and back phase uniform velocity, general reactor front portion is from balanced remote, speed of response is fast, emit reaction heat also many, rear portion approaches balance with reaction, speed of response slows down, emit reaction heat also few, if the same before and after the temperature of refrigerant, if reduce like this coolant temperature, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of top or anterior high speed of response and strong reaction heat, reactor lower part or rear portion reaction heat reduce, moving heat is greater than reaction heat and causes temperature of reaction to decline, speed of response is further slowed down until catalyst activity is following with regard to stopped reaction, therefore be difficult to the way making the best of both worlds of accomplishing that front and rear part reaction is all carried out under optimal reaction temperature.The present invention is directed to this fundamental contradiction, break through the existing refrigerant with same temperature, and adopt the different sections of reactor to adopt differing temps refrigerant to solve, make the size that in reaction, heat exchange is shifted out by reaction heat need design, a plurality of districts before and after specifically can being sequentially divided into by reaction gas flow direction in catalyst layer, by refrigerant, by heat transfer tube, carry out indirect heat exchange, thereby realize the equiblibrium mass distribution of full bed temperature, this is for the efficiency of maximized performance catalyzer, farthest reduce the loss of sub-ester, improve the selectivity of object product, useful effect is provided.
The present invention's Fig. 1 shown device, adopts multi-region heat exchanging pipe reactor, and adopting precious metal palladium or platinum Supported alumina is catalyzer, and the mixed gas that contains nitrous acid ester and CO of take is raw material, and 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1reaction pressure is-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 condition, raw material contacts with the noble metal catalyst in multi-region heat exchanging pipe reactor, reaction generates the effluent containing barkite, its result is: the selectivity of barkite can be greater than 99%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the reactor that adopts of the present invention.
In Fig. 1,1 is feed(raw material)inlet, the 2nd, porous gas sparger, the 3rd, reactor upper cover, the 4th, upper tubesheet, the 5th, bundle of reaction tubes, 6 is first subregion dividing plates, the 7th, catalyst bed, the 8th, reactor tank body, 9 is second subregion dividing plates, the 10th, lower tubesheet, the 11st, porous gas collection plate, the 12nd, product outlet, the 13rd, collection chamber, the 14th, reactor lower cover, 15 Shi tri-district's heat transferring medium entrances, 16 is the 3rd heat exchange blocks, 17 Shi 3rd district heat transferring medium outlets, the 18th, Second Region heat transferring medium entrance, 19 is second heat exchange blocks, the 20th, the outlet of Second Region heat transferring medium, 21 is first district's heat transferring medium entrances, 22 is first heat exchange blocks, 23 is the heat transferring medium outlets of the firstth district, the 24th, gas distribution chamber,
Fig. 1 Raw is introduced by feed(raw material)inlet 1, after distributing, porous gas sparger 2 enters gas distribution chamber 24, enter afterwards in bundle of reaction tubes 5 and catalyst bed 7 contact reactss, the heat producing in reaction process is taken away by the heat transferring medium outside bundle of reaction tubes 5, reacted gas enters collection chamber 13, then by porous gas collection plate 11, by product outlet 12, enters follow-up system.In reaction raw materials gas enters bundle of reaction tubes 5 and in catalyst bed 7 contact reacts processes, successively through the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16), the temperature of each heat exchange block can be controlled by entering temperature and the flow philosophy of the heat transferring medium of each heat exchange block, thereby reaches the effect that temperature all walks.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
With reactor shown in Fig. 1, it is multi-region heat exchanging pipe reactor, and wherein the first subregion dividing plate is apart from being 1/4 of reactor length under reactor upper tubesheet; Under second subregion dividing plate distance the first subregion dividing plate, it is 1/6 of reactor length.Its first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, the catalyzer of the palladium Supported alumina that the palladium content of take is 0.5% is catalyzer, with the mixed gas that the mol ratio of CO and methyl nitrite is 1.2: 1, being raw material, is 130 ℃ in temperature of reaction, and reaction volume air speed is 1000 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 is 99.2%, reactor catalyst bed temperature is poor is less than 6 ℃.
[embodiment 2]
With reactor shown in Fig. 1, it is multi-region heat exchanging pipe reactor, and wherein the first subregion dividing plate is apart from being 1/7 of reactor length under reactor upper tubesheet; Under second subregion dividing plate distance the first subregion dividing plate, it is 1/4 of reactor length.Its first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, the catalyzer of the palladium Supported alumina that the palladium content of take is 0.2% is catalyzer, with the mixed gas that the mol ratio of CO and ethyl nitrite is 0.6: 1, be raw material, 120 ℃ of temperature of reaction, reaction volume air speed is 2000 hours
-1, under the condition that reaction pressure is 0.03MPa, raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 94.2%, the selectivity of oxalic acid diethyl ester is 98.8%, reactor catalyst bed temperature is poor is less than 6 ℃.
[embodiment 3]
With reactor shown in Fig. 1, it is multi-region heat exchanging pipe reactor, and wherein the first subregion dividing plate is apart from being 1/5 of reactor length under reactor upper tubesheet; Under second subregion dividing plate distance the first subregion dividing plate, it is 1/7 of reactor length.Its first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, the catalyzer of the palladium Supported alumina that the palladium content of take is 0.3% is catalyzer, with the mixed gas that the mol ratio of CO and methyl nitrite is 1.2: 1, being raw material, is 140 ℃ in temperature of reaction, and reaction volume air speed is 6000 hours
-1, reaction pressure is-condition of 0.02MPa under, raw material contacts with catalyzer, reacts, its reaction result is: CO per pass conversion 77.1%, the selectivity of dimethyl oxalate is 99.1%, reactor catalyst bed temperature is poor is less than 7 ℃.
[embodiment 4]
With reactor shown in Fig. 1, it is multi-region heat exchanging pipe reactor, and wherein the first subregion dividing plate is apart from being 1/3 of reactor length under reactor upper tubesheet; Under second subregion dividing plate distance the first subregion dividing plate, it is 1/6 of reactor length.Its first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, take palladium content as 0.28%, and the catalyzer of the palladium that the content of iron is 0.9% and iron Supported alumina is catalyzer, with the mixed gas that the mol ratio of CO and methyl nitrite is 1.5: 1, is raw material, in temperature of reaction, be 150 ℃, reaction volume air speed is 5000 hours
-1, under the condition that reaction pressure is 0.02MPa, raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 60.1%, the selectivity of dimethyl oxalate is 99.4%, reactor catalyst bed temperature is poor is less than 10 ℃.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, be CO gas coupling producing oxalic ester insulation fix bed reactor, reaction result is: CO per pass conversion 76.4%, the selectivity of dimethyl oxalate is 96.1%, reactor catalyst bed temperature is poor is 15 ℃.
[comparative example 2]
Each step and reaction conditions with reference to embodiment 2, just the method for CO gas gas phase coupling producing oxalic ester adopts insulation fix bed reactor, reaction result is: CO per pass conversion 88.1%, and the selectivity of oxalic acid diethyl ester is 95.6%, reactor catalyst bed temperature is poor is 16 ℃.
Claims (1)
1. the method for a CO (carbon monoxide converter) gas gas phase coupling producing oxalic ester, multi-region heat exchanging pipe reactor used is comprised of feed(raw material)inlet (1), porous gas sparger (2), gas distribution chamber (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product outlet (12) substantially, it is characterized in that catalyst bed (7) is sequentially divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) according to the mobile direction of reaction gas; The first heat exchange block (22) is connected with first district's heat transferring medium entrance (21) with first district's heat transferring medium outlet (23), the second heat exchange block (19) is connected with Second Region heat transferring medium outlet (20) with Second Region heat transferring medium entrance (8), is connected with the 3rd heat exchange block (16) Yu tri-district's heat transferring medium entrance (15) He tri-district's heat transferring medium outlets (17);
Wherein, porous gas sparger (2) is positioned at gas distribution chamber (24), and is connected with feed(raw material)inlet (1), and porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12); Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outer is heat transferring medium; Between the first heat exchange block (22) and the second heat exchange block (19), by the first subregion dividing plate (6), separate, between the second heat exchange block (19) and the 3rd heat exchange block (16), by the second subregion dividing plate (9), separate;
With above-mentioned multi-region heat exchanging pipe reactor, wherein the first subregion dividing plate is apart from being 1/7 of reactor length under reactor upper tubesheet; Under second subregion dividing plate distance the first subregion dividing plate, it is 1/4 of reactor length; Its first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, the catalyzer of the palladium Supported alumina that the palladium content of take is 0.2% is catalyzer, with the mixed gas that the mol ratio of CO and ethyl nitrite is 0.6: 1, be raw material, 120 ℃ of temperature of reaction, reaction volume air speed is 2000 hours
-1reaction pressure is under the condition of 0.03MPa, raw material contacts with the noble metal catalyst in multi-region heat exchanging pipe reactor, react, generate the effluent containing barkite, its reaction result is: CO per pass conversion 94.2%, and the selectivity of oxalic acid diethyl ester is 98.8%, reactor catalyst bed temperature is poor is less than 6 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110046378.1A CN102649739B (en) | 2011-02-25 | 2011-02-25 | Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110046378.1A CN102649739B (en) | 2011-02-25 | 2011-02-25 | Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102649739A CN102649739A (en) | 2012-08-29 |
| CN102649739B true CN102649739B (en) | 2014-11-26 |
Family
ID=46691869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110046378.1A Active CN102649739B (en) | 2011-02-25 | 2011-02-25 | Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102649739B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566836A (en) * | 2013-11-25 | 2014-02-12 | 南京国昌化工科技有限公司 | Uniform-temperature hydrogenation reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| CN101475473A (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 |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
| CN101851160A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst |
-
2011
- 2011-02-25 CN CN201110046378.1A patent/CN102649739B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
| CN101475473A (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 |
| CN101851160A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102649739A (en) | 2012-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101492370B (en) | Method for producing oxalic ester with CO coupling | |
| CN101475472A (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
| CN102649735B (en) | Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction | |
| CN102649734B (en) | Method for producing oxalate through catalytic coupling reaction of carbon monoxide | |
| CN102649563B (en) | Method for dehydrogenation through catalytic oxidation of carbon monoxide gas | |
| CN102649562B (en) | Method for dehydrogenation of CO gas raw material in virtue of catalytic oxidation | |
| CN102649739B (en) | Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling | |
| CN102649738B (en) | Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide | |
| CN102649554B (en) | Method for CO gas oxidative dehydrogenation | |
| CN102649566B (en) | Method for dehydrogenating CO-containing gas mixture by oxidizing reaction | |
| CN102219679B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102649740B (en) | Method for preparing oxalate through CO catalytic coupling reaction | |
| CN102649736B (en) | Method for producing oxalate through carbon monoxide gas phase- coupled catalytic reaction | |
| CN102649737B (en) | Method for producing oxalate through gas-phase coupling of carbon monoxide | |
| CN102649564B (en) | Method for dehydrogenating CO-containing mixed gas raw material by means of catalytic oxidation reaction | |
| CN102649570B (en) | Method for oxidative dehydrogenation of CO gas through catalytic reaction | |
| CN101993369B (en) | Method for producing oxalic ester by gas phase CO coupling | |
| CN102219678B (en) | Starting-up method for producing oxalic acid ester with CO | |
| CN102219681B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102649732B (en) | Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide | |
| CN102649741A (en) | Method for preparing oxalic ester by carbon monoxide gaseous phase catalytic coupling reaction | |
| CN102219682A (en) | Method for preparing oxalic ester by CO coupling | |
| CN102649567B (en) | Method for dehydrogenating CO-containing raw material by catalytic oxidation reaction | |
| CN102219676B (en) | Method for preparing oxalate by CO coupling | |
| CN102649728B (en) | Method for producing oxalate through gas-phase reaction of carbon monoxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |