CN102649734A - Method for producing oxalate through catalytic coupling reaction of carbon monoxide - Google Patents
Method for producing oxalate through catalytic coupling reaction of carbon monoxide Download PDFInfo
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Abstract
The invention relates to a method for producing oxalate through catalytic coupling reaction of carbon monoxide, and mainly solves the technical problems in the prior art that in the reaction process of producing oxalate through catalytic coupling of carbon monoxide, the temperature control is difficult and oxalate is low in selectivity. The method adopts a mixed gas of both nitrous acid ester and carbon monoxide as the raw material and comprises the step that under the conditions that the reaction temperature is 100-180 DEG C, the hourly space velocity is 500-10,000 hours<-1>, the reaction pressure is -0.08-1.5MPa and the carbon monoxide/nitrous acid ester molar ratio is 1-5:1, the raw material is in contact with a precious metal catalyst in a compound reactor adopting an inner-tube and outer-tube sleeve structure and a hotspot distribution area for heat transfer enhancement, so as to react to produce an effluent containing oxalate. By adopting the technical scheme, the problems are better solved, and the method provided by the invention can be used for industrial production of oxalate through catalytic coupling of carbon monoxide.
Description
Technical field
The present invention relates to a kind of method through CO gas catalyzed coupling reaction producing oxalic ester; Particularly catalyzer is reacted the reaction that realizes carbon monoxide gas phase coupling catalyzed reaction production barkite with heat exchange, be useful in the CO gas catalytic coupling producing oxalic ester reaction process about the sleeve structure of pipe and outer tube in adopting and the compound reactor of focus range of distribution intensifying heat transfer.
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 merely 95%.
The subject matter that the related technology of above-mentioned document exists is that the barkite selectivity of product is low.
Summary of the invention
Technical problem to be solved by this invention is to be used for CO gas catalytic coupling producing oxalic ester reaction process in the technical literature in the past; Temperature control difficulty; The technical problem that the barkite selectivity is low provides a kind of new method of passing through CO gas catalyzed coupling reaction producing oxalic ester.Should be used for CO gas catalytic coupling producing oxalic ester process through the method for CO gas catalyzed coupling reaction producing oxalic ester, temperature control evenly 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 through CO gas catalyzed coupling reaction producing oxalic ester; 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
-1Reaction pressure is-0.08～1.5MPa; The mol ratio of CO and nitrous acid ester is under 1～5: 1 the condition; Raw material contacts with the interior noble metal catalyst of compound reactor of sleeve structure that adopts interior pipe and outer tube and focus range of distribution intensifying heat transfer; Reaction generates the elute that contains barkite; Wherein the compound reactor of pipe and the sleeve structure of outer tube and focus range of distribution intensifying heat transfer basically by feed(raw material)inlet (1), feed(raw material)inlet (2), a distributing chamber of gas (26), a distributing chamber of gas (27), down pipe (28), Isothermal Catalyst bed (7) in adiabatic catalyst layer (30), bundle of reaction tubes outer tube (5), the bundle of reaction tubes, go up adiabatic catalyst layer (31), gas quadratic distribution chamber (24), collection chamber (13), porous gas collection plate (11) and product and export (12) and form, it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) in proper order according to the mobile direction of reaction gas; On the top of reactor drum upper tubesheet (4) adiabatic catalyst layer (31) is set, adiabatic catalyst layer (30) down is set in the bottom of reactor drum lower tubesheet (10).
Be provided with in the isothermal catalyst bed (7) in the technique scheme and manage (28) in the bundle of reaction tubes, the interior pipe of bundle of reaction tubes (28) connects flexible pipe (29) through inlet gas and links to each other with a distributing chamber of gas (27) with the interior distributing chamber of gas (26) of collection chamber (13).Porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12).The first heat exchange block (22) links to each other with first district's heat transferring medium inlet (21) with first district's heat transferring medium outlet (23); The second heat exchange block (19) links to each other with second district's heat transferring medium outlet (20) with second district's heat transferring medium inlet (8), links to each other with the 3rd district's heat transferring medium outlet (17) with the 3rd district's heat transferring medium inlet (15) with the 3rd heat exchange block (16); Separate through the first subregion dividing plate (6) between the first heat exchange block (22) and the second heat exchange block (19), separate through the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).The first subregion dividing plate (6) is preferably 1/8～1/3 of reactor length apart from the following distance of reactor drum cover plate (25); The second subregion dividing plate (9) distance, the first subregion dividing plate (6) distance down is preferably 1/8～1/3 of reactor length.The height of following adiabatic catalyst layer (30) preferably Isothermal Catalyst bed (7) height 1/20～1/3; The height of last adiabatic catalyst layer (31) preferably Isothermal Catalyst bed (7) height 1/20～1/3.
To be preferably temperature of reaction be 100～160 ℃ to reaction conditions in the technique scheme, 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.The noble metal catalyst active constituent is preferably selected from least a in platinum or the palladium, and carrier is preferably selected from least a in aluminum oxide or the silicon oxide.
As everyone knows; The reaction of CO and nitrous acid ester gas phase coupling producing oxalic ester is a strong exothermal reaction; Reaction kinetics research shows; Being uniformly distributed with the influence of purpose selectivity of product of temperature of reaction is very remarkable, and especially the decomposition loss of nitrous acid ester and temperature of reaction cognation are very strong in the reactor feed gas, and the decomposition loss of the high more inferior acid esters of temperature of reaction is just high more.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 drum is anterior from balanced remote, and speed of response is fast, and it is also many to emit reaction heat; Near balance, speed of response slows down with reaction at the rear portion, emits reaction heat and also lacks; If the same before and after the temperature of refrigerant,, strengthen heat transfer temperature difference and move heat if reduce coolant temperature like this; Reach the heat request that moves of top or anterior high speed of response and strong reaction heat, then reactor lower part or rear portion reaction heat reduce, and move heat and cause temperature of reaction to descend greater than reaction heat; Speed of response is further slowed down below catalyst activity with regard to stopped reaction, therefore be difficult to the way that makes the best of both worlds of accomplishing that the front and rear part reaction is all carried out under optimal reaction temperature.The present invention is directed to this fundamental contradiction; Break through existing refrigerant with same temperature; And adopt the different sections of reactor drum to adopt the differing temps refrigerant to solve; Make the size that heat exchange is shifted out by reaction heat in the reaction need design, a plurality of districts before and after specifically can being divided in proper order by reaction gas flow direction in catalyst layer come indirect heat exchange by refrigerant through heat transfer tube.On the other hand, the present invention also adopts interior pipe is set in the catalyst bed for the reaction heat of catalyzer; And the counter-current flow virgin gas, virgin gas is carried out preheating has practiced thrift energy consumption on the one hand, has optimized the reaction bed temperature distribution simultaneously; Thereby realize the equiblibrium mass distribution of full bed temperature, in addition, the present invention is at the entrance and the outlet section of reactor drum; All adopted adiabatic reactor, this is for the efficient of maximized performance catalyzer, and this is for the efficient of maximized performance catalyzer; Farthest reduce the loss of inferior ester, improve the purpose product selectivity, useful effect is provided.
Pipe and the sleeve structure of outer tube and the compound reactor of focus range of distribution intensifying heat transfer in the employing of the present invention; Device as shown in Figure 1; Adopting precious metal palladium load aluminum oxide is catalyzer; 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-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 the condition; Raw material contacts with catalyzer; Nitrous acid ester and CO reaction generates barkite in the raw material, and its result is: the selectivity of barkite can obtain better technical effect greater than 99%.
Description of drawings
Fig. 1 is the synoptic diagram of the reactor drum that the present invention adopted.
1 and 2 is feed(raw material)inlets among Fig. 1, the 3rd, and the reactor drum upper cover, the 4th, upper tubesheet, the 5th, the bundle of reaction tubes outer tube, 6 is first subregion dividing plates; The 7th, catalyst bed, the 8th, the reactor drum 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 drum lower cover; 15 is the 3rd district's heat transferring medium inlets, and 16 is the 3rd heat exchange blocks, and 17 is the heat transferring medium outlets of the 3rd district, and 18 is second district's heat transferring medium inlets; 19 is second heat exchange blocks, and 20 is the heat transferring medium outlets of second district, and 21 is first district's heat transferring medium inlets, and 22 is first heat exchange blocks; 23 is the heat transferring medium outlets of first district, the 24th, and gas quadratic distribution chamber, the 25th, the reactor drum cover plate, 26 and 27 is distributing chamber of gas; The 28th, pipe in the bundle of reaction tubes, the 29th, inlet gas connects flexible pipe, the 30th, following adiabatic catalyst layer, the 31st, last adiabatic catalyst layer.
Raw material is introduced by feed(raw material)inlet 1 and 2 among Fig. 1; Respectively through distributing chamber 26 of gas and 27, connect flexible pipe 29 through inlet gas and introduce in the bundle of reaction tubes and manage 28, and get in the gas quadratic distribution chamber 24 after the reaction heat heat exchange in the Isothermal Catalyst bed 7; Be introduced into adiabatic catalyst layer 31 afterwards and carry out initial reaction; Reacted product gets in the Isothermal Catalyst bed 7 of managing in bundle of reaction tubes outer tube 5 and the bundle of reaction tubes between 28 again, and with the catalyzer contact reacts, reacted product gets into down adiabatic catalyst layer 31 again and continues reaction; After getting into collection chamber 13 at last, get into follow-up system through product outlet 12 through porous gas collection plate 11.In the Isothermal Catalyst bed 7 in reaction raw materials gas gets into bundle of reaction tubes outer tube 5 and bundle of reaction tubes between the pipe 28; With the reaction heat in the catalyzer contact reacts process; 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 through getting into each heat exchange block the controls respectively such as temperature and flow of heat transferring medium, in addition, unstripped gas in bundle of reaction tubes, manage 28 and reactant gases counter current contact process; Also catalyst bed 7 heat balances are played better promoter action, thereby reach the effect that the whole reactor catalyst bed temperature is uniformly distributed with.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With reactor drum shown in Fig. 1; It is the sleeve structure of interior pipe and outer tube and the compound reactor of focus range of distribution intensifying heat transfer; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature, the first subregion dividing plate of reactor drum is 1/5 of a reactor length apart from the length under the reactor drum cover plate; Length under second subregion dividing plate distance, the first subregion dividing plate is 1/6 of reactor length.The height of the following adiabatic catalyst layer of reactor drum is 1/6 of an Isothermal Catalyst bed height; The height of last adiabatic catalyst layer is 1/10 of an Isothermal Catalyst bed height; The catalyzer that with palladium content is 0.5% palladium load aluminum oxide is a catalyzer; The mol ratio of using CO and methyl nitrite is that 1.2: 1 mixed gas is raw material; In temperature of reaction is 130 ℃, and 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%, reactor catalyst bed temperature difference is less than 8 ℃.
[embodiment 2]
With reactor drum shown in Fig. 1; It is the sleeve structure of interior pipe and outer tube and the compound reactor of focus range of distribution intensifying heat transfer; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature, the first subregion dividing plate of reactor drum is 1/8 of a reactor length apart from the length under the reactor drum cover plate; Length under second subregion dividing plate distance, the first subregion dividing plate is 1/5 of reactor length.The height of the following adiabatic catalyst layer of reactor drum is 1/15 of an Isothermal Catalyst bed height; The height of last adiabatic catalyst layer is 1/15 of an Isothermal Catalyst bed height; The catalyzer that with palladium content is 0.2% palladium load aluminum oxide is a catalyzer; The mol ratio of using CO and ethyl nitrite is that 0.6: 1 mixed gas is raw material, and 110 ℃ of temperature of reaction, the reaction volume air speed is 1000 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 94.5%, the selectivity of oxalic acid diethyl ester are 99.3%, and reactor catalyst bed temperature difference is less than 6 ℃.
[embodiment 3]
With reactor drum shown in Fig. 1; It is the sleeve structure of interior pipe and outer tube and the compound reactor of focus range of distribution intensifying heat transfer; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature, the first subregion dividing plate of reactor drum is 1/4 of a reactor length apart from the length under the reactor drum cover plate; Length under second subregion dividing plate distance, the first subregion dividing plate is 1/3 of reactor length.The height of the following adiabatic catalyst layer of reactor drum is 1/8 of an Isothermal Catalyst bed height; The height of last adiabatic catalyst layer is 1/6 of an Isothermal Catalyst bed height; The catalyzer that with palladium content is 0.2% palladium load aluminum oxide is a catalyzer; The mol ratio of using CO and methyl nitrite is that 1.3: 1 mixed gas is raw material, is 150 ℃ in temperature of reaction, and the reaction volume air speed is 5000 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 72.1%, the selectivity of dimethyl oxalate are 99.4%, and reactor catalyst bed temperature difference is less than 8 ℃.
[embodiment 4]
With reactor drum shown in Fig. 1; It is the sleeve structure of interior pipe and outer tube and the compound reactor of focus range of distribution intensifying heat transfer; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature, the first subregion dividing plate of reactor drum is 1/4 of a reactor length apart from the length under the reactor drum cover plate; Length under second subregion dividing plate distance, the first subregion dividing plate is 1/8 of reactor length.The height of the following adiabatic catalyst layer of reactor drum is 1/18 of an Isothermal Catalyst bed height; The height of last adiabatic catalyst layer is 1/6 of an Isothermal Catalyst bed height; The catalyzer that with palladium content is 0.5% palladium load aluminum oxide is a catalyzer; The mol ratio of using CO and methyl nitrite is that 1.1: 1 mixed gas is raw material, is 130 ℃ in temperature of reaction, and the reaction volume air speed is 4000 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 88.4%, the selectivity of dimethyl oxalate are 99.3%, and reactor catalyst bed temperature difference is less than 10 ℃.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just CO gas coupling producing oxalic ester adopts insulation fix bed reactor, and reaction result is: CO per pass conversion 76.4%, the selectivity of dimethyl oxalate are 96.1%, and reactor catalyst bed temperature difference is 15 ℃.
[comparative example 2]
Each step and reaction conditions with reference to embodiment 2; Just CO gas coupling producing oxalic ester reactor drum adopts insulation fix bed reactor; Reaction result is: CO per pass conversion 88.1%, the selectivity of oxalic acid diethyl ester are 95.6%, and reactor catalyst bed temperature difference is 16 ℃.
Claims (8)
1. the method through CO gas catalyzed coupling reaction producing oxalic ester 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
-1Reaction pressure is-0.08～1.5MPa; The mol ratio of CO and nitrous acid ester is under 1～5: 1 the condition; Raw material contacts with the interior noble metal catalyst of compound reactor of sleeve structure that adopts interior pipe and outer tube and focus range of distribution intensifying heat transfer; Reaction generates the elute that contains barkite; Wherein the compound reactor of pipe and the sleeve structure of outer tube and focus range of distribution intensifying heat transfer basically by feed(raw material)inlet (1), feed(raw material)inlet (2), a distributing chamber of gas (26), a distributing chamber of gas (27), down pipe (28), Isothermal Catalyst bed (7) in adiabatic catalyst layer (30), bundle of reaction tubes outer tube (5), the bundle of reaction tubes, go up adiabatic catalyst layer (31), gas quadratic distribution chamber (24), collection chamber (13), porous gas collection plate (11) and product and export (12) and form, it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) in proper order according to the mobile direction of reaction gas; On the top of reactor drum upper tubesheet (4) adiabatic catalyst layer (31) is set, adiabatic catalyst layer (30) down is set in the bottom of reactor drum lower tubesheet (10).
2. according to the said method of claim 1 through CO gas catalyzed coupling reaction producing oxalic ester; It is characterized in that pipe (28) in the bundle of reaction tubes is set in the Isothermal Catalyst bed (7) of reactor drum, pipe (28) connects flexible pipe (29) through inlet gas and links to each other with a distributing chamber of gas (27) with the interior distributing chamber of gas (26) of collection chamber (13) in the bundle of reaction tubes.
3. according to the said method of claim 1, it is characterized in that the porous gas collection plate (11) of reactor drum is positioned at collection chamber (13), and be connected with product outlet (12) through CO gas catalyzed coupling reaction producing oxalic ester.
4. according to the said method of claim 1 through CO gas catalyzed coupling reaction producing oxalic ester; The first heat exchange block (22) that it is characterized in that reactor drum links to each other with first district's heat transferring medium inlet (21) with first district's heat transferring medium outlet (23); The second heat exchange block (19) links to each other with second district's heat transferring medium outlet (20) with second district's heat transferring medium inlet (8), links to each other with the 3rd district's heat transferring medium outlet (17) with the 3rd district's heat transferring medium inlet (15) with the 3rd heat exchange block (16); Separate through the first subregion dividing plate (6) between the first heat exchange block (22) and the second heat exchange block (19), separate through the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).
5. according to the said method of claim 1, it is characterized in that the first subregion dividing plate (6) of reactor drum is 1/8～1/3 of a reactor length apart from the length under the reactor drum cover plate (25) through CO gas catalyzed coupling reaction producing oxalic ester; Length under the second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length.
6. according to the said method through CO gas catalyzed coupling reaction producing oxalic ester of claim 1, the height that it is characterized in that the following adiabatic catalyst layer (30) of reactor drum is 1/20～1/3 of Isothermal Catalyst bed (a 7) height; The height of last adiabatic catalyst layer (31) is 1/20～1/3 of Isothermal Catalyst bed (a 7) height.
7. according to the said method through CO gas catalyzed coupling reaction producing oxalic ester of claim 1, it is characterized in that temperature of reaction is 100～160 ℃, 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.
8. according to the said method through CO gas catalyzed coupling reaction producing oxalic ester of claim 1, it is characterized in that the noble metal catalyst active constituent is selected from least a in platinum or the palladium, carrier is selected from least a in aluminum oxide or the silicon oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468043A (en) * | 2020-03-13 | 2020-07-31 | 宁波巨化化工科技有限公司 | Fixed bed reactor with bed temperature uniformly distributed |
| CN115463618A (en) * | 2022-08-08 | 2022-12-13 | 北京鑫缘化工有限公司 | Reactor for preparing maleic anhydride by oxidizing n-butane |
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| EP0056993A1 (en) * | 1981-01-23 | 1982-08-04 | Ube Industries, Ltd. | Process for preparing oxalic acid diesters |
| CN2621805Y (en) * | 2003-06-03 | 2004-06-30 | 华东理工大学 | Shell external cooling-thermal insulating and combined fixed bed catalyst chember |
| 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 | Catalyst for synthesizing oxalate and preparation method thereof |
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2011
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| EP0056993A1 (en) * | 1981-01-23 | 1982-08-04 | Ube Industries, Ltd. | Process for preparing oxalic acid diesters |
| EP0056993B1 (en) * | 1981-01-23 | 1984-12-27 | Ube Industries, Ltd. | Process for preparing oxalic acid diesters |
| CN2621805Y (en) * | 2003-06-03 | 2004-06-30 | 华东理工大学 | Shell external cooling-thermal insulating and combined fixed bed catalyst chember |
| 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 | Catalyst for synthesizing oxalate and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468043A (en) * | 2020-03-13 | 2020-07-31 | 宁波巨化化工科技有限公司 | Fixed bed reactor with bed temperature uniformly distributed |
| CN111468043B (en) * | 2020-03-13 | 2022-04-08 | 宁波巨化化工科技有限公司 | Fixed bed reactor with bed temperature uniformly distributed |
| CN115463618A (en) * | 2022-08-08 | 2022-12-13 | 北京鑫缘化工有限公司 | Reactor for preparing maleic anhydride by oxidizing n-butane |
| CN115463618B (en) * | 2022-08-08 | 2023-11-10 | 北京鑫缘化工有限公司 | Reactor for preparing maleic anhydride by oxidizing n-butane |
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