CN102649738A - Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide - Google Patents
Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide Download PDFInfo
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Abstract
The invention relates to a method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide, and mainly solves the technical problem in the prior art that in the reaction process of producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide, oxalate is low in selectivity. The method adopts a mixed gas of both nitrous acid ester and carbon monoxide as the raw material and palladium-containing metal oxide as the catalyst, and comprises the step that the raw material is in contact with the catalyst in a reactor to produce an effluent containing oxalate under the conditions that the carbon monoxide/nitrous acid ester molar ratio is 0.8-5:1, 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. By adopting the technical scheme, the problem is better solved and the method provided by the invention can be used for industrial production of oxalate through gas-phase coupled catalytic reaction of carbon monoxide.
Description
Technical field
The present invention relates to a kind of carbon monoxide gas phase coupling catalyzed reaction and produce the method for barkite, particularly about adopting subregion heat exchanging pipe reactor drum to realize the reaction that carbon monoxide gas phase coupling catalyzed reaction is produced barkite.
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. AR carbon monoxide 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 carbon monoxide 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 carbon monoxide preparing diethyl oxalate by coupling, adopts vapor phase process, and carbon monoxide 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; Carbon monoxide 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 the technology carbon monoxide is 20～60%, and the purpose selectivity of product all remains further to be improved about 96%.
Document CN95116136.9 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.
The subject matter that the related technology of above-mentioned document exists is that the selectivity of barkite is low, need further improve.
Summary of the invention
Technical problem to be solved by this invention is to exist in the technical literature to be used for carbon monoxide gas phase coupling catalyzed reaction and to produce the barkite reaction process in the past; There is the low technical problem of barkite selectivity, the method that provides a kind of new carbon monoxide gas phase coupling catalyzed reaction to produce barkite.This method is used for carbon monoxide gas phase coupling catalyzed reaction and produces the barkite reaction process, 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 carbon monoxide gas phase coupling catalyzed reaction is produced the method for barkite; With the mixed gas that contains nitrous acid ester and carbon monoxide is raw material, is catalyzer with the palladium-containing metal oxide compound, is 0.8～5: 1 in the mol ratio of CO and nitrous acid ester; Temperature of reaction is 100～180 ℃, and volume space velocity is 500～10000 hours
-1, reaction pressure is under the condition of-0.08～1.5MPa, raw material contacts with catalyst reactor, generates the elute that contains barkite, it is characterized in that said reactor drum is the shell-and-tube reactor of subregion heat exchange.
The reaction conditions of reactor drum is preferably in the technique scheme: the mol ratio of CO and nitrous acid ester is 1～3: 1, and temperature of reaction is 110～160 ℃, and volume space velocity is 1000～6000 hours
-1, reaction pressure is-0.02～1.0MPa.The catalyzer preferred version is selected from: alumina supporter is 89～99.8% of a catalyst weight in the catalyst weight consumption; Be 0.003～1% active component palladium of catalyst weight and be 0.005～10% rhenium, cobalt or the silver-colored auxiliary agent of catalyst weight in the simple substance consumption in the simple substance consumption.
The reactor drum of inventive method mainly is made up 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) in the technique scheme, 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; 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).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 to be heat transferring medium.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 following apart from reactor drum upper tubesheet (4) to be 1/8～1/3 of reactor length; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
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; It is also many to emit reaction heat, and near balance, speed of response slows down with reaction at the rear portion; It is also few to emit reaction heat, if the same before and after the temperature of refrigerant, if reduce coolant temperature like this; 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, 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, and adopt the different sections of reactor drum to adopt the differing temps refrigerant to solve with same temperature; 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, thereby realize the equiblibrium mass distribution of full bed temperature; 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.
Carbon monoxide gas phase coupling catalyzed reaction of the present invention is produced the method for barkite, uses device shown in Figure 1, adopts the subregion heat exchange; Accurate controlled temperature; With the mixed gas that contains nitrous acid ester and carbon monoxide is raw material, is catalyzer with the palladium-containing metal oxide compound, is 0.8～5: 1 in the mol ratio of CO and nitrous acid ester; 100～180 ℃ of temperature of reaction, volume space velocity are 500～10000 hours
-1, reaction pressure is under the condition of-0.08～1.5MPa, and raw material contacts with catalyzer, and nitrous acid ester and reaction of carbon monoxide generate barkite in the raw material, and the selectivity of barkite can obtain better technical effect greater than 99%.
Description of drawings
Fig. 1 is reactor drum synoptic diagram in the method for carbon monoxide gas phase coupling catalyzed reaction production barkite of the present invention.
1 is the feed(raw material)inlet among Fig. 1, the 2nd, and porous gas sparger, the 3rd, reactor drum upper cover, the 4th, upper tubesheet, the 5th, bundle of reaction tubes; 6 is first subregion dividing plates, the 7th, and 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, the 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; 18 is second district's heat transferring medium inlets, and 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; 22 is first heat exchange blocks, and 23 is the heat transferring medium outlets of first district, the 24th, and the gas distribution chamber
Raw material is introduced by feed(raw material)inlet 1 among Fig. 1;, porous gas sparger 2 gets into gas distribution chamber 24 after distributing; Get in the bundle of reaction tubes 5 afterwards and catalyst bed 7 contact reactss; The heat that produces in the reaction process is taken away through bundle of reaction tubes 5 outer heat transferring mediums, and reacted gas gets into collection chamber 13, gets into follow-up systems through porous gas collection plate 11 after product exports 12 then.In reaction raw materials gas gets into bundle of reaction tubes 5 and in the 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 through getting into each heat exchange block the controls respectively such as temperature and flow of heat transferring medium, thereby reach the effect that temperature all goes on foot.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Cobalt oxalate is dissolved in the water, is heated to 70 ℃, the vacuum rotary dipping is 10 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, then in 120 ℃ of dryings 6 hours.A certain amount of Palladous nitrate is dissolved in the water, and using the nitric acid regulator solution to make its pH value is about 4, then this solution is heated to 80 ℃; Be immersed on the carrier once more; Then in 140 ℃ of dryings 8 hours, then roasting 4 hours in 450 ℃ of air atmospheres, reductase 12 hour in 400 ℃ of hydrogen atmospheres; Obtain catalyst A, consist of 0.17%Pd+0.28% carbon monoxide/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.2: 1; 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: carbon monoxide per pass conversion 78.4%, the selectivity of dimethyl oxalate are 99.2%.
[embodiment 2]
Xiao Suangu is dissolved in the water, is heated to 80 ℃, the vacuum rotary dipping is 8 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, then in 120 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the water, and using the nitric acid regulator solution to make its pH value is about 4, then this solution is heated to 80 ℃; Be immersed on the carrier once more; Then in 140 ℃ of dryings 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres, reductase 12 hour in 400 ℃ of hydrogen atmospheres; Obtain catalyst B, consist of 0.45%Pd+0.40% carbon monoxide/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.5: 1; In temperature of reaction is 110 ℃, and 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: carbon monoxide per pass conversion 63.2%, the selectivity of dimethyl oxalate are 99.7%.
[embodiment 3]
Silver Nitrate is dissolved in the water, and vacuum impregnation is 15 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Palladous nitrate is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 4 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer C, consist of 0.01%Pd+1%Ag/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide 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: carbon monoxide per pass conversion 45.2%, the selectivity of dimethyl oxalate are 99.1%.
[embodiment 4]
Silver Nitrate is dissolved in the water, and the vacuum rotary dipping is 20 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.The inferior palladium acid of chlorine is dissolved in the aqueous solution; Be immersed on the carrier 140 ℃ of dryings 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres once more; Reduction is 4 hours in 450 ℃ of hydrogen atmospheres; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer D, consist of 0.34%Pd+0.46%Ag/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide and methyl nitrite is 4: 1; 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: carbon monoxide per pass conversion 22.2%, the selectivity of dimethyl oxalate are 98.3%.
[embodiment 5]
The nitric acid rhenium is dissolved in the water, and the vacuum rotary dipping is 30 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then 450 ℃ of roastings 4 hours, reduction was 4 hours in 350 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer E, consist of 0.11%Pd+0.6%Re/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide 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: carbon monoxide per pass conversion 74.6%, the selectivity of dimethyl oxalate are 97.3%.
[embodiment 6]
Getting 200 gram specific surface agent is 40 meters
2The Al of/gram
2O
3Bead; Be immersed in and contain in 8.0 gram Palladous nitrates, the 14 gram nitric acid rhenium aqueous solution, and use nitric acid to regulate its pH value to be 2, to take out the back 140 ℃ of oven dry 4 hours; Then roasting 2 hours in 450 ℃ of air atmospheres; Reduction is 4 hours in 350 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtains catalyzer F and consists of 0.6%Pd+1.1%Re/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.5: 1; 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: carbon monoxide per pass conversion 63.8%, the selectivity of dimethyl oxalate are 99.5%.
[embodiment 7]
Silver Nitrate is dissolved in the water, and vacuum impregnation is 50 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 2 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer G, consist of 0.8%Pd+10%Ag/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide 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: carbon monoxide per pass conversion 73.9%, the selectivity of dimethyl oxalate are 99.8%.
[embodiment 8]
The nitric acid rhenium is dissolved in the water, and vacuum impregnation is 30 meters in the specific surface agent
2/ gram Al
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 4 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer H, consist of 0.2%Pd+1%Re/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, first, second and third heat transferring medium all adopts saturation steam; Just adopt the difference of pressure, realize the difference of temperature, thus the control of realization response device catalyst bed temperature; Be raw material with carbon monoxide and methyl nitrite then, wherein, the mol ratio of carbon monoxide 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: carbon monoxide per pass conversion 96.2%, the selectivity of dimethyl oxalate are 99.1%.
[comparative example 1]
Adopt the catalyzer and [embodiment 1] same reaction conditions and the reaction raw materials of [embodiment 1], just adopt insulation fix bed reactor, its reaction result is: carbon monoxide per pass conversion 77.1%, the selectivity of dimethyl oxalate are 96.8%.
[comparative example 2]
Adopt the catalyzer and [embodiment 2] same reaction conditions and the reaction raw materials of [embodiment 2], just adopt insulation fix bed reactor, its reaction result is: carbon monoxide per pass conversion 60.4%, the selectivity of dimethyl oxalate are 94.3%.
Claims (7)
1. a carbon monoxide gas phase coupling catalyzed reaction is produced the method for barkite; With the mixed gas that contains nitrous acid ester and carbon monoxide is raw material; With the palladium-containing metal oxide compound is catalyzer; Mol ratio at CO and nitrous acid ester is 0.8～5: 1, and temperature of reaction is 100～180 ℃, and volume space velocity is 500～10000 hours
-1, reaction pressure is under the condition of-0.08～1.5MPa, raw material contacts with catalyst reactor, generates the elute that contains barkite, it is characterized in that said reactor drum is the shell-and-tube reactor of subregion heat exchange.
2. produce the method for barkite according to the said carbon monoxide gas phase of claim 1 coupling catalyzed reaction, the mol ratio that it is characterized in that CO and nitrous acid ester is 1～3: 1, and the temperature of reaction of reactor drum is 110～160 ℃, and volume space velocity is 1000～6000 hours
-1, reaction pressure is-0.02～1.0MPa.
3. producing the method for barkite according to the said carbon monoxide gas phase of claim 1 coupling catalyzed reaction, it is characterized in that catalyzer comprises alumina supporter, is 89～99.8% of catalyst weight in the catalyst weight consumption; Be 0.003～1% active component palladium of catalyst weight and be 0.005～10% rhenium, cobalt or the silver-colored auxiliary agent of catalyst weight in the simple substance consumption in the simple substance consumption.
4. produce the method for barkite according to the said carbon monoxide gas phase of claim 1 coupling catalyzed reaction; It is characterized in that reactor drum mainly exports (12) 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) and product and forms, 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; 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).
5. produce the method for barkite according to the said carbon monoxide gas phase of claim 1 coupling catalyzed reaction; It is characterized in that reactor drum porous gas sparger (2) is positioned at gas distribution chamber (24); And be connected with feed(raw material)inlet (1); 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 to be heat transferring medium.
6. produce the method for barkite according to the said carbon monoxide gas phase of claim 4 coupling catalyzed reaction; It is characterized in that separating through the first subregion dividing plate (6) between the reactor drum 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).
7. produce the method for barkite according to the said carbon monoxide gas phase of claim 6 coupling catalyzed reaction, it is characterized in that the reactor drum first subregion dividing plate (6) following apart from reactor drum upper tubesheet (4) be 1/8～1/3 of reactor length; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109789380A (en) * | 2016-10-13 | 2019-05-21 | 株式会社Ihi | Fluid dispersing device and annealing device |
| KR20220135485A (en) * | 2021-03-30 | 2022-10-07 | 한국항공우주연구원 | 3D Heat Exchanger Heat Transfer Enhancement Device |
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| US12163541B2 (en) | 2021-03-30 | 2024-12-10 | Korea Aerospace Research Institute | 3D heat exchanger heat transfer enhancement device |
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