CN102649741A - Method for preparing oxalic ester by carbon monoxide gaseous phase catalytic coupling reaction - Google Patents
Method for preparing oxalic ester by carbon monoxide gaseous phase catalytic coupling reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing oxalic ester by a CO (carbon monoxide) gaseous phase catalytic coupling reaction, which mainly solves the technical problem in the prior art that in a reaction process of preparing the oxalic ester by the CO-catalyzed gaseous phase catalytic coupling reaction, the selectivity of the oxalic ester is low. The invention adopts the technical scheme that a mixed gas of nitrous acid ester and CO is taken as raw material, palladium contained metal oxides are taken as catalysts, and the raw material is sequentially in contact with the catalysts in a reactor under the conditions that the molar ratio of the carbon monoxide to the nitrous acid ester is (0.8-5):1, the reaction temperature is 100-180 DEG C, the volume space velocity is 500-10,000 h<-1>, wherein the reactor is a combined reactor with a composite bed structure, and an heat exchange pipe is arranged in a heat exchange catalyst bed. According to the invention, the problem is better solved, and the method can be used in the industrial production of preparing the oxalic ester by the carbon monoxide gaseous phase catalytic coupling reaction.
Description
Technical field
The present invention relates to a kind of method, particularly realize the reaction of carbon monoxide gas-phase catalytic coupling prepared in reaction barkite about the combined reactor that adopts the multiple-hearth structure through carbon monoxide gas-phase catalytic coupling prepared in reaction 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 barkite selectivity is low, remains further to be improved.
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 catalytic coupling prepared in reaction barkite reaction process in the past; There is the low technical problem of barkite selectivity, a kind of new method of passing through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite is provided.This method is used for carbon monoxide and produces the barkite reaction process through the coupling catalyzed reaction, 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 carbon monoxide gas-phase catalytic coupling prepared in reaction 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 carbon monoxide and nitrous acid ester; 100～180 ℃ of temperature of reaction, volume space velocity are 500～10000 hours
-1, reaction pressure is that raw material contacts with catalyst reactor successively under the condition of-0.08～1.5MPa, comprises the steps:
A) raw material is at first introduced by feed(raw material)inlet (1), and the further mixed distribution of gas entering distributing chamber (4) after porous gas grid distributor (3) distributes gets into then and goes up adiabatic catalyst beds (5) and catalyzer contact reacts, gets reaction effluent I;
B) reaction effluent I gets into heat exchange catalyst bed (6), with the catalyzer contact reacts, gets reaction effluent II;
C) reaction effluent II gets into down adiabatic catalyst beds (7) and catalyzer again and further reacts, and reacted elute gets into collection chamber (8), gets into follow-up system through porous gas collection plate (9) through pneumatic outlet (10).
Wherein, said reactor drum is the combined reactor of multiple-hearth structure, in the heat exchange beds heat transfer tube is set.
In the technique scheme, the mol ratio preferable range of carbon monoxide and nitrous acid ester is 1～3: 1, and the reaction conditions of reactor drum is preferably: 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 comprises a) alumina supporter, is 90～99.8% of catalyst weight in its consumption of catalyst weight; B) active component palladium, its consumption is counted 0.003～1% of catalyst weight with simple substance; C) being selected from least a in rhenium, cobalt or the silver is auxiliary agent, is 0.005～9% of catalyst weight in its consumption of simple substance.
In the technique scheme; Reactor drum mainly is made up of feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), last adiabatic catalyst beds (5), heat exchange catalyst bed (6), following adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9); Be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5); The top of following adiabatic catalyst beds (7), and heat transfer tube (13) is set in the heat exchange catalyst bed (6).
In the technique scheme, porous gas collection plate (9) is positioned at collection chamber (8), and is connected with pneumatic outlet (10).Porous gas grid distributor (3) is positioned at gas distribution chamber (4), and is connected with feed(raw material)inlet (1).Last adiabatic catalyst beds (5) top is 1/30～1/6 of reactor length apart from the length of porous gas grid distributor (3) bottom; The bottom of following adiabatic catalyst beds (7) is 1/30～1/6 of a height for reactor apart from the vertical height on porous gas collection plate (9) top.The height of last adiabatic catalyst beds (5) is 1/6～3/2 of heat exchange catalyst bed (a 6) height, and following adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (a 6) height.
For the catalytic exothermic reaction of routine, 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; Speed of response is fast, and it is also many to emit reaction heat, shows as anterior mid-way partially and occurs significant hot spot region easily; And the rear portion with reaction near balance, speed of response slows down, it is also few to emit reaction heat; If adopt conventional shell-and-tube reactor, the same before and after the temperature of its refrigerant, if reduce coolant temperature like this; Strengthen heat transfer temperature difference and move heat; Reach the heat request that moves of high speed of response of middle front part 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, and, heat transfer zone is set at the reactor drum middle part according to the characteristic exotherm that reacts; And the reactor drum two ends are provided with adiabatic region, make the hot spot region flattening, and temperature distribution more becomes evenly rationally; 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.
Method through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite of the present invention; Use device shown in Figure 1; Adopting focus distributed areas heat exchange, is raw material with the mixed gas that contains nitrous acid ester and carbon monoxide, is catalyzer with the palladium-containing metal oxide compound; 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is under the condition of-0.08～1.5MPa, and raw material contacts with 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 passes through reactor drum synoptic diagram in the method for carbon monoxide gas-phase catalytic coupling prepared in reaction barkite for the present invention.
1 is the feed(raw material)inlet among Fig. 1, the 2nd, and manhole, the 3rd, porous gas grid distributor, the 4th, gas distribution chamber; The 5th, last adiabatic catalyst beds, the 6th, heat exchange catalyst bed, the 7th, following adiabatic catalyst beds, the 8th, collection chamber; The 9th, porous gas collection plate, the 10th, pneumatic outlet, the 11st, catalyzer unloads outlet, and the 12nd, the heat transferring medium outlet; The 13rd, heat transfer tube, the 14th, heat transferring medium inlet, the 15th, reactor drum tank body.
Raw material is introduced by feed(raw material)inlet 1 among Fig. 1; Gas gets into distributing chamber's 4 further mixed distribution after porous gas grid distributor 3 distributes; Get into then and go up adiabatic catalyst beds 5 and catalyzer contact reacts, have the reaction effluent of certain temperature rise to get into heat exchange catalyst bed 6 again, the heat that discharges in the reaction process carries out shifting out of heat through heat transfer tube 13; Keep the temperature in the heat exchange catalyst bed 6 even; After adiabatic catalyst beds 7 further reacted completely under the last entering of elute behind most of raw material reaction, elute got into collection chamber 8, gets into follow-up system through porous gas collection plate 9 through pneumatic outlet 10.Because the hot(test)-spot temperature distributed areas adopt heat transfer tube to carry out shifting out and controlling of heat, 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]
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%Co carbon monoxide/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, wherein; The height of following adiabatic catalyst layer is 1/20 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/15 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 1.2: 1, and concrete steps are (as follows): (a) raw material is at first introduced by feed(raw material)inlet 1, and gas gets into distributing chamber's 4 further mixed distribution after porous gas grid distributor 3 distributes; Get into then and go up adiabatic catalyst beds 5 and catalyzer contact reacts, get reaction effluent I; (b) reaction effluent I gets into heat exchange catalyst bed 6, with the catalyzer contact reacts, gets reaction effluent II; (c) reaction effluent II gets into down adiabatic catalyst beds 7 again and further reacts with catalyzer, and reacted elute gets into collection chamber 8, gets into follow-up systems through porous gas collection plate 9 through pneumatic outlet 10.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%Co carbon monoxide/Al
2O
3Take by weighing the catalyzer that aequum makes, pack into shown in the accompanying drawing in the reactor drum, wherein; The height of following adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 1.5: 1, is 110 ℃ in temperature of reaction, 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, wherein; The height of following adiabatic catalyst layer is 1/8 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/6 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 2: 1, and 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, wherein; The height of following adiabatic catalyst layer is 1/20 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/15 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 4: 1, and 160 ℃ of temperature of reaction, the reaction volume air speed is 6000 hours
-1, reaction pressure is under the condition of 0.02MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: 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, wherein; The height of following adiabatic catalyst layer is 1/50 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/4 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, and 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, wherein; The height of following adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/18 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 1.5: 1, and 130 ℃ of temperature of reaction, the reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.2MPa, and raw material contacts with catalyzer, reacts, and its reaction result is: 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, wherein; The height of following adiabatic catalyst layer is 1/15 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/15 of a heat exchange catalyst bed height, is raw material with carbon monoxide and methyl nitrite then; Wherein, The mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, and 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, wherein; The height of following adiabatic catalyst layer be the heat exchange catalyst bed height 1/12 on the height of adiabatic catalyst layer be 1/10 of heat exchange catalyst bed height; 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 of [embodiment 1].According to [embodiment 1] same reaction conditions and reaction raw materials, just adopt insulation fix bed reactor, react, its reaction result is: carbon monoxide per pass conversion 73.8%, the selectivity of dimethyl oxalate are 96.5%.
Claims (8)
1. method through carbon monoxide gas-phase catalytic coupling prepared in reaction 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 carbon monoxide and nitrous acid ester is 0.8～5: 1,100～180 ℃ of temperature of reaction, and volume space velocity is 500～10000 hours
-1, reaction pressure is that raw material contacts with catalyst reactor successively under the condition of-0.08～1.5MPa, comprises the steps:
A) raw material is at first introduced by feed(raw material)inlet (1), and the further mixed distribution of gas entering distributing chamber (4) after porous gas grid distributor (3) distributes gets into then and goes up adiabatic catalyst beds (5) and catalyzer contact reacts, gets reaction effluent I;
B) reaction effluent I gets into heat exchange catalyst bed (6), with the catalyzer contact reacts, gets reaction effluent II;
C) reaction effluent II gets into down adiabatic catalyst beds (7) and catalyzer again and further reacts, and reacted elute gets into collection chamber (8), gets into follow-up system through porous gas collection plate (9) through pneumatic outlet (10).
Wherein, said reactor drum is the combined reactor of multiple-hearth structure, in the heat exchange beds heat transfer tube is set.
2. according to the said method of claim 1 through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite; The mol ratio that it is characterized in that carbon monoxide and nitrous acid ester is 1～3: 1; 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. according to the said method through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite of claim 1, it is characterized in that catalyzer comprises a) alumina supporter, is 90～99.8% of catalyst weight in its consumption of catalyst weight; B) active component palladium, its consumption is counted 0.003～1% of catalyst weight with simple substance; C) being selected from least a in rhenium, cobalt or the silver is auxiliary agent, is 0.005～9% of catalyst weight in its consumption of simple substance.
4. according to the said method of claim 1 through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite; It is characterized in that reactor drum mainly is made up of feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), last adiabatic catalyst beds (5), heat exchange catalyst bed (6), following adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9); Wherein, Heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5); The top of following adiabatic catalyst beds (7), and heat transfer tube (13) is set in the heat exchange catalyst bed (6).
5. according to the said method of claim 4, it is characterized in that porous gas collection plate (9) is positioned at collection chamber (8), and be connected with pneumatic outlet (10) through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite.
6. according to the said method of claim 4, it is characterized in that porous gas grid distributor (3) is positioned at gas distribution chamber (4), and be connected with feed(raw material)inlet (1) through the CO gas catalytic oxidative dehydrogenation.
7. according to the said method of claim 4, it is characterized in that adiabatic catalyst beds (5) top is 1/30～1/6 of reactor length apart from the length of porous gas grid distributor (3) bottom through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite; The bottom of following adiabatic catalyst beds (7) is 1/30～1/6 of a height for reactor apart from the vertical height on porous gas collection plate (9) top.
8. according to the said method of claim 4 through carbon monoxide gas-phase catalytic coupling prepared in reaction barkite; The height that it is characterized in that adiabatic catalyst beds (5) is 1/6～3/2 of heat exchange catalyst bed (a 6) height, and following adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (a 6) height.
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| CN103901132A (en) * | 2014-04-10 | 2014-07-02 | 中国科学院福建物质结构研究所 | Device and method for evaluating catalyst during preparation of oxalate through CO gas phase oxidative coupling |
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| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
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