CN102649735B - Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction - Google Patents
Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction Download PDFInfo
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Abstract
The invention relates to a method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction and mainly solves the technical problem of low oxalate selectivity in the reaction process of producing the oxalate through the carbon monoxide gas phase-coupled catalytic reaction existing in the prior art. With the adoption of the technical scheme that the method for producing the oxalate through the carbon monoxide gas phase-coupled catalytic reaction comprises the following steps that: mixed gas containing nitrite and carbon monoxide is taken as a raw material, a palladium-contained metallic oxide is taken as a catalyst, and under the conditions that the molar ratio of the carbon monoxide to the nitrite is (0.8-5):1, the reaction temperature is 100-180 DEG C, the volume airspeed is 500-10000 hour<-1>, and the reaction pressure is -0.08 MPa to 1.5 MPa, the raw material is in contact with a catalyst in a reactor, wherein the reactor is a combined tubular reactor which is used for partition heat exchange and adopts both a sleeve structure composed of an inner tube and an outer tube and a composite bed structure, so the problem is better solved. The method can be used in the industrial production for producing the oxalate through the carbon monoxide gas phase-coupled catalytic reaction.
Description
Technical field
The present invention relates to a kind of method of producing barkite of reacting by carbon monoxide gas-phase catalytic coupling, particularly about adopting subregion heat exchange and adopting the sleeve structure of inner and outer tubes and the composite column pipe reactor of multiple-hearth structure to realize the reaction that barkite is produced in carbon monoxide gas-phase catalytic coupling reaction.
Background technology
Barkite is important Organic Chemicals, in a large number for fine chemistry industry, produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.Enter 21 century, barkite is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, barkite ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example, carry out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize pharmaceutically as the chest acyl alkali of hormone.In addition, barkite low-voltage hydrogenation can be prepared very important industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, and within 2007 years, import volume is nearly 4,800,000 tons.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and production technique cost is high, and energy consumption is large, seriously polluted, and prepared using is unreasonable.For many years, people are finding an operational path that cost is low, environment is good always.The sixties in last century, the D.F.Fenton of U.S. Associated Oil Company finds, carbon monoxide, alcohol and oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. AR carbon monoxide company have carried out research and development in succession in this field since then.
For Oxidation of Carbon Monoxide coupling method synthesis of oxalate, from development course, divide and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is harsher, and reaction is under high pressure carried out, liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.The tool advantage of the vapor phase process of 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 technique of Yu Buxingchan company exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
Along with Oxidation of Carbon Monoxide coupling method in the world, prepare the research and development of barkite Technology, domestic many research institutions have also carried out research work to this field.According to china natural resources characteristic distributions, the carbon monoxide of take is prepared organic oxygen-containing compound as raw material, for alleviate petroleum products pressure, rationally utilize coal and natural gas source to there is very important strategic importance.At present, by Oxidation of Carbon Monoxide coupling method synthesis of oxalate, become important research topic in domestic one-carbon chemical and organic chemical industry field, successively You Duojia research institution and research institutions are devoted to catalyst preparation, process exploitation and the engineering amplification work in this field, and have obtained greater advance.
Although above-mentioned numerous research institution, has obtained technically compared with much progress, technology itself still needs to be further improved and develops, and especially how, improves reaction preference, and the aspects such as activity that improve catalyzer all need further research and break through.
Document CN200710060003.4 discloses a kind of method that carbon monoxide coupling is prepared oxalic acid diethyl ester, adopt vapor phase process, carbon monoxide is under the participation of ethyl nitrite, under the catalysis of bimetal supported catalyst, coupling oxalic diethyl ester crude product, reaction is self-closing circulating process, carbon monoxide gas enters coupler reactor with the ethyl nitrite from regeneration reactor through mixing preheating, after reaction, gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, non-condensable gas containing NO enters regeneration reactor, in regeneration reactor and ethanol, the recirculation of oxygen reaction generation ethyl nitrite is returned coupler reactor and is used continuously, this invention is on the basis of lab scale research in early stage, the industrial production of take is carried out as background, continuous operation examination is amplified in the mould examination and the pilot scale that have completed under industrial operation condition, linked reaction temperature is low, product concentration improves, present method is more energy-conservation, pollution-free, high efficiency.But the per pass conversion of this technology carbon monoxide is 20～60%, and object selectivity of product, in 96% left and right, all needs further to be improved.
Document CN95116136.9 discloses the catalyzer of the synthetic use of a kind of barkite, selects Zr to make auxiliary agent, by pickling process, develops novel Pd-Zr/Al
2o
3catalyzer.It is to adopt fixed-bed reactor that this catalyzer reacts with nitrous acid ester synthesis of oxalic ester by gaseous catalysis as carbon monoxide.But the yield of its barkite of catalyzer adopting in this patent is lower, and the impurity of unstripped gas is had relatively high expectations, the selectivity of product barkite is 95%, and the per pass conversion of nitrous acid ester is up to 64%, all needs further to be improved.
The subject matter that the related technology of above-mentioned document exists is that barkite selectivity is low, needs further to be improved.
Summary of the invention
Technical problem to be solved by this invention is in previous literature technology, to exist for carbon monoxide gas-phase catalytic coupling reaction to produce barkite reaction process, there is the technical problem that barkite selectivity is low, a kind of new method of react production barkite by carbon monoxide gas-phase catalytic coupling is provided.The method is produced barkite reaction process for carbon monoxide by coupled catalytic reaction, has advantages of that barkite selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing barkite of reacting by carbon monoxide gas-phase catalytic coupling, the mixed gas that contains nitrous acid ester and carbon monoxide of take is raw material, take palladium-containing metal oxide compound as catalyzer, mol ratio at carbon monoxide and nitrous acid ester is 0.8～5: 1,100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, under the condition that reaction pressure is-0.08～1.5MPa, raw material contacts with catalyst reactor successively, comprises the steps:
A) raw material is first by feed(raw material)inlet (1) and (20 introducings, respectively through gas Yi Ci distributing chamber (26) and (27), through inlet gas connecting hose (29), introduce bundle of reaction tubes inner tube (28), with Isothermal Catalyst bed (7) in reaction heat heat exchange after enter in gas quadratic distribution chamber (24), be introduced into afterwards adiabatic catalyst layer (31) and carry out initial reaction, obtain reaction effluent I;
B) reaction effluent I enters in the Isothermal Catalyst bed (7) between bundle of reaction tubes outer tube (5) and bundle of reaction tubes inner tube (28), with catalyzer contact reacts, obtains reaction effluent II;
C) reaction effluent II enters lower adiabatic catalyst layer (31) again, contact with catalyzer and continue reaction, obtain reaction effluent III, reaction effluent III enters after collection chamber (13), exports (12) enter follow-up system through porous gas collection plate (11) by product.
Wherein, described reactor is subregion heat exchange and adopts the sleeve structure of inner and outer tubes and the composite column pipe reactor of multiple-hearth structure.
In technique scheme, the mol ratio of carbon monoxide and nitrous acid ester is preferably 1～3: 1, and the reaction conditions of reactor is preferably: temperature of reaction is 110～160 ℃, and volume space velocity is 1000～6000 hours
-1, reaction pressure is-0.02～1.0MPa.Catalyzer take that palladium simple substance preferable amount is catalyst weight 0.003～1%.
In technique scheme, reactor is mainly by feed(raw material)inlet (1), feed(raw material)inlet (2), gas Yi Ci distributing chamber (26), gas Yi Ci distributing chamber (27), lower adiabatic catalyst layer (30), bundle of reaction tubes outer tube (5), bundle of reaction tubes inner tube (28), Isothermal Catalyst bed (7), upper adiabatic catalyst layer (31), gas quadratic distribution chamber (24), collection chamber (13), porous gas collection plate (11) and product outlet (12) form, it is characterized in that catalyst bed (7) is sequentially divided into the first heat exchange block (22) according to the mobile direction of reaction gas, the second heat exchange block (19) and the 3rd heat exchange block (16), on the top of reactor upper tubesheet (4), upper adiabatic catalyst layer (31) is set, in the bottom of reactor lower tubesheet (10), lower adiabatic catalyst layer (30) is set.
Bundle of reaction tubes inner tube (28) is set in isothermal catalyst bed (7) in technique scheme, and bundle of reaction tubes inner tube (28) is connected with gas Yi Ci distributing chamber (27) with the gas Yi Ci distributing chamber (26) in collection chamber (13) by inlet gas connecting hose (29).Porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12).The first heat exchange block (22) is connected with first district's heat transferring medium entrance (21) with first district's heat transferring medium outlet (23), the second heat exchange block (19) is connected with Second Region heat transferring medium outlet (20) with Second Region heat transferring medium entrance (8), is connected with the 3rd heat exchange block (16) Yu tri-district's heat transferring medium entrance (15) He tri-district's heat transferring medium outlets (17); Between the first heat exchange block (22) and the second heat exchange block (19), by the first subregion dividing plate (6), separate, between the second heat exchange block (19) and the 3rd heat exchange block (16), by the second subregion dividing plate (9), separate.The first subregion dividing plate (6) is preferably 1/8～1/3 of reactor length apart from the lower distance of reactor cover plate (25); The lower distance of second subregion dividing plate (9) distance the first subregion dividing plate (6) is preferably 1/8～1/3 of reactor length.The height of lower adiabatic catalyst layer (30) preferably Isothermal Catalyst bed (7) height 1/20～1/3; The height of upper adiabatic catalyst layer (31) preferably Isothermal Catalyst bed (7) height 1/20～1/3.
Because catalyzed reaction is carried out on catalyzer and not according to front and back phase uniform velocity, general reactor front portion is from balanced remote, speed of response is fast, emit reaction heat also many, rear portion approaches balance with reaction, speed of response slows down, emit reaction heat also few, if the same before and after the temperature of refrigerant, if reduce like this coolant temperature, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of top or anterior high speed of response and strong reaction heat, reactor lower part or rear portion reaction heat reduce, moving heat is greater than reaction heat and causes temperature of reaction to decline, speed of response is further slowed down until catalyst activity is following with regard to stopped reaction, therefore be difficult to the way making the best of both worlds of accomplishing that front and rear part reaction is all carried out under optimal reaction temperature.The present invention is directed to this fundamental contradiction, break through the existing refrigerant with same temperature, and adopt the different sections of reactor to adopt differing temps refrigerant to solve, make the size that in reaction, heat exchange is shifted out by reaction heat need design, a plurality of districts before and after specifically can being sequentially divided into by reaction gas flow direction in catalyst layer, carry out indirect heat exchange by refrigerant by heat transfer tube.On the other hand, the present invention is for the reaction heat of catalyzer, also adopts inner tube counter-current flow unstripped gas are set in catalyst bed, unstripped gas is carried out to preheating has saved energy consumption on the one hand, optimized reaction bed temperature distribution simultaneously, thereby realized the equiblibrium mass distribution of full bed temperature, in addition, the present invention is at entrance and the outlet section of reactor, all adopted adiabatic reactor, this is for the efficiency of maximized performance catalyzer, farthest
Reduce the loss of sub-ester, improve the selectivity of object product, useful effect is provided.
The method of producing barkite of reacting by carbon monoxide gas-phase catalytic coupling of the present invention, use Fig. 1 shown device, adopt subregion heat exchange, accurately control temperature, adopt the sleeve structure of inner and outer tubes catalyzer to be carried out to the catalyst loading method of heat exchange and multiple-hearth structure, the mixed gas that contains nitrous acid ester and carbon monoxide of take is raw material, take palladium-containing metal oxide compound as catalyzer simultaneously, 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, under the condition that reaction pressure is-0.08～1.5MPa, raw material contacts with catalyzer, nitrous acid ester and reaction of carbon monoxide oxalic ester in raw material, and the selectivity of barkite can be greater than 99%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is that the present invention reacts reactor schematic diagram in the method for producing barkite by carbon monoxide gas-phase catalytic coupling.
In Fig. 1,1 and 2 is feed(raw material)inlets, the 3rd, reactor upper cover, the 4th, upper tubesheet, the 5th, bundle of reaction tubes outer tube, 6 is first subregion dividing plates, the 7th, catalyst bed, the 8th, reactor tank body, 9 is second subregion dividing plates, the 10th, lower tubesheet, the 11st, porous gas collection plate, the 12nd, product outlet, the 13rd, collection chamber, the 14th, reactor lower cover, 15 Shi tri-district's heat transferring medium entrances, 16 is the 3rd heat exchange blocks, 17 Shi 3rd district heat transferring medium outlets, the 18th, Second Region heat transferring medium entrance, 19 is second heat exchange blocks, the 20th, the outlet of Second Region heat transferring medium, 21 is first district's heat transferring medium entrances, 22 is first heat exchange blocks, 23 is the heat transferring medium outlets of the firstth district, the 24th, gas quadratic distribution chamber, the 25th, reactor cover plate, 26 and 27 is gas Yi Ci distributing chamber, the 28th, bundle of reaction tubes inner tube, the 29th, inlet gas connecting hose, the 30th, lower adiabatic catalyst layer, the 31st, upper adiabatic catalyst layer.
Fig. 1 Raw is introduced by feed(raw material)inlet 1 and 2, respectively through gas Yi Ci distributing chamber 26 and 27, through inlet gas connecting hose 29, introduce bundle of reaction tubes inner tube 28, with after reaction heat heat exchange in Isothermal Catalyst bed 7, enter in gas quadratic distribution chamber 24, be introduced into afterwards adiabatic catalyst layer 31 and carry out initial reaction, reacted product enters in the Isothermal Catalyst bed 7 between bundle of reaction tubes outer tube 5 and bundle of reaction tubes inner tube 28 again, with catalyzer contact reacts, reacted product enters lower adiabatic catalyst layer 31 again and continues reaction, finally enter after collection chamber 13, through porous gas collection plate 11, by product, export 12 and enter follow-up system.In reaction raw materials gas enters the Isothermal Catalyst bed 7 between bundle of reaction tubes outer tube 5 and bundle of reaction tubes inner tube 28, with the reaction heat in 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 controlled by entering temperature and the flow philosophy of the heat transferring medium of each heat exchange block, in addition, unstripped gas is from bundle of reaction tubes inner tube 28 and reactant gases counter current contact process, also catalyst bed 7 heat balances are played to better promoter action, thereby reach the uniform effect of whole reactor catalyst bed tempertaure.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Cobalt oxalate is dissolved in water, is heated to 70 ℃, it is 10 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, then in 120 ℃, be dried 6 hours.A certain amount of Palladous nitrate is dissolved in the water, with nitric acid regulator solution, making its pH value is 4 left and right, then this solution is heated to 80 ℃, again be immersed on carrier, then in 140 ℃ dry 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+0.28Co% carbon monoxide/Al
2o
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/20 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/15 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.2: 1, concrete steps are (as follows): (a) first raw material is introduced by feed(raw material)inlet 1 and 2, respectively through gas Yi Ci distributing chamber 26 and 27, through inlet gas connecting hose 29, introduce bundle of reaction tubes inner tube 28, with after reaction heat heat exchange in Isothermal Catalyst bed 7, enter in gas quadratic distribution chamber 24, be introduced into afterwards adiabatic catalyst layer 31 and carry out initial reaction, obtain reaction effluent I, (b) reaction effluent I enters in the Isothermal Catalyst bed 7 between bundle of reaction tubes outer tube 5 and bundle of reaction tubes inner tube 28, with catalyzer contact reacts, obtains reaction effluent II, (c) reaction effluent II enters lower adiabatic catalyst layer 31 again, contacts continue reaction with catalyzer, obtains reaction effluent III, and reaction effluent III enters after collection chamber 13, exports 12 enter follow-up system through porous gas collection plate 11 by product.In temperature of reaction, be 130 ℃, 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 is 99.2%.
[embodiment 2]
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is dissolved in water, is heated to 80 ℃, it is 8 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, then in 120 ℃, be dried 4 hours.Ammonium palladic chloride is dissolved in the water, with nitric acid regulator solution, making its pH value is 4 left and right, then this solution is heated to 80 ℃, again be immersed on carrier, then in 140 ℃ dry 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+0.40Co% carbon monoxide/Al
2o
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/10 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/10 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.5: 1, in temperature of reaction, it is 110 ℃, 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 is 99.7%.
[embodiment 3]
Silver Nitrate is dissolved in the water, and vacuum impregnation is 15 meters in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Palladous nitrate is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres is reduced 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
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/8 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/6 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 2: 1, 140 ℃ of temperature of reaction, 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 is 99.1%.
[embodiment 4]
The sub-palladium acid of chlorine is dissolved in the aqueous solution, and it is 20 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ dry 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres is reduced 4 hours in 450 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtains catalyzer D, consists of 0.34%Pd/Al
2o
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/20 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/15 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 4: 1, 160 ℃ of temperature of reaction, reaction volume air speed is 6000 hours
-1, under the condition that reaction pressure is 0.02MPa, raw material contacts with catalyzer, reacts, and its reaction result is: carbon monoxide per pass conversion 22.2%, the selectivity of dimethyl oxalate is 98.3%.
[embodiment 5]
Nitric acid rhenium is dissolved in the water, and it is 30 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then 450 ℃ of roastings 4 hours, in 350 ℃ of hydrogen atmospheres, reduce 4 hours, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer E, consist of 0.11%Pd+0.6%Re/Al
2o
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/50 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/4 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, 170 ℃ of temperature of reaction, reaction volume air speed is 8000 hours
-1, under the condition that reaction pressure is 0.5MPa, raw material contacts with catalyzer, reacts, and its reaction result is: carbon monoxide per pass conversion 74.6%, the selectivity of dimethyl oxalate is 97.3%.
[embodiment 6]
Getting 200 grams of specific surface agent is 40 meters
2/ gram Al
2o
3bead, be immersed in containing in 8.0 grams of Palladous nitrates, 14 grams of nitric acid rhenium aqueous solution, and with nitric acid, regulating its pH value is 2, after taking-up, at 140 ℃, dry 4 hours, then roasting 2 hours in 450 ℃ of air atmospheres, in 350 ℃ of hydrogen atmospheres, reduce 4 hours, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer F and consist of 0.6%Pd+1.1%Re/Al
2o
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/10 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/18 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.5: 1, 130 ℃ of temperature of reaction, reaction volume air speed is 2000 hours
-1, under the condition that reaction pressure is 0.2MPa, raw material contacts with catalyzer, reacts, and its reaction result is: carbon monoxide per pass conversion 63.8%, the selectivity of dimethyl oxalate is 99.5%.
[embodiment 7]
Silver Nitrate is dissolved in the water, and vacuum impregnation is 50 meters in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 2 hours in 450 ℃ of air atmospheres is reduced 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
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer is 1/15 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/15 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, 120 ℃ of temperature of reaction, reaction volume air speed is 1500 hours
-1, under the condition that reaction pressure is 0.1MPa, raw material contacts with catalyzer, reacts, and its reaction result is: carbon monoxide per pass conversion 73.9%, the selectivity of dimethyl oxalate is 99.8%.
[embodiment 8]
Nitric acid rhenium is dissolved in the water, and vacuum impregnation is 30 meters in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres is reduced 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
3.Take the catalyzer that aequum makes, pack into shown in accompanying drawing in reactor, wherein, the height of lower adiabatic catalyst layer be Isothermal Catalyst bed height 1/12 on the height of adiabatic catalyst layer be 1/10 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 0.6: 1, 120 ℃ of temperature of reaction, reaction volume air speed is 2000 hours
-1, under the condition that reaction pressure is 0.03MPa, raw material contacts with catalyzer, reacts, and its reaction result is: carbon monoxide per pass conversion 96.2%, the selectivity of dimethyl oxalate is 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 74.0%, the selectivity of dimethyl oxalate is 96.6%.
Claims (1)
1. by carbon monoxide gas-phase catalytic coupling, react a method of producing barkite, cobalt oxalate is dissolved in water, be heated to 70 ℃, it is 10 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, then in 120 ℃, be dried 6 hours, a certain amount of Palladous nitrate is dissolved in the water, with nitric acid regulator solution, making its pH value is 4 left and right, then this solution is heated to 80 ℃, again be immersed on carrier, then in 140 ℃ dry 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+0.28Co%/Al
2o
3, take the catalyzer that aequum makes, pack in reactor, wherein, the height of lower adiabatic catalyst layer is 1/20 of Isothermal Catalyst bed height, the height of upper adiabatic catalyst layer is 1/15 of Isothermal Catalyst bed height, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, adopt in addition the sleeve structure of inner and outer tubes and the catalyst loading method of multiple-hearth structure, then take carbon monoxide and methyl nitrite as raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.2: 1, concrete steps are: (a) first raw material is introduced by feed(raw material)inlet (1) and (2), respectively through gas Yi Ci distributing chamber (26) and (27), through inlet gas connecting hose (29), introduce bundle of reaction tubes inner tube (28), with Isothermal Catalyst bed (7) in reaction heat heat exchange after enter in gas quadratic distribution chamber (24), be introduced into afterwards adiabatic catalyst layer (31) and carry out initial reaction, obtain reaction effluent I, (b) reaction effluent I enters in the Isothermal Catalyst bed (7) between bundle of reaction tubes outer tube (5) and bundle of reaction tubes inner tube (28), with catalyzer contact reacts, obtains reaction effluent II, (c) reaction effluent II enters lower adiabatic catalyst layer (30) again, contact with catalyzer and continue reaction, obtain reaction effluent III, reaction effluent III enters after collection chamber (13), exports (12) enter follow-up system through porous gas collection plate (11) by product, in temperature of reaction, be 130 ℃, 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 is 99.2%.
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| CN107441909B (en) * | 2017-08-29 | 2019-10-18 | 萍乡市华星环保工程技术有限公司 | Desulphurization denitration mixed reactor and desulfurization and denitrification integral process |
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| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
| CN101791555A (en) * | 2010-03-19 | 2010-08-04 | 丹阳市丹化金煤化工有限公司 | Catalyst for gas-phase dimethyloxalate synthesis by CO and preparation method thereof |
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| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
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