CN102649740B - Method for preparing oxalate through CO catalytic coupling reaction - Google Patents
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- CN102649740B CN102649740B CN201110047258.3A CN201110047258A CN102649740B CN 102649740 B CN102649740 B CN 102649740B CN 201110047258 A CN201110047258 A CN 201110047258A CN 102649740 B CN102649740 B CN 102649740B
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Abstract
The invention relates to a method for preparing oxalate through CO catalytic coupling reaction. The technical problems of difficulty in temperature control and low selectivity of target product during the process of preparing oxalate through CO catalytic coupling reaction in the prior art are solved. The method comprises the following steps of: taking a mixed gas containing nitrous acid ester and CO as a raw material, and contacting the raw material with a noble metal catalyst in an upper heat-insulating catalytic bed, a heat-exchange catalytic bed and a lower heat-insulating catalytic bed in a heat-point distributed area enhanced heat-exchange combined reactor in turn, under the conditions of reaction temperature at 100-180 DEG C, volume hourly space velocity at 500-10000 per hour, reaction pressure at -0.08-1.5MPa and mole ratio of CO to nitrous acid ester being (1-5):1, thereby generating an effluent containing the oxalate by reacting. According to the technical scheme, the problem is more efficiently solved. The method is suitable for the industrial production for preparing oxalate through CO catalytic coupling.
Description
Technical field
The present invention relates to a kind of method of preparing barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction, particularly about adopting hotspot's distribution region enhanced heat exchange combined reactor, realize carbon monoxide gas phase coupled catalytic reaction and produce the reaction of barkite, be practically applicable to prepare in barkite reaction process by CO (carbon monoxide converter) gas catalytic coupling.
Background technology
Barkite is important Organic Chemicals, in a large number produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate for fine chemistry industry.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 at the chest acyl alkali that is pharmaceutically used as 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, 2007 years nearly 4,800,000 tons of import volumes.
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 Associated Oil Company of the U.S. 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 ARCO company of the U.S. have carried out research and development in succession in this field since then.
Divide and can be divided into liquid phase method and vapor phase process from development course for Oxidation of Carbon Monoxide coupling method synthesis of oxalate.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is harsher, and reaction is under high pressure carried out, liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technique of Yu Buxingchan company exploitation, reaction pressure 0.5MPa, temperature is 80 DEG C～150 DEG C.
Prepare the research and development of barkite Technology along with Oxidation of Carbon Monoxide coupling method in the world, domestic many research institutions have also carried out research work to this field.According to china natural resources characteristic distributions, prepare organic oxygen-containing compound taking carbon monoxide as raw material, for alleviate petroleum products pressure, rationally utilize coal and natural gas source to there is very important strategic importance.At present, become important research topic in domestic one-carbon chemical and organic chemical industry field by Oxidation of Carbon Monoxide coupling method synthesis of oxalate, 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.
The aspects such as 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 improves reaction preference how, the activity of raising catalyzer all need further research and break through.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopt vapor phase process, CO is under the participation of ethyl nitrite, under the catalysis of bimetal supported catalyst, coupling oxalic diethyl ester crude product, reaction is self-closing circulating process, CO gas enters coupler reactor with the ethyl nitrite from regeneration reactor through mixing preheating, after reaction, gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, non-condensable gas containing NO enters regeneration reactor, in regeneration reactor and ethanol, the recirculation of oxygen reaction generation ethyl nitrite is returned coupler reactor and is used continuously, this invention is on the basis of lab scale research in early stage, carry out taking industrial production as background, continuous operation examination is amplified in the mould examination and the pilot scale that have completed under industrial operation condition, linked reaction temperature is low, product concentration improves, present method is more energy-conservation, pollution-free, high efficiency.But the per pass conversion of this technology CO is 20～60%, and object selectivity of product, in 96% left and right, all needs further to be improved.
Document CN 95116136.9 discloses the catalyzer of the synthetic use of a kind of barkite, selects Zr to make auxiliary agent, develops novel Pd-Zr/Al by pickling process
2o
3catalyzer.It is to adopt fixed-bed reactor that this catalyzer reacts with nitrous acid ester synthesis of oxalic ester by gaseous catalysis as carbon monoxide.But the yield of its barkite of catalyzer adopting in this patent is lower, and the impurity of unstripped gas is had relatively high expectations, the selectivity of product barkite is only 95%.
The subject matter that the related technology of above-mentioned document exists is that barkite selectivity of product is low.
Summary of the invention
Technical problem to be solved by this invention is to prepare barkite reaction process for CO (carbon monoxide converter) gas catalytic coupling in previous literature technology, temperature control difficulty, the technical problem that barkite selectivity is low, provides a kind of new method that CO (carbon monoxide converter) gas catalyzed coupling reaction is prepared barkite of passing through.This method of preparing barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction is prepared barkite process for CO (carbon monoxide converter) gas catalytic coupling, and temperature control is even, 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 preparing barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction, taking the mixed gas that contains nitrous acid ester and CO as raw material, 100～180 DEG C of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 condition, raw material successively with hotspot's distribution region enhanced heat exchange combined reactor in upper adiabatic catalyst beds, heat exchange catalyst bed contacts with the noble metal catalyst in lower adiabatic catalyst beds, reaction generates the effluent containing barkite, wherein enhanced heat exchange combined reactor in hotspot's distribution region is mainly by feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), upper adiabatic catalyst beds (5), heat exchange catalyst bed (6), lower adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9) form, be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5), the top of lower adiabatic catalyst beds (7), and heat transfer tube (13) is set in heat exchange catalyst bed (6).
In 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).Upper 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 lower adiabatic catalyst beds (7) is 1/30～1/6 of height for reactor apart from the vertical height on porous gas collection plate (9) top.The height of upper adiabatic catalyst beds (5) is 1/6～3/2 of heat exchange catalyst bed (6) height, and lower adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (6) height.
In technique scheme, to be preferably temperature of reaction be 100～160 DEG C to reaction conditions, and volume space velocity is 500～5000 hours
-1, reaction pressure is-0.05～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1.Noble metal catalyst active constituent is preferably selected from palladium, and carrier is preferably selected from least one in aluminum oxide or silicon oxide.
As everyone knows, CO is strong exothermal reaction with reacting of nitrous acid ester gas phase coupling producing oxalic ester, reaction kinetics research shows, temperature of reaction uniform very remarkable on the impact of object selectivity of product, especially in reactor feed gas, the decomposition loss of nitrous acid ester and temperature of reaction cognation are very strong, and the decomposition loss of the higher sub-acid esters of temperature of reaction is just higher.We know, for conventional catalytic exothermic reaction, 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, show as anterior mid-way partially and easily occur significant hot spot region, and rear portion approaches balance with reaction, speed of response slows down, emit reaction heat also few, if adopt conventional shell-and-tube reactor, the same before and after the temperature of its refrigerant, if reduce like this coolant temperature, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of the high speed of response of middle front part and strong reaction heat, reactor lower part or rear portion reaction heat reduce, move heat be greater than reaction heat cause temperature of reaction decline, speed of response is further slowed down until catalyst activity is following with regard to stopped reaction, therefore be difficult to accomplish that front and rear part reacts the way making the best of both worlds of all carrying out under optimal reaction temperature.The present invention is directed to this fundamental contradiction, and according to the characteristic exotherm reacting, at reactor middle part, heat transfer zone is set, and reactor two ends arrange adiabatic region, make hot spot region flattening, temperature distribution is more evenly rationally, 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.
Method Fig. 1 shown device of preparing barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction of the present invention, adopt hotspot's distribution region enhanced heat exchange combined reactor technology, adopting precious metal palladium Supported alumina is catalyzer, taking the mixed gas that contains nitrous acid ester and CO as raw material, 100～180 DEG C of temperature of reaction, volume space velocity is 500～10000 hours
-1reaction pressure is-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 condition, raw material contacts with the noble metal catalyst in upper adiabatic catalyst beds, heat exchange catalyst bed and lower adiabatic catalyst beds in the enhanced heat exchange combined reactor of hotspot's distribution region successively, reaction generates the effluent containing barkite, its result is: the selectivity of barkite can be greater than 99%, has obtained good technique effect.
Brief description of the drawings
Fig. 1 be the present invention adopt pass through the reactor schematic diagram that CO (carbon monoxide converter) gas catalyzed coupling reaction is prepared barkite.
In Fig. 1,1 is feed(raw material)inlet, the 2nd, and manhole, the 3rd, porous gas grid distributor, the 4th, gas distribution chamber, the 5th, upper adiabatic catalyst beds, the 6th, heat exchange catalyst bed, the 7th, lower 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, heat transferring medium outlet, the 13rd, heat transfer tube, the 14th, heat transferring medium entrance, the 15th, reactor tank body.
Fig. 1 Raw is introduced by feed(raw material)inlet 1, gas enters the further mixed distribution of distributing chamber 4 after porous gas grid distributor 3 distributes, then enter adiabatic catalyst beds 5 and catalyzer contact reacts, there is the reaction effluent of certain temperature rise to enter again heat exchange catalyst bed 6, the heat discharging in reaction process carries out shifting out of heat by heat transfer tube 13, keep the temperature in heat exchange catalyst bed 6 even, effluent after most of raw material reaction finally enters after lower adiabatic catalyst beds 7 further reacts completely, effluent enters collection chamber 8, enter follow-up system by porous gas collection plate 9 through pneumatic outlet 10.Carry out shifting out and controlling of heat because hot(test)-spot temperature distributed areas adopt heat transfer tube, thereby reach the uniform effect of whole reactor catalyst bed tempertaure.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/20 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/10 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/8 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/4 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.5% is as catalyzer, with the mixed gas that the mol ratio of CO and methyl nitrite is 1.2: 1 be raw material, be 130 DEG C in temperature of reaction, reaction volume air speed is 2000 hours
-1, reaction pressure is-condition of 0.08MPa under, raw material contacts with catalyzer, reacts, its reaction result is: CO per pass conversion 78.4%, the selectivity of dimethyl oxalate is 99.2%, reactor catalyst bed temperature is poor is less than 6 DEG C.
[embodiment 2]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/10 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/20 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/3 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/4 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.2% is as catalyzer, wherein, the height of lower adiabatic catalyst layer is 1/10 of Isothermal Catalyst bed height; The height of upper adiabatic catalyst layer is 1/8 of Isothermal Catalyst bed height, with the mixed gas that the mol ratio of CO and ethyl nitrite is 0.6: 1 be raw material, 120 DEG C of temperature of reaction, reaction volume air speed is 2000 hours
-1, under the condition that reaction pressure is 0.03MPa, raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 94.2%, the selectivity of oxalic acid diethyl ester is 98.8%, reactor catalyst bed temperature is poor is less than 6 DEG C.
[embodiment 3]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/8 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/5 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/3 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/6 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.25% is as catalyzer, with the mixed gas that the mol ratio of CO and methyl nitrite is 1.2: 1 be raw material, be 135 DEG C in temperature of reaction, reaction volume air speed is 5000 hours
-1, reaction pressure is-condition of 0.05MPa under, raw material contacts with catalyzer, reacts, its reaction result is: CO per pass conversion 77.0%, the selectivity of dimethyl oxalate is 99.0%, reactor catalyst bed temperature is poor is less than 7 DEG C.
[embodiment 4]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/15 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/20 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/3 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/4 of heat exchange catalyst bed height, taking palladium content as 0.4%, the content of iron is that 0.5% palladium and the catalyzer of iron Supported alumina are catalyzer, with the mixed gas that the mol ratio of CO and methyl nitrite is 1.4: 1 be raw material, be 145 DEG C in temperature of reaction, reaction volume air speed is 55000 hours
-1, under the condition that reaction pressure is 0.05MPa, raw material contacts with catalyzer, reacts, and its reaction result is: CO per pass conversion 65.3%, the selectivity of dimethyl oxalate is 99.5%, reactor catalyst bed temperature is poor is less than 12 DEG C.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just CO gas coupling producing oxalic ester adopts insulation fix bed reactor, and reaction result is: CO per pass conversion 76.4%, and the selectivity of dimethyl oxalate is 96.1%, reactor catalyst bed temperature is poor is 15 DEG C.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just CO gas coupling producing oxalic ester reactor adopts adiabatic fixed-bed reactor, reaction result is: CO per pass conversion 88.1%, and the selectivity of oxalic acid diethyl ester is 95.6%, reactor catalyst bed temperature is poor is 16 DEG C.
Claims (3)
1. prepare a method for barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction, taking the mixed gas that contains nitrous acid ester and CO as raw material, 100～180 DEG C of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 condition, raw material successively with hotspot's distribution region enhanced heat exchange combined reactor in upper adiabatic catalyst beds, heat exchange catalyst bed contacts with the noble metal catalyst in lower adiabatic catalyst beds, reaction generates the effluent containing barkite, wherein enhanced heat exchange combined reactor in hotspot's distribution region is mainly by feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), upper adiabatic catalyst beds (5), heat exchange catalyst bed (6), lower adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9) form, be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5), the top of lower adiabatic catalyst beds (7), and heat transfer tube (13) is set in heat exchange catalyst bed (6), wherein, the porous gas collection plate (9) of reactor is positioned at collection chamber (8), and is connected with pneumatic outlet (10), the porous gas grid distributor (3) of reactor is positioned at gas distribution chamber (4), and is connected with feed(raw material)inlet (1), upper adiabatic catalyst beds (5) top of reactor is 1/30～1/6 of reactor length apart from the length of porous gas grid distributor (3) bottom, the bottom of lower adiabatic catalyst beds (7) is 1/30～1/6 of height for reactor apart from the vertical height on porous gas collection plate (9) top, the height of the upper adiabatic catalyst beds (5) of reactor is 1/6～3/2 of heat exchange catalyst bed (6) height, and lower adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (6) height.
2. prepare according to claim 1 the method for barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction, it is characterized in that temperature of reaction is 100～160 DEG C, volume space velocity is 500～5000 hours
-1, reaction pressure is-0.05～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1.
3. prepare according to claim 1 the method for barkite by CO (carbon monoxide converter) gas catalyzed coupling reaction, it is characterized in that noble metal catalyst active constituent is selected from palladium, carrier is selected from least one in aluminum oxide or silicon oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2621805Y (en) * | 2003-06-03 | 2004-06-30 | 华东理工大学 | Shell external cooling-thermal insulating and combined fixed bed catalyst chember |
| CN101475473A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2621805Y (en) * | 2003-06-03 | 2004-06-30 | 华东理工大学 | Shell external cooling-thermal insulating and combined fixed bed catalyst chember |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
| CN101475473A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO |
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