CN102649733B - Method for preparing oxalate through CO gas phase catalytic coupling - Google Patents
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- CN102649733B CN102649733B CN201110045609.7A CN201110045609A CN102649733B CN 102649733 B CN102649733 B CN 102649733B CN 201110045609 A CN201110045609 A CN 201110045609A CN 102649733 B CN102649733 B CN 102649733B
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Abstract
The invention relates to a method for preparing oxalate through CO gas phase catalytic coupling and mainly solves the technical problem of low oxalate selectivity in the reaction process of preparing the oxalate through the CO gas phase catalytic coupling existing in the prior art. With the adoption of the technical scheme that the method for preparing the oxalate through the CO gas phase catalytic coupling comprises the following steps that: mixed gas containing nitrite and CO is taken as a raw material, methanol, ethanol or water are taken as a terminating agent, and under the conditions that 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 molar ratio of the CO to the nitrite is (1-5):1, the raw material is in contact with a palladium-contained fluidized bed catalyst in a fluidized bed reactor for reaction to generate an effluent containing the oxalate, so the problem is better solved. The method can be used in the industrial production for preparing the oxalate through the CO gas phase catalytic coupling.
Description
Technical field
The present invention relates to a kind of method of CO gas gas-phase catalytic coupling producing oxalic ester, particularly about employing CO gas coupling producing oxalic ester fluidized-bed reactor coupling riser reactor, fast separating device, is practically applicable in CO gas coupling producing oxalic ester reaction process.
Background technology
Barkite is important Organic Chemicals, produces various dyestuff, medicine, important solvent in a large number for fine chemistry industry, 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., such as, carries out various condensation reaction with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali being pharmaceutically used as hormone.In addition, barkite low-voltage hydrogenation can prepare 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, and seriously polluted, prepared using is unreasonable.For many years, people's, operational path that environment good low at searching cost always.The sixties in last century, American Association oil company D.F.Fenton finds, carbon monoxide, alcohol and oxygen are by 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.
From development course, division is carried out for Oxidation of Carbon Monoxide 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 harsher, and reaction is under high pressure carried out, liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.The vapor phase process most advantage of CO coupling producing oxalic ester, company of external Ube Industries Ltd. and Italian Montedisons SPA have 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.
Along with Oxidation of Carbon Monoxide coupling method prepares the research and development of barkite Technology in the world, domestic many research institutions have also carried out research work to this field.According to china natural resources characteristic distributions, being that organic oxygen-containing compound prepared by raw material with carbon monoxide, for alleviating the pressure of petroleum products, Appropriate application coal and natural gas source, there is very important strategic importance.At present, research topic important in domestic one-carbon chemical and organic chemical industry field has been become by Oxidation of Carbon Monoxide coupling method synthesis of oxalate, successively You Duojia research institution and research institutions are devoted to the catalyst preparation in this field, process exploitation and engineering amplification work, and achieve greater advance.
Although above-mentioned numerous research institution, has obtained comparatively much progress technically, technology itself has still needed to be further improved and has developed, and especially how to improve reaction preference, and improving the aspects such as the activity of catalyzer all needs research further 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, be that background is carried out with industrial production, examination that the mould completed under commercial operating conditions tries and enlarged experiment operates continuously, 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%, object selectivity of product, about 96%, all needs to be improved further.
Document CN 95116136.9 discloses the catalyzer of a kind of barkite synthesis, selects Zr to make auxiliary agent, develops novel Pd-Zr/Al by pickling process
2o
3catalyzer.It is adopt fixed-bed reactor that this catalyzer reacts as carbon monoxide and nitrous acid ester synthesis of oxalic ester by gaseous catalysis.But the yield of its barkite of catalyzer adopted in this patent is lower, and require higher to the impurity of unstripped gas, the selectivity of product barkite is 95%, and the per pass conversion of nitrous acid ester is up to 64%, all needs to be improved further.
The subject matter that technology involved by above-mentioned document exists is the technical problem that the selectivity selectivity of barkite is low.
Summary of the invention
Technical problem to be solved by this invention is in the reaction process of CO gas gas-phase catalytic coupling producing oxalic ester in previous literature technology, the technical problem that object selectivity of product is low, provides a kind of method of new CO gas gas-phase catalytic coupling producing oxalic ester.The method is used for, in CO gas coupling producing oxalic ester process, having the advantage that barkite object selectivity of product 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 CO gas gas-phase catalytic coupling producing oxalic ester, with the mixed gas containing nitrous acid ester and CO for raw material, with methyl alcohol, ethanol or water for terminator, temperature of reaction 100 ~ 180 DEG C, 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 the condition of 1 ~ 5: 1, raw material and contacting containing palladium fluid catalyst in fluidized-bed reactor, reaction generates the effluent containing barkite, wherein fluidized-bed reactor, basic by settling vessel (5), stripper (11) and interchanger (3) composition, comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), fast separating device (6), airway (7), cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13), wherein emulsion zone (A) is connected with riser tube (4) after the zone of transition (B) of undergauge structure, riser tube (4) upper end or end are provided with fast separating device (6), the spiral arm of fast separating device (6) is positioned at riser tube (4) outward, in the airway (7) coaxially communicated with riser tube (4), airway (7) is positioned at settling vessel (5), and the freeboard of fluidized bed on negative area (C) top is stretched in its upper end, and its lower end is positioned at riser tube (4) outer zone of transition (B) outer upper ends, cyclonic separator (8) is positioned at settling vessel (5), and outward, its upper outlet communicates with collection chamber (9) airway (7), collection chamber (9) is positioned at settling vessel (5) top and is connected with product gas outlet (10), stripper (11) one end is connected with the bottom of settling vessel (5), and the other end of stripper (11) is connected with inclined tube to be generated (13), interchanger (3) is set between the bottom of settling vessel (5) and emulsion zone (A) hypomere, one end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A), sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, the bottom of sparger or grid distributor (2) is provided with material inlet (1), it is characterized in that arranging terminator inlet (15) near riser tube (4) lower region.
In technique scheme, terminator inlet 15 is 0 ~ 4/5 of riser tube 4 length apart from the vertical range bottom riser tube 4; Terminator inlet 15 distributes ringwise along riser tube 4 lower region; The internal diameter of riser tube 4 is 1/15 ~ 1/2 of emulsion zone A external diameter, and the height of riser tube 4 is 1/5 ~ 5/1 of emulsion zone A height; Regenerator sloped tube 12 is 1/10 ~ 1/2 of emulsion zone A vertical height with emulsion zone A Link Port distance emulsion zone A bottom vertical distance; The vertical height of zone of transition B is 1/20 ~ 1/2 of emulsion zone A vertical height; The gas inlet distance set air chamber 9 plan vertical distance of cyclonic separator 8 is 1/10 ~ 1/1 of settling vessel diameter.
In technique scheme, reaction conditions is preferably: temperature of reaction is 100 ~ 160 DEG C, and volume space velocity is 500 ~ 5000 hours
-1, reaction pressure is the mol ratio of-0.05 ~ 1.0MPa, CO and nitrous acid ester is 1 ~ 3: 1, and containing the preferred self-alumina of palladium fluidized bed catalytic agent carrier, particle diameter average preferred range is 30 ~ 200 microns.
As everyone knows, the reaction of CO and nitrous acid ester gas phase coupling producing oxalic ester is strong exothermal reaction, reaction kinetics research shows, the uniform impact on object selectivity of product of temperature of reaction is very remarkable, the present invention adopt fluidized-bed reactor can realization response beds homogeneous temperature distribution, this is to the selectivity Be very effective improving object product, and also find in research process, 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 higher.And adopt in CO gas coupling producing oxalic ester fluidized-bed reaction process, raw material contacts in situation with long-lasting catalytic, still can continue to transform, especially at the settling zone of CO gas coupling producing oxalic ester fluidized-bed reactor, a large amount of unsegregated catalyzer can continue to react with sub-ester at high operating temperatures, causes the decomposition of sub-ester and rate of loss is high.The present invention injects terminator by the region, outlet position leaving catalytic bed at catalyzer and reaction product, on the one hand, the terminator that temperature is lower and pyroreaction mixture and catalyst exposure, significantly can reduce the temperature of reaction mixture and catalyzer, this can accelerate the sharply temperature-fall period of pyroreaction mixture and catalyzer further, after the reaction mixture that temperature sharply reduces and catalyzer leave reaction zone, side reaction is few, continue reaction odds little, reduce the rate of loss of raw material, further increase yield or the selectivity of product.
In reaction process for CO gas gas-phase catalytic coupling producing oxalic ester of the present invention, use Fig. 1 shown device, precious metal palladium Supported alumina is adopted to be catalyzer, water, methyl alcohol or ethanol are terminator, with the mixed gas containing nitrous acid ester and CO for raw material, temperature of reaction 100 ~ 180 DEG C, volume space velocity is 500 ~ 10000 hours
-1, reaction pressure is the mol ratio of-0.08 ~ 1.5MPa, CO and nitrous acid ester is under the condition of 1 ~ 5: 1, raw material and contacting containing palladium fluid catalyst in fluidized-bed reactor, reaction generates the effluent containing barkite, and the selectivity of barkite can be greater than 99%, achieves good technique effect.
Accompanying drawing explanation
The fluidized-bed reactor schematic diagram that the method that Fig. 1 is CO gas gas-phase catalytic coupling producing oxalic ester of the present invention adopts.
In Fig. 1, A is emulsion zone, B is zone of transition, C be negative area, 1 is material inlet, and 2 is sparger or grid distributor, and 3 is interchanger, 4 is riser tubes, and 5 is settling vessels, and 6 is fast separating devices, 7 is airways, and 8 is cyclonic separators, and 9 is collection chambers, 10 product gas outlet, 11 is strippers, and 12 is regenerator sloped tubes, and 13 is inclined tubes to be generated, 14 is stripped vapor entrances, and 15 is terminator inlets.
Fig. 1 Raw is introduced by material inlet 1, through gas distributor or grid distributor 2 distribute laggard enter the emulsion zone A of fluidized-bed and catalyst exposure react, catalyzer and reaction mixture enter riser tube 4 through zone of transition B; After vortex quick separation device 6 sharp separation of riser tube 4 upper end (end), major part catalyzer enters the lower region of settling vessel C, the partially catalyzed agent that reaction mixture is carried secretly enters settling vessel 5 top dilute phase space and carries out secondary separation through cyclonic separator 8, gas product after separation enters collection chamber 9 through the outlet of cyclonic separator 8, is drawn by product gas outlet 10.Catalyzer after being separated from cyclonic separator 8 returns the lower region of settling vessel 5 through the dipleg of cyclonic separator 8.The reclaimable catalyst of the C bottom, negative area in settling vessel 5 enters stripper 11, through from after the stripped vapor stripping of stripped vapor entrance 14, enter revivifier (in figure, revivifier omits) through inclined tube 12 to be generated, regenerator enters CO gas coupling producing oxalic ester fluidized-bed reactor emulsion zone A through regenerator sloped tube 12.In addition, the partially catalyzed agent in settling vessel 5 enters bottom CO gas coupling producing oxalic ester fluidized-bed reactor emulsion zone A and continues to react with catalyst mix after interchanger 3 heat exchange, and whole process circulation is carried out.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
With the device shown in Fig. 1, employing palladium content is the palladium Supported alumina fluid catalyst of 0.5%, its average diameter of particles is 50 microns, methyl alcohol is terminator, be raw material with the mixed gas that the mol ratio of CO and methyl nitrite is 1.2: 1, the weight ratio of raw material and terminator is 10: 1, and terminator feeding temperature is 40 DEG C, be 130 DEG C in temperature of reaction, reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of-0.08MPa, and raw material and catalyst exposure, react, and its reaction result is: the selectivity of dimethyl oxalate is 99.2%, the space-time yield of dimethyl oxalate is 800 grams/(gram catalyzer. hour).
[embodiment 2]
With the device shown in Fig. 1, employing palladium content is the palladium Supported alumina fluid catalyst of 0.3%, its average diameter of particles is 80 microns, ethanol is terminator, be raw material with the mixed gas that the mol ratio of CO and ethyl nitrite is 0.6: 1, the weight ratio of raw material and terminator is 5: 1, and terminator feeding temperature is 40 DEG C, temperature of reaction 120 DEG C, reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.03MPa, and raw material and catalyst exposure, react, and its reaction result is: the selectivity of oxalic acid diethyl ester is 98.8%, the space-time yield of dimethyl oxalate is 710 grams/(gram catalyzer. hour).
[embodiment 3]
With the device shown in Fig. 1, employing palladium content is the palladium Supported alumina fluid catalyst of 0.2%, its average diameter of particles is 150 microns, water is terminator, be raw material with the mixed gas that the mol ratio of CO and methyl nitrite is 2.0: 1, the weight ratio of raw material and terminator is 50: 1, and terminator feeding temperature is 60 DEG C, be 150 DEG C in temperature of reaction, reaction volume air speed is 6000 hours
-1, reaction pressure is under the condition of 0.5MPa, and raw material and catalyst exposure, react, and its reaction result is: the selectivity of dimethyl oxalate is 99.1%, the space-time yield of dimethyl oxalate is 880 grams/(gram catalyzer. hour).
[embodiment 4]
With the device shown in Fig. 1, employing palladium content is the palladium Supported alumina fluid catalyst of 0.2%, its average diameter of particles is 180 microns, methyl alcohol is terminator, be raw material with the mixed gas that the mol ratio of CO and methyl nitrite is 3.0: 1, the weight ratio of raw material and terminator is 100: 1, and terminator feeding temperature is 20 DEG C, be 160 DEG C in temperature of reaction, reaction volume air speed is 4000 hours
-1, reaction pressure is under the condition of 0.8MPa, and raw material and catalyst exposure, react, and its reaction result is: the selectivity of dimethyl oxalate is 99.4%, the space-time yield of dimethyl oxalate is 980 grams/(gram catalyzer. hour).
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just CO gas coupling producing oxalic ester reactor adopts fixed-bed reactor, and do not add terminator, reaction result is: the selectivity of dimethyl oxalate is 96.1%, the space-time yield of dimethyl oxalate is 705 grams/(gram catalyzer. hour).
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just CO gas coupling producing oxalic ester reactor adopts fixed-bed reactor, and do not add terminator, reaction result is: the selectivity of oxalic acid diethyl ester is 95.6%, the space-time yield of oxalic acid diethyl ester is 650 grams/(gram catalyzer. hour).
Claims (1)
1. the method for a CO gas gas-phase catalytic coupling producing oxalic ester, with fluidized bed reaction, employing palladium content is the palladium Supported alumina fluid catalyst of 0.5%, its average diameter of particles is 50 microns, and methyl alcohol is terminator, is raw material with the mixed gas that the mol ratio of CO and methyl nitrite is 1.2: 1, the weight ratio of raw material and terminator is 10: 1, terminator feeding temperature is 40 DEG C, is 130 DEG C in temperature of reaction, and reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of-0.08MPa, and raw material and catalyst exposure, react, and its reaction result is: the selectivity of dimethyl oxalate is 99.2%, and the space-time yield of dimethyl oxalate is 800 grams of/gram of catalyzer hour;
Wherein, described fluidized bed reaction comprises emulsion zone, zone of transition, negative area, material inlet, sparger or grid distributor, interchanger, riser tube, settling vessel, fast separating device, airway, cyclonic separator, collection chamber, product gas outlet, stripper, regenerator sloped tube, inclined tube to be generated, stripped vapor entrance, terminator inlet;
Raw material is introduced by material inlet, through gas distributor or grid distributor distribution laggard enter the emulsion zone A of fluidized-bed and catalyst exposure react, catalyzer and reaction mixture enter riser tube through zone of transition B; After the vortex quick separation device sharp separation of riser tube upper end, major part catalyzer enters the lower region of settling vessel C, the partially catalyzed agent that reaction mixture is carried secretly enters settling vessel top dilute phase space and carries out secondary separation through cyclonic separator, gas product after separation enters collection chamber through the outlet of cyclonic separator, is drawn by product gas outlet; Catalyzer after being separated from cyclonic separator returns the lower region of settling vessel through the dipleg of cyclonic separator; The reclaimable catalyst of the C bottom, negative area in settling vessel enters stripper, through from after the stripped vapor stripping of stripped vapor entrance, enters revivifier through inclined tube to be generated, and regenerator enters CO gas coupling producing oxalic ester fluidized-bed reactor emulsion zone A through regenerator sloped tube; In addition, the partially catalyzed agent in settling vessel enters bottom CO gas coupling producing oxalic ester fluidized-bed reactor emulsion zone A and continues to react with catalyst mix after interchanger heat exchange, and whole process circulation is carried out.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101279257A (en) * | 2008-03-27 | 2008-10-08 | 上海焦化有限公司 | Catalyst for synthesizing oxalic ester and preparation method and application thereof |
| CN101475472A (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 in gaseous phase |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
-
2011
- 2011-02-25 CN CN201110045609.7A patent/CN102649733B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101279257A (en) * | 2008-03-27 | 2008-10-08 | 上海焦化有限公司 | Catalyst for synthesizing oxalic ester and preparation method and application thereof |
| CN101475472A (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 in gaseous phase |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
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