CN102649731B - Method for producing oxalate through CO gas phase coupling - Google Patents
Method for producing oxalate through CO gas phase coupling Download PDFInfo
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- CN102649731B CN102649731B CN201110045202.4A CN201110045202A CN102649731B CN 102649731 B CN102649731 B CN 102649731B CN 201110045202 A CN201110045202 A CN 201110045202A CN 102649731 B CN102649731 B CN 102649731B
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Abstract
The invention relates to a method for producing oxalate through CO gas phase coupling and mainly solves the technical problem of low objective product selectivity existing in the prior art. With the adoption of the technical scheme that the method for producing the oxalate through the CO gas phase coupling comprises the following steps that: mixed gas containing nitrite and CO is taken as a raw material, a fluidized bed reactor is adopted, 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 raw material is in contact with an assistant selected from rhenium, cobalt or silver and a precious metal catalyst selected from palladium for reaction to generate the oxalate, so the problem is better solved. The method can be used in the industrial production for increasing the yield of the oxalate.
Description
Technical field
The present invention relates to and a kind ofly produce the method for barkite by CO gas phase coupling, particularly about the method adopting fluidized-bed reactor by CO and methyl nitrite or ethyl nitrite coupling production dimethyl oxalate or oxalic acid diethyl ester.
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.
Summary of the invention
Technical problem to be solved by this invention is the problem that the barkite selectivity that exists in previous literature is low, provides a kind of method of being produced barkite by CO gas phase coupling newly.The method has the high advantage of barkite selectivity.
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 being produced barkite by CO gas phase coupling, with the mixed gas containing nitrous acid ester and CO for raw material, adopts fluidized-bed reactor, temperature of reaction 100 ~ 180 DEG C, volume space velocity is 500 ~ 10000 hours
-1, reaction pressure is that under the condition of-0.08 ~ 1.5MPa, raw material contacts with noble metal catalyst, reaction oxalic ester; Wherein, noble metal catalyst, comprises carrier, active ingredient and auxiliary agent, and by weight percentage, catalyzer comprises following component:
A) being selected from palladium is active ingredient, be catalyst weight in simple substance consumption 0.003 ~ 1%;
B) being selected from rhenium, cobalt or silver is auxiliary agent, be catalyst weight in simple substance consumption 0.005 ~ 10%;
C) carrier of 89 ~ 99.5%;
Wherein carrier is selected from ball-aluminium oxide, and alumina particle diameter average out to 20 ~ 300 microns.
In technique scheme, noble metal catalyst alumina catalyst support particle diameter preferable range average out to 30 ~ 200 microns; Active component palladium, be catalyst weight in simple substance consumption preferable range 0.02 ~ 0.8%.Auxiliary agent is preferably selected from rhenium or silver, and be catalyst weight in simple substance consumption preferable range 0.01 ~ 5%.
In technique scheme, the reaction conditions preferable range of fluidized-bed reactor is: temperature of reaction 110 ~ 160 DEG C, and volume space velocity is 1000 ~ 6000 hours-1, and reaction pressure is-0.02 ~ 1.0MPa; Reaction conditions more preferably scope is: temperature of reaction 110 ~ 150 DEG C, and volume space velocity is 2000 ~ 5000 hours
-1, reaction pressure is-0.01 ~ 0.5MPa.Containing in the mixed gas feed of nitrous acid ester and CO, the mol ratio of CO and nitrous acid ester is 0.5 ~ 5: 1; The preferable range of the mol ratio of CO and nitrous acid ester is 1.0 ~ 2: 1.Nitrous acid ester is selected from methyl nitrite, ethyl nitrite or its mixture, preferably from methyl nitrite.Fluidized-bed reactor is preferably selected from bubbling fluidized bed, turbulent fluidized bed, fast fluidized bed or riser reactor
The preparation method of catalyzer of the present invention is as follows:
Catalyst activity component palladium, promoter elements, can be dispersed on carrier by any method being suitable for obtaining surface impregnation.When preparing catalyzer of the present invention, any decomposable palladium compound can be used, as halogenide, nitrate, oxide compound etc.; Such as chlorine palladium acid sodium, tetrachloro-palladium acid sodium, potassium palladichloride, chlorine four ammonia palladium, palladous oxide, the acid of chlorine palladium, ammonium palladic chloride, the sub-palladium acid of chlorine.Auxiliary agent can be combined with carrier with random order.Can first platinum-impregnated Group Component on carrier surface, then again at one or more auxiliary agents of surface impregnation or modifier, also first one or more auxiliary agents or modifier can be flooded on carrier surface, then again in surface impregnation platinum-group component, palladium-impregnated component and auxiliary agent or modifier also can of course simultaneously.
Promotor there is no special restriction to its source, comparatively suitable with nitrate, oxalate, ammonium salt or muriate.Promotor can first load on carrier, also after palladium load, surface impregnation can be carried out again.Comparatively conventional method is first load cocatalyst, after drying and roasting, adopts Surface soaking method dipping containing palladium solution.Finally, by the catalyst precursor containing active ingredient first 80 ~ 140 DEG C of dryings 2 ~ 20 hours, then 180 ~ 700 DEG C of roastings 2 ~ 20 hours, namely obtain the catalyzer for the reaction of CO coupling producing oxalic ester.
Adopt technical scheme of the present invention, with the mixed gas containing nitrous acid ester and CO for raw material, adopt fluidized-bed reactor, be 110 ~ 160 DEG C in temperature of reaction, volume space velocity is 1000 ~ 6000 hours
-1, reaction pressure is under the condition of-0.02 ~ 1.0MPa, raw material and catalyst exposure, and in raw material, nitrous acid ester and CO react oxalic ester, and the selectivity of barkite can be greater than 99%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Be dissolved in by cobalt oxalate in water, be heated to 70 DEG C, vacuum rotating is immersed in the Al that average particulate diameter is 50 microns
2o
3on bead, then in 120 DEG C of dryings 6 hours.A certain amount of Palladous nitrate is dissolved in the water, its pH value is made to be about 4 with nitric acid regulator solution, then this solution is heated to 80 DEG C, again be immersed on carrier, then in 140 DEG C of dryings 8 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reductase 12 hour in 400 DEG C of hydrogen atmospheres, obtain catalyst A, consist of 0.17%Pd+0.28%Co/Al
2o
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 1.2: 1, 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: CO per pass conversion 78.4%, and the selectivity of dimethyl oxalate is 99.2%.
[embodiment 2]
Be dissolved in by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in water, be heated to 80 DEG C, vacuum rotating is immersed in the Al that average particulate diameter is 60 microns
2o
3on bead, then in 120 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in the water, its pH value is made to be about 4 with nitric acid regulator solution, then this solution is heated to 80 DEG C, again be immersed on carrier, then in 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reductase 12 hour in 400 DEG C of hydrogen atmospheres, obtain catalyst B, consist of 0.45%Pd+0.40%Co/Al
2o
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 1.5: 1, is 110 DEG C in temperature of reaction, and reaction volume air speed is 800 hours
-1, reaction pressure is under the condition of-0.05MPa, and raw material and catalyst exposure, react, and its reaction result is: CO per pass conversion 63.2%, and the selectivity of dimethyl oxalate is 99.7%.
[embodiment 3]
Be dissolved in the water by Silver Nitrate, vacuum impregnation is the Al of 100 microns at average particulate diameter
2o
3on bead, 140 DEG C of dryings 4 hours.Palladous nitrate is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer C, consist of 0.01%Pd+1%Ag/Al
2o
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 2: 1, and temperature of reaction 140 DEG C, reaction volume air speed is 3000 hours
-1, reaction pressure is under the condition of-0.02MPa, and raw material and catalyst exposure, react, and its reaction result is: CO per pass conversion 45.2%, and the selectivity of dimethyl oxalate is 99.1%.
[embodiment 4]
Be dissolved in the water by Silver Nitrate, vacuum rotating is immersed in the Al that average particulate diameter is 80 microns
2o
3on bead, 140 DEG C of dryings 4 hours.By sub-for chlorine palladium acid dissolve in the aqueous solution, again be immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduce 4 hours in 450 DEG C 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
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 4: 1, and temperature of reaction 160 DEG C, reaction volume air speed is 6000 hours
-1, reaction pressure is under the condition of 0.02MPa, and raw material and catalyst exposure, react, and its reaction result is: CO per pass conversion 22.2%, and the selectivity of dimethyl oxalate is 98.3%.
[embodiment 5]
Be dissolved in the water by nitric acid rhenium, vacuum rotating is immersed in the Al that average particulate diameter is 100 microns
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then 450 DEG C of roastings 4 hours, reduce 4 hours in 350 DEG C of hydrogen atmospheres, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer E, consist of 0.11%Pd+0.6%Re/Al
2o
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 1.3: 1, and temperature of reaction 170 DEG C, reaction volume air speed is 8000 hours
-1, reaction pressure is under the condition of 0.5MPa, and raw material and catalyst exposure, react, and its reaction result is: CO per pass conversion 74.6%, and the selectivity of dimethyl oxalate is 97.3%.
[embodiment 6]
Get the Al that 200 grams of average particulate diameters are 120 microns
2o
3on bead, be immersed in containing in 8.0 grams of Palladous nitrates, 14 grams of nitric acid rhenium aqueous solution, and regulate its pH value to be 2 with nitric acid, dry 4 hours at 140 DEG C after taking-up, then roasting 2 hours in 450 DEG C of air atmospheres, reduce 4 hours in 350 DEG C of hydrogen atmospheres, 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 obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 1.5: 1, and temperature of reaction 130 DEG C, reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.2MPa, and raw material and catalyst exposure, react, and its reaction result is: CO per pass conversion 63.8%, and the selectivity of dimethyl oxalate is 99.5%.
[embodiment 7]
Be dissolved in the water by Silver Nitrate, vacuum impregnation is the Al of 150 microns at average particulate diameter
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 2 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer G, consist of 0.8%Pd+10%Ag/Al
2o
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 1.3: 1, and temperature of reaction 120 DEG C, reaction volume air speed is 1500 hours
-1, reaction pressure is under the condition of 0.1MPa, and raw material and catalyst exposure, react, and its reaction result is: CO per pass conversion 73.9%, and the selectivity of dimethyl oxalate is 99.8%.
[embodiment 8]
Be dissolved in the water by nitric acid rhenium, vacuum impregnation is the Al of 200 microns at average particulate diameter
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer H, consist of 0.2%Pd+1%Re/Al
2o
3.Take obtained catalyzer 500 grams, be encased in fluidized-bed reactor, then with CO and methyl nitrite for raw material, wherein, the mol ratio of CO and methyl nitrite is 0.6: 1, and 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: CO per pass conversion 96.2%, and 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: CO per pass conversion 73.8%, and the selectivity of dimethyl oxalate is 96.1%.
Claims (4)
1. produced a method for barkite by CO gas phase coupling, with the mixed gas containing nitrous acid ester and CO for raw material, adopt fluidized-bed reactor, temperature of reaction 110 ~ 150 DEG C, volume space velocity is 2000 ~ 5000 hours
-1, reaction pressure is that under the condition of-0.01 ~ 0.5MPa, raw material contacts with noble metal catalyst, reaction oxalic ester; Wherein, noble metal catalyst, is made up of carrier, active ingredient and auxiliary agent, and by weight percentage, catalyzer is made up of following component:
A) being selected from palladium is active ingredient, be catalyst weight in simple substance consumption 0.003 ~ 1%;
B) rhenium or silver is selected from for auxiliary agent, be catalyst weight in simple substance consumption preferable range 0.01 ~ 5%;
C) carrier of 89 ~ 99.5%;
And above-mentioned each component sum is 100%;
Wherein carrier is selected from ball-aluminium oxide, and alumina particle diameter average out to 30 ~ 200 microns; Containing in the mixed gas feed of nitrous acid ester and CO, the mol ratio of CO and nitrous acid ester is 0.5 ~ 5: 1; Fluidized-bed reactor is selected from bubbling fluidized bed, turbulent fluidized bed, fast fluidized bed or riser reactor.
2. produced the method for barkite according to claim 1 by CO gas phase coupling, it is characterized in that noble metal catalyst activity group palladium, be catalyst weight in simple substance consumption 0.02 ~ 0.8%.
3. produce the method for barkite by CO gas phase coupling according to claim 1, it is characterized in that in the mixed gas feed containing nitrous acid ester and CO, the mol ratio of CO and nitrous acid ester is 1.0 ~ 2: 1.
4. produced the method for barkite according to claim 1 by CO gas phase coupling, it is characterized in that nitrous acid ester is selected from methyl nitrite, ethyl nitrite or its mixture.
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| CN105435783B (en) * | 2014-08-27 | 2018-02-13 | 中国石油化工股份有限公司 | The catalyst of CO gas phase coupling synthesis of oxalate |
| CN106914240A (en) * | 2015-12-25 | 2017-07-04 | 上海华谊能源化工有限公司 | A kind of catalyst of CO gas phase couplings synthesis of oxalate and preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| 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 |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101851160A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| 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 |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101851160A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst |
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