CN102649056B - The catalyst of CO preparing oxalate coupling reaction - Google Patents
The catalyst of CO preparing oxalate coupling reaction Download PDFInfo
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- CN102649056B CN102649056B CN201110045081.3A CN201110045081A CN102649056B CN 102649056 B CN102649056 B CN 102649056B CN 201110045081 A CN201110045081 A CN 201110045081A CN 102649056 B CN102649056 B CN 102649056B
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Abstract
The present invention relates to a kind of catalyst of CO preparing oxalate coupling reaction.Mainly solve in conventional art and there is the low technical problem of object selectivity of product.The present invention comprises carrier, active component and auxiliary agent by adopting catalyst, and by weight percentage, catalyst comprises following component: (a) is selected from palladium is active component, and be catalyst weight in simple substance consumption 0.003 ~ 1.5%; B () is selected from praseodymium or neodymium is auxiliary agent, and be catalyst weight in simple substance consumption 0.005 ~ 10%; The carrier of (c) 89 ~ 99.5%; Wherein, the composite carrier of support selected from alumina and silica, and the weight ratio of aluminium oxide and silica is the technical scheme of 0.01 ~ 120: 1, solves this problem preferably, can be used for increasing production in the industrial production of oxalate.
Description
Technical field
The present invention relates to a kind of catalyst of CO preparing oxalate coupling reaction, particularly about the catalyst of CO and methyl nitrite or nitrous ether (ethyl nitrite) coupling production dimethyl oxalate or diethy-aceto oxalate.
Background technology
Oxalate is important Organic Chemicals, produces various dyestuff, medicine, important solvent in a large number for fine chemistry industry, extractant and various intermediate.Enter 21 century, oxalate is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, oxalate ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high-quality slow chemical fertilizer oxalyl ammonia.Oxalate can also be used as solvent, produces medicine and dyestuff intermediate etc., such as, carries out various condensation reaction with fatty acid ester, hexamethylene acetophenone, amido alcohol and many heterocyclic compounds.It can also synthesize at the chest acyl alkali being pharmaceutically used as hormone.In addition, oxalate 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 oxalate utilizes oxalic acid to prepare with alcohol generation esterification, and production technology cost is high, and energy consumption is large, and seriously polluted, raw material utilizes unreasonable.For many years, people's, process route 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 method.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 course of reaction, catalyst easily runs off.The vapor phase method most advantage of CO preparing oxalate coupling reaction, company of external Ube Industries Ltd. and Italian Montedisons SPA have carried out vapor phase method 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 oxalate 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 oil product, Appropriate application coal and natural gas resource, 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 selectivity, and improving the aspects such as the activity of catalyst 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 method, CO is under the participation of nitrous ether (ethyl nitrite), under the catalysis of bimetal supported catalyst, coupling oxalic diethylester crude product, reaction is self-closing circulating process, CO gas enters coupler reactor with the nitrous ether (ethyl nitrite) from regeneration reactor through mixing preheating, after reaction, gas is through condensation separation, obtain water white diethy-aceto oxalate lime set, fixed gas containing NO enters regeneration reactor, in regeneration reactor and ethanol, oxygen reaction generation nitrous ether (ethyl nitrite) recycles back coupler reactor and uses continuously, but the conversion per pass of this technology CO is 20 ~ 60%, object selectivity of product is about 96%, all need to be improved further.
Document CN95116136.9 discloses the catalyst of a kind of oxalate synthesis, selects Zr to make auxiliary agent, develops novel Pd-Zr/Al by infusion process
2o
3catalyst.It is adopt fixed-bed reactor that this catalyst reacts as carbon monoxide and nitrites synthesis of oxalic ester by gaseous catalysis.But the yield of its oxalate of catalyst adopted in this patent is lower, and require higher to the impurity of unstripped gas, the selective of product oxalate is 95%, and the conversion per pass of nitrites is up to 64%, all needs to be improved further.
Summary of the invention
Technical problem to be solved by this invention is the selective low problem of oxalate existed in previous literature, provides a kind of catalyst of new CO preparing oxalate coupling reaction.This catalyst has the selective high advantage of oxalate.
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 catalyst of CO preparing oxalate coupling reaction, comprises carrier, active component and auxiliary agent, and by weight percentage, catalyst comprises following component:
A) being selected from palladium is active component, be catalyst weight in simple substance consumption 0.003 ~ 1.5%;
B) praseodymium is selected from or neodymium is auxiliary agent, be catalyst weight in simple substance consumption 0.005 ~ 10%;
C) carrier of 89 ~ 99.5%;
Wherein, the composite carrier of support selected from alumina and silica, and the weight ratio of aluminium oxide and silica is 0.01 ~ 120: 1.
In technique scheme, carrier is preferably selected from the composite carrier of aluminium oxide and silica, and the weight ratio of aluminium oxide and silica is 10 ~ 100: 1, and its specific surface preferable range is 2 ~ 400 meters squared per gram.Palladium active component, the preferable range being catalyst weight in simple substance consumption is 0.1 ~ 1%.Praseodymium or neodymium auxiliary agent, the preferable range being catalyst weight in simple substance consumption is 0.01 ~ 5%.
The preparation process of the catalyst of CO preparing oxalate coupling reaction is as follows:
A) be mixed with maceration extract with the soluble-salt of palladium and praseodymium or neodymium by metering, the pH value adjusting maceration extract is 0.8 ~ 9;
B) carrier is soaked in maceration extract;
C) after drying, roasting under air or nitrogen atmosphere.
The catalyst of CO preparing oxalate coupling reaction of the present invention, in turn include the following steps: according to the load capacity of catalyst activity metal component and auxiliary agent, select the halide of praseodymium or neodymium and Metal Palladium, nitrate, acetate or oxalates and water to be mixed with hybrid infusion solution.In order to prevent Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide precipitation, generally also needing to add a small amount of sour accordingly with metal salt anion in maceration extract, making the pH value of the aqueous solution be between 0.8 ~ 9.Then carrier is immersed in the maceration extract prepared, to ensure that maceration extract energy uniform load is on carrier.After abundant absorbing load, take out carrier, drop a hint and middlely naturally to dry, after 120 DEG C of dryings, through roasting, just can obtain CO preparing oxalate coupling reaction catalyst of the present invention.
The discovery that present inventor is surprised in research process, adopt the composite carrier being selected from aluminium oxide and silica be the catalyst prepared of carrier in the course of reaction of CO coupling producing oxalic ester, oxalate selective has to be improved preferably.
Adopt technical scheme of the present invention, the composite carrier being selected from aluminium oxide and silica is adopted to be palladium noble metal catalyst prepared by carrier, with the mist containing nitrites and CO for raw material, be 110 ~ 160 DEG C in reaction temperature, 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, nitrites and CO react oxalic ester, and the selective of oxalate is 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.
Detailed description of the invention
[embodiment 1]
To take average specific surface area be 100 grams of aluminium oxide of 68 meters squared per gram and the weight ratio of silica is the composite carrier of 5: 1, by 0.1wt%Pd+0.3wt%Pr/ composite carrier content Kaolinite Preparation of Catalyst, its step is as follows: select palladium nitrate and praseodymium nitrate, load capacity according to Pd and praseodymium prepares maceration extract, fixed in order to prevent Hydrolysis Reactions of Metal-ions generation hydroxide or oxide from sinking, a small amount of nitric acid is added in maceration extract, make the pH=0.8 of maceration extract, composite carrier is put into the mixed impregnant liquor prepared and soak a period of time, then take out to put and dry in atmosphere, dry, at air, roasting under nitrogen or argon gas atmosphere, just catalyst A is made.
[embodiment 2]
To take average specific surface area be 100 grams of aluminium oxide of 210 meters squared per gram and the weight ratio of silica is the composite carrier of 25: 1, by 0.3wt%Pd+0.8wt%Pr/ composite carrier content Kaolinite Preparation of Catalyst, its step is as follows: select palladium nitrate and praseodymium nitrate, load capacity according to Pd and praseodymium prepares maceration extract, fixed in order to prevent Hydrolysis Reactions of Metal-ions generation hydroxide or oxide from sinking, a small amount of nitric acid is added in maceration extract, make the pH=6 of maceration extract, composite carrier is put into the mixed impregnant liquor prepared and soak a period of time, then take out to put and dry in atmosphere, dry, at air, roasting under nitrogen or argon gas atmosphere, just catalyst B is made.
[embodiment 3]
To take average specific surface area be 100 grams of aluminium oxide of 280 meters squared per gram and the weight ratio of silica is the composite carrier of 30: 1, by 0.8wt%Pd+2.5wt%Pr/ composite carrier content Kaolinite Preparation of Catalyst, its step is as follows: select palladium bichloride and praseodymium nitrate, load capacity according to Pd and praseodymium prepares maceration extract, fixed in order to prevent Hydrolysis Reactions of Metal-ions generation hydroxide or oxide from sinking, a small amount of nitric acid is added in maceration extract, make the pH=3 of maceration extract, composite carrier is put into the mixed impregnant liquor prepared and soak a period of time, then take out to put and dry in atmosphere, dry, at air, roasting under nitrogen or argon gas atmosphere, just catalyst C is made.
[embodiment 4]
To take average specific surface area be 100 grams of aluminium oxide of 17 meters squared per gram and the weight ratio of silica is the composite carrier of 85: 1, by 0.3wt%Pd+3wt%Nd/ composite carrier content Kaolinite Preparation of Catalyst, its step is as follows: select palladium nitrate and neodymium nitrate, load capacity according to Pd and neodymium prepares maceration extract, fixed in order to prevent Hydrolysis Reactions of Metal-ions generation hydroxide or oxide from sinking, a small amount of nitric acid is added in maceration extract, make the pH=2 of maceration extract, composite carrier is put into the mixed impregnant liquor prepared and soak a period of time, then take out to put and dry in atmosphere, dry, at air, roasting under nitrogen or argon gas atmosphere, just catalyst D is made.
[embodiment 5]
To take average specific surface area be 100 grams of aluminium oxide of 11 meters squared per gram and the weight ratio of silica is the composite carrier of 95: 1, by 0.2wt%Pd+1wt%Nd/ composite carrier content Kaolinite Preparation of Catalyst, its step is as follows: select palladium nitrate and neodymium nitrate, load capacity according to Pd and neodymium prepares maceration extract, fixed in order to prevent Hydrolysis Reactions of Metal-ions generation hydroxide or oxide from sinking, a small amount of nitric acid is added in maceration extract, make the pH=4 of maceration extract, composite carrier is put into the mixed impregnant liquor prepared and soak a period of time, then take out to put and dry in atmosphere, dry, at air, roasting under nitrogen or argon gas atmosphere, just catalyst E is made.
[embodiment 6]
To take average specific surface area be 100 grams of aluminium oxide of 13 meters squared per gram and the weight ratio of silica is the composite carrier of 110: 1, by 0.2wt%Pd+0.1wt%Pr/ composite carrier content Kaolinite Preparation of Catalyst, its step is as follows: select palladium bichloride and praseodymium nitrate, load capacity according to Pd and praseodymium prepares maceration extract, fixed in order to prevent Hydrolysis Reactions of Metal-ions generation hydroxide or oxide from sinking, a small amount of nitric acid is added in maceration extract, make the pH=2 of maceration extract, composite carrier is put into the mixed impregnant liquor prepared and soak a period of time, then take out to put and dry in atmosphere, dry, at air, roasting under nitrogen or argon gas atmosphere, just catalyst F is made.
[comparative example 1]
Adopt the identical catalyst formulation of embodiment 6, just the single silica support of carrier to be specific area be 350 meters squared per gram, the catalyst made is G.
Catalyst activity is tested:
The reaction of CO preparing oxalate coupling reaction is carried out in the stainless steel reaction pipe that internal diameter is 18 millimeters, the catalyst prepared by in-built 20 grams.Catalyst before the reaction first logical hydrogen reduce, then with the mol ratio of CO and methyl nitrite be the gaseous mixture of 1.2: 1 for raw material, reaction temperature 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.Reaction result is as shown in table 1:
The reactivity worth of table 1 catalyst
Claims (2)
1. a catalyst for CO preparing oxalate coupling reaction, comprises carrier, active component and auxiliary agent, and by weight percentage, catalyst comprises following component:
A) being selected from palladium is active component, be catalyst weight in simple substance consumption 0.1 ~ 1%;
B) praseodymium is selected from or neodymium is auxiliary agent, be catalyst weight in simple substance consumption 0.01 ~ 5%;
C) carrier of 89 ~ 99.5%;
Wherein, the composite carrier of support selected from alumina and silica, and the weight ratio of aluminium oxide and silica is 0.01 ~ 120: 1.
2. the catalyst of CO preparing oxalate coupling reaction according to claim 1, it is characterized in that the composite carrier of support selected from alumina and silica, and the weight ratio of aluminium oxide and silica is 10 ~ 100: 1, its specific surface is 2 ~ 400 meters squared per gram.
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| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
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