CN102649056A - Catalyst for preparing oxalate through coupling of CO (carbon monoxide) - Google Patents
Catalyst for preparing oxalate through coupling of CO (carbon monoxide) Download PDFInfo
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- CN102649056A CN102649056A CN2011100450813A CN201110045081A CN102649056A CN 102649056 A CN102649056 A CN 102649056A CN 2011100450813 A CN2011100450813 A CN 2011100450813A CN 201110045081 A CN201110045081 A CN 201110045081A CN 102649056 A CN102649056 A CN 102649056A
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Abstract
The invention relates to a catalyst for preparing oxalate through coupling of CO (carbon monoxide), which mainly solves the technical problem that in the prior art, the selectivity of a target product is low. The catalyst comprises a carrier, an active component and an accessory ingredient in percentage by weight: (a) the active component which is selected from palladium, and has the dosage being 0.003-1.5 percent of the weight of the catalyst in a metering manner of a simple substance; (b) the accessory ingredient which is selected from praseodymium or neodymium, and has the dosage being 0.005-10 percent of the weight of the catalyst in a metering manner of a simple substance; and (c) 89-99.5 percent of carrier, wherein the carrier is selected from a compound type carrier of aluminum oxide and silicon oxide, and the weight ratio of the aluminum oxide to the silicon oxide is 0.01-120:1. According to the technical scheme, the problem is better solved, and the catalyst can be applied in industrial production of production increase 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, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extractant and various intermediate.Get into 21 century, oxalate receives international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the oxalate ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxalyl ammonia.Oxalate can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty acid ester, hexamethylene acetophenone, amido alcohol and many heterocyclic compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the oxalate low-voltage hydrogenation can prepare crucial industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition oxalate utilizes oxalic acid to prepare with alcohol generation esterification, and the production technology cost is high, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking a process route that cost is low, environment is good always.The sixties in last century; The D.F.Fenton of U.S. Associated Oil Company finds; Carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative 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 relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyst is prone to run off in the course of reaction.The tool advantage of the vapor phase method of CO preparing oxalate coupling reaction, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase method research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
Along with carbon monoxide oxidative coupling legal system in the world is equipped with the research and development of oxalate technology, domestic many research institutions have also carried out research work to this field.According to the china natural resources characteristic distributions, be the feedstock production organic oxygen-containing compound with the carbon monoxide, for the pressure of alleviating oil product, rationally utilize coal and natural gas resource to have crucial strategic importance.At present; Become important research project in domestic one-carbon chemical and the organic chemical industry field by carbon monoxide oxidative coupling method synthesis of oxalate; Successively there are how tame research institution and research institutions to be devoted to catalyst development, process exploitation and the engineering amplification work in this field, and obtained bigger progress.
Although above-mentioned numerous research institution has obtained than much progress technically, technology itself still remains further to be improved and development, especially improves reaction selectivity how, and aspects such as raising activity of such catalysts all need further research and break through.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopts vapor phase method, and CO is under the participation of nitrous ether (ethyl nitrite); Under the catalysis of bimetallic loaded catalyst, coupling generates the diethy-aceto oxalate bullion, reacts to be self-enclosed cyclic process; CO gas with get into coupler reactor from the nitrous ether (ethyl nitrite) of regeneration reactor through mixing preheating; Reaction back gas obtains water white diethy-aceto oxalate lime set through condensation separation, and the fixed gas that contains NO gets into regeneration reactor; In regeneration reactor, recycle back coupler reactor and use continuously with ethanol, oxygen reaction generation nitrous ether (ethyl nitrite); But conversion per pass that should technology CO is 20～60%, and the purpose selectivity of product all remains further to be improved about 96%.
Document CN 95116136.9 discloses the catalyst of the synthetic usefulness of a kind of oxalate, selects for use Zr to make auxiliary agent, develops novel Pd-Zr/Al with infusion process
2O
3Catalyst.This catalyst is to adopt fixed-bed reactor as carbon monoxide and the reaction of nitrites synthesis of oxalic ester by gaseous catalysis.But the yield of its oxalate of catalyst that is adopted in this patent is lower, and the impurity of unstripped gas is had relatively high expectations, and the selectivity of product oxalate is 95%, and the conversion per pass of nitrites is up to 64%, all remains further to be improved.
Summary of the invention
Technical problem to be solved by this invention is the low problem of oxalate selectivity that in the past exists in the document, and a kind of catalyst of new CO preparing oxalate coupling reaction is provided.This catalyst has the high advantage of oxalate selectivity.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of catalyst of CO preparing oxalate coupling reaction, comprise carrier, active component and auxiliary agent, and by weight percentage, catalyst comprises following component:
A) being selected from palladium is active component, is 0.003～1.5% of catalyst weight in the simple substance consumption;
B) being selected from praseodymium or neodymium is auxiliary agent, is 0.005～10% of catalyst weight in the simple substance consumption;
C) 89～99.5% carrier;
Wherein, carrier is selected from the composite carrier of aluminium oxide and silica, and the weight ratio of aluminium oxide and silica is 0.01～120: 1.
In the 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.The palladium active component is that the preferable range of catalyst weight is 0.1～1% in the simple substance consumption.Praseodymium or neodymium auxiliary agent are that the preferable range of catalyst weight is 0.01～5% in the simple substance consumption.
The Preparation of catalysts process of CO preparing oxalate coupling reaction is following:
A) soluble-salt with palladium and praseodymium or neodymium is mixed with maceration extract by metering, and transferring the pH value of maceration extract is 0.8～9;
B) carrier is soaked in maceration extract;
C) after the 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:, select for use halide, nitrate, acetate or the oxalates of praseodymium or neodymium and Metal Palladium and water to be mixed with hybrid infusion solution according to the load capacity of catalyst activity metal component and auxiliary agent.In order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide precipitation, in maceration extract, generally also need add on a small quantity with metal salt anion acid accordingly, making pH value of aqueous solution is between 0.8～9.Be immersed in carrier in the maceration extract for preparing then, to guarantee that dipping fluid power uniform load is on carrier.After abundant absorbing load, take out carrier, dry naturally in dropping a hint, after 120 ℃ of dryings, pass through roasting, just can make CO preparing oxalate coupling reaction catalyst according to the invention.
Present inventor's surprised discovery in research process, adopt the composite carrier that is selected from aluminium oxide and silica be the catalyst of preparing carriers in the course of reaction of CO coupling producing oxalic ester, the selectivity of oxalate has preferably to be improved.
Adopt technical scheme of the present invention; The composite carrier that employing is selected from aluminium oxide and silica is the palladium noble metal catalyst of preparing carriers; With the mist that contains nitrites and CO is raw material, is 110～160 ℃ in reaction temperature, and volume space velocity is 1000～6000 hours
-1, reaction pressure is under the condition of-0.02～1.0MPa, and raw material contacts with catalyst, and nitrites and CO reaction generates oxalate in the raw material, and the selectivity of oxalate can obtain better technical effect greater than 99%.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
The weight ratio that takes by weighing average specific surface area and be 100 gram aluminium oxide and the silica of 68 meters squared per gram is 5: 1 a composite carrier; Prepare catalyst by 0.1wt%Pd+0.3wt%Pr/ composite carrier content; Its step is following: select palladium nitrate and praseodymium nitrate for use, according to the load capacity preparation maceration extract of Pd and praseodymium, in order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide is heavy fixed; In maceration extract, add a small amount of nitric acid; Make the pH=0.8 of maceration extract, composite carrier is put into the mixed impregnant liquor for preparing soak a period of time, take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process catalyst A.
[embodiment 2]
The weight ratio that takes by weighing average specific surface area and be 100 gram aluminium oxide and the silica of 210 meters squared per gram is 25: 1 a composite carrier; Prepare catalyst by 0.3wt%Pd+0.8wt%Pr/ composite carrier content; Its step is following: select palladium nitrate and praseodymium nitrate for use, according to the load capacity preparation maceration extract of Pd and praseodymium, in order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide is heavy fixed; In maceration extract, add a small amount of nitric acid; Make the pH=6 of maceration extract, composite carrier is put into the mixed impregnant liquor for preparing soak a period of time, take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process catalyst B.
[embodiment 3]
The weight ratio that takes by weighing average specific surface area and be 100 gram aluminium oxide and the silica of 280 meters squared per gram is 30: 1 a composite carrier; Prepare catalyst by 0.8wt%Pd+2.5wt%Pr/ composite carrier content; Its step is following: select palladium bichloride and praseodymium nitrate for use, according to the load capacity preparation maceration extract of Pd and praseodymium, in order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide is heavy fixed; In maceration extract, add a small amount of nitric acid; Make the pH=3 of maceration extract, composite carrier is put into the mixed impregnant liquor for preparing soak a period of time, take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process catalyst C.
[embodiment 4]
The weight ratio that takes by weighing average specific surface area and be 100 gram aluminium oxide and the silica of 17 meters squared per gram is 85: 1 a composite carrier; Prepare catalyst by 0.3wt%Pd+3wt%Nd/ composite carrier content; Its step is following: select palladium nitrate and neodymium nitrate for use, according to the load capacity preparation maceration extract of Pd and neodymium, in order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide is heavy fixed; In maceration extract, add a small amount of nitric acid; Make the pH=2 of maceration extract, composite carrier is put into the mixed impregnant liquor for preparing soak a period of time, take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process catalyst D.
[embodiment 5]
The weight ratio that takes by weighing average specific surface area and be 100 gram aluminium oxide and the silica of 11 meters squared per gram is 95: 1 a composite carrier; Prepare catalyst by 0.2wt%Pd+1wt%Nd/ composite carrier content; Its step is following: select palladium nitrate and neodymium nitrate for use, according to the load capacity preparation maceration extract of Pd and neodymium, in order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide is heavy fixed; In maceration extract, add a small amount of nitric acid; Make the pH=4 of maceration extract, composite carrier is put into the mixed impregnant liquor for preparing soak a period of time, take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process catalyst E.
[embodiment 6]
The weight ratio that takes by weighing average specific surface area and be 100 gram aluminium oxide and the silica of 13 meters squared per gram is 110: 1 a composite carrier; Prepare catalyst by 0.2wt%Pd+0.1wt%Pr/ composite carrier content; Its step is following: select palladium bichloride and praseodymium nitrate for use, according to the load capacity preparation maceration extract of Pd and praseodymium, in order to prevent that Hydrolysis Reactions of Metal-ions from generating hydroxide or oxide is heavy fixed; In maceration extract, add a small amount of nitric acid; Make the pH=2 of maceration extract, composite carrier is put into the mixed impregnant liquor for preparing soak a period of time, take out then to be placed in the air and dry, drying, roasting under air, nitrogen or argon gas atmosphere, just process catalyst F.
[comparative example 1]
Adopt the identical catalyst formulation of embodiment 6, just carrier is that specific area is the single silica support of 350 meters squared per gram, and the catalyst of processing is G.
The catalyst activity property testing:
It is to carry out in 18 millimeters the stainless steel reaction pipe that the CO preparing oxalate coupling reaction is reflected at internal diameter, in adorn the prepared catalyst of 20 grams.Catalyst earlier logical hydrogen before reaction reduces, and is that 1.2: 1 gaseous mixture is a raw material with the mol ratio of CO and methyl nitrite then, and 130 ℃ of reaction temperatures, the reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.2MPa, raw material contacts with catalyst, reacts.Reaction result is as shown in table 1:
The reactivity worth of table 1 catalyst
Claims (4)
1. the catalyst of a 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, is 0.003～1.5% of catalyst weight in the simple substance consumption;
B) being selected from praseodymium or neodymium is auxiliary agent, is 0.005～10% of catalyst weight in the simple substance consumption;
C) 89～99.5% carrier;
Wherein, carrier is selected from the composite carrier of aluminium oxide and silica, and the weight ratio of aluminium oxide and silica is 0.01～120: 1.
2. according to the catalyst of the said CO preparing oxalate coupling reaction of claim 1, it is characterized in that carrier is selected from the composite carrier of aluminium oxide 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.
3. according to the catalyst of the said CO preparing oxalate coupling reaction of claim 1, it is characterized in that palladium is an active component, is 0.1～1% of catalyst weight in the simple substance consumption.
4. according to the catalyst of the said CO preparing oxalate coupling reaction of claim 1, it is characterized in that praseodymium or neodymium auxiliary agent, is 0.01～5% of catalyst weight in the simple substance consumption.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607024A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through CO gas phase synthesis and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607024A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through CO gas phase synthesis and preparation method and application thereof |
| CN106607024B (en) * | 2015-10-21 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing oxalate by CO gas phase, preparation method and application |
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