CN102649082A - Method for enhancing activity of catalyst for preparing oxalic ester from CO - Google Patents
Method for enhancing activity of catalyst for preparing oxalic ester from CO Download PDFInfo
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Abstract
The invention relates to a method for enhancing activity of catalyst for preparing oxalic ester from CO, which mainly solves the problem that the space time yield of aiming product oxalic ester is low during the process of preparing oxalic ester by CO in the traditional technology. The invention adopts the technical scheme that mixed gases containing nitrite ester and CO are used as raw materials, and a mole ratio of nitrite ester to CO is larger than (0-1.5):1, under the conditions that the volume space velocity is 500-10,000h -1, the pressure is -0.05-1.5MPa, and the temperature is 60-180 DEG C, the reaction temperature is higher than normal reaction temperature by 3-30 DEG C, and is maintained for 0.1-100 hours, then the temperature is lowered to normal reaction temperature, and raw materials are contacted with the catalyst containing palladium to generate effluent containing oxalic ester; and carrier of the catalyst containing palladium is at least one selected from aluminium oxide, silicon oxide, molecular sieve, magnesium oxide and calcium oxide, the content of palladium is 0.02-0.8 percent in percentage by weight of the catalyst. According to the technical scheme, the problem is better solved, and the method can be applied in the industrial production of oxalic ester prepared by CO.
Description
Technical field
The present invention relates to a kind of raising CO producing oxalic ester catalyst activity method, particularly about a kind of method that improves CO system dimethyl oxalate or diethy-aceto oxalate catalyst activity.
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 coupling producing oxalic ester, 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 0.5MP, 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; By carbon monoxide oxidative coupling method synthesis of oxalate to become important research project in domestic one-carbon chemical and the organic chemical industry field; 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.
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; 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), the present invention is on the basis of lab scale research in early stage, is that background is carried out with the commercial production; Running examination is continuously amplified in mould examination and the pilot scale accomplished under the industrial operation condition; But the space-time yield of its oxalate 500 grams/(rise. hour), reactivity is lower, space-time yield is lower.
Although above-mentioned numerous research institution has obtained than much progress technically, the method that more effectively improves catalyst activity how rarely has report.
Summary of the invention
Technical problem to be solved by this invention be in the past in the document in CO producing oxalic ester process; There is the low technical problem of purpose product oxalate space-time yield; A kind of new raising CO producing oxalic ester catalyst activity method is provided, and this method has the high advantage of purpose product oxalate space-time yield in CO producing oxalic ester process.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of raising CO producing oxalic ester catalyst activity method; To contain nitrites and CO mol ratio be greater than 0～1.5: 1 mist is a raw material, is 500～10000 hours at volume space velocity
-1, pressure is-0.05～1.5MPa, temperature is under 60～180 ℃ of conditions; Adopt the raising reaction temperature to exceed 3～30 ℃ of well-defined reaction temps, and kept 0.1～100 hour, afterwards; Cool the temperature to former well-defined reaction temp, raw material is contacted with palladium-containing catalyst, generate the effluent that contains oxalate; Wherein, the carrier of palladium-containing catalyst is selected from least a in aluminium oxide, silica, molecular sieve, magnesia, the calcium oxide, and the content of palladium counts 0.02～0.8% with catalyst weight percentage.
In the technique scheme, the reaction condition preferable range is: volume space velocity is 1000～8000 hours
-1, pressure is 0～1.0MPa, temperature is 80～160 ℃; Nitrites and CO mol ratio preferable range are 0.1～1.0: 1 in the raw material; Adopt the raising reaction temperature to exceed 5～25 ℃ of well-defined reaction temp preferable range, and the maintenance preferred reaction time is 1～80 hour; Reaction condition more preferably scope is: volume space velocity is 2000～6000 hours
-1, pressure is 0～0.8MPa, temperature is 80～150 ℃; In the raw material nitrites and CO mol ratio more preferably scope be 0.2～0.8: 1.Adopt to improve reaction temperature exceed well-defined reaction temp more preferably temperature range be 10～25 ℃, and keep more preferably that the reaction time is 5～60 hours.
In the technique scheme, the carrier preferred version of palladium-containing catalyst is selected from least a in aluminium oxide, the silica, and more preferably scheme is selected from aluminium oxide; The content of palladium is 0.02～0.6% in catalyst weight percentage preferable range.
As everyone knows, the reaction of CO producing oxalic ester is complicated course of reaction, and key reaction comprises following a few step:
Coupling reaction:
2CO+2CH
3ONO→(COOCH
3)
2+2NO (1)
Oxidative esterification reaction:
2NO+2CH
3OH+1/2O
2→2CH
3ONO+H
2O (2)
The overall reaction equation is:
2CO+2CH
3OH+1/2O
2→(COOCH
3)
2+H2O (3)
Wherein, coupling reaction is typical exothermic reaction, and this process is the simultaneous reaction atmosphere of oxidation and reducing gas, and what catalyst adopted is noble metal catalyst, through discovering CH in the reaction system
3ONO is for promoting reaction to have important effect.Research finds that also along with the carrying out in reaction time, the catalytic activity of noble metal catalyst reduces sometimes in time gradually, thinks, the variation of catalyst activity has substantial connection with the variation of catalyst surface active component valence state.The present inventor is surprised to find in process of the test, when catalyst activity has reduction trend, through reaction temperature is improved 5～30 ℃; And behind the maintenance certain hour, return original reaction temperature again, activity of such catalysts will have to be recovered preferably and improves; Think that this is under the higher temperature state, the active sites of catalyst surface is in oxidation and the simultaneous reaction atmosphere of reducing gas; Owing to main reaction speed is quickened in the raising of temperature; Thereby further the catalytic activity of activated catalyst has been improved the valence state of catalytic reaction activity position, has improved the reaction efficiency of catalyst.
Adopt the inventive method; With the aluminium oxide is carrier; The palladium content of palladium-containing catalyst counts 0.02～0.8% with catalyst weight percentage, and to contain nitrites and CO mol ratio be greater than 0～1.5: 1 mist is a raw material, is 500～10000 hours at volume space velocity
-1, pressure is-0.05～1.5MPa, temperature is under 60～180 ℃ of conditions; Adopt the raising reaction temperature to exceed 3～30 ℃ of well-defined reaction temps, and kept 0.1～100 hour, afterwards; Cool the temperature to former reaction temperature, raw material is contacted with palladium-containing catalyst, generate the effluent that contains oxalate.Its result does, the space-time yield of oxalate greater than 800 grams/(hour. rise), the selectivity of oxalate can reach more than 99%, has obtained better technical effect.
Through embodiment and Comparative Examples the present invention is done further elaboration below, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
Preparation of Catalyst:
Ferric nitrate is dissolved in the water, is heated to 80 ℃, the vacuum rotary dipping is at α-Al of 5 millimeters
2O
3On the bead, then in 120 ℃ of dryings 4 hours.Potassium chloride and ammonium chloropalladate are dissolved in the water respectively, and using the HCl regulator solution to make its pH value is about 4, then this solution is heated to 80 ℃; Be impregnated into once more on the carrier, then in 140 ℃ of dryings 4 hours, then 450 ℃ of roastings 4 hours; Reduce to room temperature, obtain required catalyst, its conversion is metal meter (below identical); With the catalyst weight is benchmark, and its weight consists of: 0.41%Pd+0.20%K+0.25%Fe/ α-Al
2O
3
Take by weighing the above-mentioned catalyst that makes 10 grams, the diameter of packing into is that the driving procatalyst is in 100 ml/min in 18 millimeters the tubular reactor; Hydrogen molar content 20%; Under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature 6 hours.Afterwards, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.1MPa, temperature is 120 ℃, methyl nitrite and CO mol ratio are reaction after 1000 hours under 0.5: 1 the condition, its result does, the space-time yield of dimethyl oxalate be 810 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.8%.Afterwards, reaction temperature is improved 10 ℃, and kept 20 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of dimethyl oxalate be 830 grams/(hour. rise), the selectivity of dimethyl oxalate is 99.1%.
[embodiment 2]
Make according to [embodiment 1] identical method and to consist of 0.16%Pd+0.15%Fe/ α-Al
2O
3Required catalyst.
Take by weighing the above-mentioned catalyst that makes 10 grams, the diameter of packing into is that the driving procatalyst is in 100 ml/min in 18 millimeters the tubular reactor; Hydrogen molar content 20%; Under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature 6 hours; Afterwards, catalyst is 1500 hours at volume space velocity
-1, pressure is-0.05MPa, temperature is 130 ℃, methyl nitrite and CO mol ratio are reaction after 800 hours under 0.6: 1 the condition, its result does, the space-time yield of dimethyl oxalate be 810 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.1%.Afterwards, reaction temperature is improved 20 ℃, and kept 10 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of dimethyl oxalate be 855 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.8%.
[embodiment 3]
Make according to [embodiment 1] identical method and to consist of 0.34%Pd+1.0%K+0.46%Mn/ α-Al
2O
3Required catalyst.
Take by weighing the above-mentioned catalyst that makes 10 grams; The diameter of packing into is in 18 millimeters the tubular reactor, and the driving procatalyst is in 100 ml/min, hydrogen molar content 20%; Under nitrogen molar content 80% condition; Be raised to 300 ℃ from room temperature with 3 ℃/minute, after the constant temperature 6 hours, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.5MPa, temperature is 135 ℃, methyl nitrite and CO mol ratio are reaction after 2000 hours under 0.8: 1 the condition, its result does, the space-time yield of dimethyl oxalate be 900 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.5%.Afterwards, reaction temperature is improved 30 ℃, and kept 10 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of dimethyl oxalate be 1000 grams/(hour. rise), the selectivity of dimethyl oxalate is 99.2%.
[embodiment 4]
Make according to [embodiment 1] identical method and to consist of the magnesian required catalyst of 0.15%Pd+0.3%Ba+0.2%Fe/.
Take by weighing the above-mentioned catalyst that makes 10 grams; The diameter of packing into is in 18 millimeters the tubular reactor, and the driving procatalyst is in 100 ml/min, hydrogen molar content 20%; Under nitrogen molar content 80% condition; Be raised to 300 ℃ from room temperature with 3 ℃/minute, after the constant temperature 6 hours, catalyst is 5000 hours at volume space velocity
-1, pressure is 0.8MPa, temperature is 150 ℃, methyl nitrite and CO mol ratio are reaction after 1000 hours under 0.9: 1 the condition, its result does, the space-time yield of dimethyl oxalate be 1010 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.3%.Afterwards, reaction temperature is improved 10 ℃, and kept 85 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of dimethyl oxalate be 1108 grams/(hour. rise), the selectivity of dimethyl oxalate is 99.3%.
[embodiment 5]
Make according to [embodiment 1] identical method and to consist of 0.8%Pd+10%Ce+0.51%Fe/TiO
2Required catalyst.
Take by weighing the above-mentioned catalyst that makes 10 grams; The diameter of packing into is in 18 millimeters the tubular reactor, and the driving procatalyst is in 100 ml/min, hydrogen molar content 20%; Under nitrogen molar content 80% condition; Be raised to 300 ℃ from room temperature with 3 ℃/minute, after the constant temperature 6 hours, catalyst is 8000 hours at volume space velocity
-1, pressure is 0.2MPa, temperature is 165 ℃, nitrous ether (ethyl nitrite) and CO mol ratio are reaction after 1000 hours under 0.8: 1 the condition, its result does, the space-time yield of diethy-aceto oxalate be 990 grams/(hour. rise), the selectivity of diethy-aceto oxalate is 98.1%.Afterwards, reaction temperature is improved 5 ℃, and kept 90 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of diethy-aceto oxalate be 1110 grams/(hour. rise), the selectivity of diethy-aceto oxalate is 99.1%.
[embodiment 6]
Make according to [embodiment 1] identical method and to consist of 0.8%Pd+0.003%Zr+0.25%Fe/ α-Al
2O
3Required catalyst.
Take by weighing the above-mentioned catalyst that makes 10 grams; The diameter of packing into is in 18 millimeters the tubular reactor, and the driving procatalyst is in 100 ml/min, hydrogen molar content 20%; Under nitrogen molar content 80% condition; Be raised to 300 ℃ from room temperature with 3 ℃/minute, after the constant temperature 6 hours, catalyst is 4000 hours at volume space velocity
-1, pressure is 0.4MPa, temperature is 135 ℃, nitrous ether (ethyl nitrite) and CO mol ratio are reaction 1000 hours under 0.6: 1 the condition, its result does, the space-time yield of diethy-aceto oxalate be 950 grams/(hour. rise), the selectivity of diethy-aceto oxalate is 97.9%.Afterwards, reaction temperature is improved 15 ℃, and kept 60 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of diethy-aceto oxalate be 1000 grams/(hour. rise), the selectivity of diethy-aceto oxalate is 99.3%.
[embodiment 7]
Make according to [embodiment 1] identical method and to consist of 0.6%Pd+0.08%Fe/ α-Al
2O
3Required catalyst.
Take by weighing the above-mentioned catalyst that makes 10 grams; The diameter of packing into is in 18 millimeters the tubular reactor, and the driving procatalyst is in 100 ml/min, hydrogen molar content 20%; Under nitrogen molar content 80% condition; Be raised to 300 ℃ from room temperature with 3 ℃/minute, after the constant temperature 6 hours, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.1MPa, temperature is 125 ℃, methyl nitrite and CO mol ratio are reaction after 1000 hours under 0.6: 1 the condition, its result does, the space-time yield of dimethyl oxalate be 910 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.3%.Afterwards, reaction temperature is improved 10 ℃, and kept 80 hours, then, be cooled to former reaction temperature again, this moment, reaction result was: the space-time yield of dimethyl oxalate be 950 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.8%.
[comparative example 1]
Adopt with [embodiment 7] identical catalyst and condition, take by weighing catalyst 10 grams that make, the diameter of packing into is in 18 millimeters the tubular reactor; The driving procatalyst is in 100 ml/min; Hydrogen molar content 20% under nitrogen molar content 80% condition, is raised to 300 ℃ from room temperature with 3 ℃/minute; After the constant temperature 6 hours, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.1MPa, temperature is 125 ℃, methyl nitrite and CO mol ratio are reaction after 1000 hours under 0.6: 1 the condition, its result does, the space-time yield of dimethyl oxalate be 910 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.3%.Afterwards, reaction condition is constant, proceed to react 800 hours after, this moment, reaction result was: the space-time yield of dimethyl oxalate be 905 grams/(hour. rise), the selectivity of dimethyl oxalate is 98.0%.
Claims (4)
1. one kind is improved CO producing oxalic ester catalyst activity method, and to contain nitrites and CO mol ratio be greater than 0～1.5: 1 mist is a raw material, is 500～10000 hours at volume space velocity
-1, pressure is-0.05～1.5MPa, temperature is under 60～180 ℃ of conditions; Adopt the raising reaction temperature to exceed 3～30 ℃ of well-defined reaction temps, and kept 0.1～100 hour, afterwards; Cool the temperature to former well-defined reaction temp, raw material is contacted with palladium-containing catalyst, generate the effluent that contains oxalate; Wherein, the carrier of palladium-containing catalyst is selected from least a in aluminium oxide, silica, molecular sieve, magnesia, the calcium oxide, and the content of palladium counts 0.02～0.8% with catalyst weight percentage.
2. according to the said raising of claim 1 CO producing oxalic ester catalyst activity method, it is characterized in that volume space velocity is 1000～8000 hours
-1, pressure is 0～1.0MPa, temperature is 80～160 ℃; Nitrites and CO mol ratio are 0.1～1.0: 1 in the raw material; Adopt the raising reaction temperature to exceed 5～25 ℃ of well-defined reaction temps, and kept 1～80 hour.
3. according to the said raising of claim 2 CO producing oxalic ester catalyst activity method, it is characterized in that volume space velocity is 2000～6000 hours
-1, pressure is 0～0.8MPa, temperature is 80～150 ℃; Nitrites and CO mol ratio are 0.2～0.8: 1 in the raw material; Adopt the raising reaction temperature to exceed 10～25 ℃ of well-defined reaction temps, and kept 5～60 hours.
4. according to the said raising of claim 1 CO producing oxalic ester catalyst activity method, the carrier that it is characterized in that palladium-containing catalyst is selected from least a in aluminium oxide, the silica, and the content of palladium counts 0.02～0.6% with catalyst weight percentage.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055851A (en) * | 2013-01-14 | 2013-04-24 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing oxalic ester through oxidative coupling of CO gas phase as well as preparation and application method thereof |
| CN106423156A (en) * | 2016-08-27 | 2017-02-22 | 宁波中科远东催化工程技术有限公司 | Catalyst for catalytically synthesizing dimethyl oxalate by CO gas phase and preparation method and application of catalyst |
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| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | Method for preparing diethyl oxalate by coupling CO |
| 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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| US4507494A (en) * | 1982-01-26 | 1985-03-26 | Ube Industries, Ltd. | Process for the production of a diester of oxalic acid |
| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | Method for preparing diethyl oxalate by coupling CO |
| 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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055851A (en) * | 2013-01-14 | 2013-04-24 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing oxalic ester through oxidative coupling of CO gas phase as well as preparation and application method thereof |
| CN106423156A (en) * | 2016-08-27 | 2017-02-22 | 宁波中科远东催化工程技术有限公司 | Catalyst for catalytically synthesizing dimethyl oxalate by CO gas phase and preparation method and application of catalyst |
| CN106423156B (en) * | 2016-08-27 | 2019-03-05 | 宁波中科远东催化工程技术有限公司 | The preparation method of catalyst for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method |
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