CN102649082B - Method for enhancing activity of catalyst for preparing oxalic ester from CO - Google Patents
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- CN102649082B CN102649082B CN201110046446.4A CN201110046446A CN102649082B CN 102649082 B CN102649082 B CN 102649082B CN 201110046446 A CN201110046446 A CN 201110046446A CN 102649082 B CN102649082 B CN 102649082B
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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 improving CO dimethyl oxalate or diethy-aceto oxalate catalyst activity.
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 coupling producing oxalic ester, 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 0.5MP, 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, by Oxidation of Carbon Monoxide coupling method synthesis of oxalate to become research topic important in domestic one-carbon chemical and organic chemical industry field, 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.
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, the present 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, 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 comparatively much progress technically, rarely has report in the method how more effectively improving catalyst activity.
Summary of the invention
Technical problem to be solved by this invention be in previous literature in CO producing oxalic ester process, there is the technical problem that object product oxalate space-time yield is low, there is provided a kind of raising CO producing oxalic ester catalyst activity method newly, the method has the advantage that object product oxalate space-time yield is high in CO producing oxalic ester process.
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 raising CO producing oxalic ester catalyst activity method, with containing nitrites and CO mol ratio for being greater than the mist of 0 ~ 1.5: 1 for raw material, be 500 ~ 10000 hours at volume space velocity
-1, pressure is-0.05 ~ 1.5MPa, and temperature is under 60 ~ 180 DEG C of conditions, adopt raising reaction temperature to exceed well-defined reaction temp 3 ~ 30 DEG C, and keep 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 containing oxalate; Wherein, at least one in the support selected from alumina of palladium-containing catalyst, silica, molecular sieve, magnesia, calcium oxide, the content of palladium counts 0.02 ~ 0.8% with catalyst weight percent.
In technique scheme, reaction condition preferable range is: volume space velocity is 1000 ~ 8000 hours
-1, pressure is 0 ~ 1.0MPa, and temperature is 80 ~ 160 DEG C; In raw material, nitrites and CO mol ratio preferable range are 0.1 ~ 1.0: 1; Adopt raising reaction temperature to exceed well-defined reaction temp preferable range 5 ~ 25 DEG C, and keep the preferred reaction time to be 1 ~ 80 hour; Reaction condition more preferably scope is: volume space velocity is 2000 ~ 6000 hours
-1, pressure is 0 ~ 0.8MPa, and temperature is 80 ~ 150 DEG C; In raw material nitrites and CO mol ratio more preferably scope be 0.2 ~ 0.8: 1.Adopt improve reaction temperature exceed well-defined reaction temp more preferably temperature range be 10 ~ 25 DEG C, and keep the more preferably reaction time to be 5 ~ 60 hours.
In technique scheme, the carrier preferred version of palladium-containing catalyst is selected from least one in aluminium oxide, silica, and more preferably scheme is selected from aluminium oxide; The content of palladium in catalyst weight percent preferable range for 0.02 ~ 0.6%.
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)
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 oxidation and the simultaneous reaction atmosphere of reducing gas, and what catalyst adopted is noble metal catalyst, is found by research, CH in reaction system
3oNO carries out having important effect for promotion reaction.Research also finds, along with the carrying out in reaction time, the catalytic activity of noble metal catalyst reduces sometimes in time gradually, thinks, the change of catalyst activity has substantial connection with the change of catalyst surface active component valence state.Present inventor is surprised to find in process of the test, when catalyst activity has reduction trend, by reaction temperature is improved 5 ~ 30 DEG C, and after keeping certain hour, return original reaction temperature again, the activity of catalyst will have to be recovered preferably and improves, think, this is under higher temperature state, the active sites of catalyst surface is in oxidation and the simultaneous reaction atmosphere of reducing gas, main reaction speed is accelerated due to the raising of temperature, thus the catalytic activity of further activated catalyst, improve the valence state of catalytic reaction activity position, improve the reaction efficiency of catalyst.
Adopt the inventive method, take aluminium oxide as carrier, the palladium content of palladium-containing catalyst counts 0.02 ~ 0.8% with catalyst weight percent, with containing nitrites and CO mol ratio for being greater than the mist of 0 ~ 1.5: 1 for raw material, be 500 ~ 10000 hours at volume space velocity
-1, pressure is-0.05 ~ 1.5MPa, and temperature is under 60 ~ 180 DEG C of conditions, adopt raising reaction temperature to exceed well-defined reaction temp 3 ~ 30 DEG C, and keep 0.1 ~ 100 hour, afterwards, cool the temperature to former reaction temperature, raw material is contacted with palladium-containing catalyst, generate the effluent containing oxalate.Its result is, the space-time yield of oxalate be greater than 800 grams/(hour. rise), the selective of oxalate can reach more than 99%, achieves good technique effect.
Below by embodiment and comparative example, the invention will be further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
Catalyst preparing:
Be dissolved in by ferric nitrate in water, be heated to 80 DEG C, vacuum rotating is immersed in the α-Al of 5 millimeters
2o
3on bead, then in 120 DEG C of dryings 4 hours.Potassium chloride and ammonium chloropalladate are dissolved in the water respectively, solution is regulated to make its pH value be about 4 with HCl, then this solution is heated to 80 DEG C, is again impregnated on carrier, then in 140 DEG C of dryings 4 hours, then 450 DEG C of roastings 4 hours, be down to room temperature, obtain required catalyst, its conversion is metal meter (following identical), take catalyst weight as benchmark, its weight consists of: 0.41%Pd+0.20%K+0.25%Fe/ α-Al
2o
3.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, and driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, constant temperature 6 hours.Afterwards, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.1MPa, and temperature is 120 DEG C, methyl nitrite and CO mol ratio are react after 1000 hours under the condition of 0.5: 1, its result is, the space-time yield of dimethyl oxalate is 810 grams/(hour. rise), the selective of dimethyl oxalate is 98.8%.Afterwards, reaction temperature is improved 10 DEG C, and keep 20 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of dimethyl oxalate is 830 grams/(hour. rise), the selective of dimethyl oxalate is 99.1%.
[embodiment 2]
0.16%Pd+0.15%Fe/ α-Al is consisted of according to the method that [embodiment 1] is identical is obtained
2o
3required catalyst.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, constant temperature 6 hours, afterwards, catalyst is 1500 hours at volume space velocity
-1, pressure is-0.05MPa, and temperature is 130 DEG C, methyl nitrite and CO mol ratio are react after 800 hours under the condition of 0.6: 1, its result is, the space-time yield of dimethyl oxalate is 810 grams/(hour. rise), the selective of dimethyl oxalate is 98.1%.Afterwards, reaction temperature is improved 20 DEG C, and keep 10 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of dimethyl oxalate is 855 grams/(hour. rise), the selective of dimethyl oxalate is 98.8%.
[embodiment 3]
0.34%Pd+1.0%K+0.46%Mn/ α-Al is consisted of according to the method that [embodiment 1] is identical is obtained
2o
3required catalyst.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, after constant temperature 6 hours, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.5MPa, and temperature is 135 DEG C, methyl nitrite and CO mol ratio are react after 2000 hours under the condition of 0.8: 1, its result is, the space-time yield of dimethyl oxalate is 900 grams/(hour. rise), the selective of dimethyl oxalate is 98.5%.Afterwards, reaction temperature is improved 30 DEG C, and keep 10 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of dimethyl oxalate is 1000 grams/(hour. rise), the selective of dimethyl oxalate is 99.2%.
[embodiment 4]
The magnesian required catalyst of 0.15%Pd+0.3%Ba+0.2%Fe/ is consisted of according to the method that [embodiment 1] is identical is obtained.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, after constant temperature 6 hours, catalyst is 5000 hours at volume space velocity
-1, pressure is 0.8MPa, and temperature is 150 DEG C, methyl nitrite and CO mol ratio are react after 1000 hours under the condition of 0.9: 1, its result is, the space-time yield of dimethyl oxalate is 1010 grams/(hour. rise), the selective of dimethyl oxalate is 98.3%.Afterwards, reaction temperature is improved 10 DEG C, and keep 85 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of dimethyl oxalate is 1108 grams/(hour. rise), the selective of dimethyl oxalate is 99.3%.
[embodiment 5]
0.8%Pd+10%Ce+0.51%Fe/TiO is consisted of according to the method that [embodiment 1] is identical is obtained
2required catalyst.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, after constant temperature 6 hours, catalyst is 8000 hours at volume space velocity
-1, pressure is 0.2MPa, and temperature is 165 DEG C, nitrous ether (ethyl nitrite) and CO mol ratio are react after 1000 hours under the condition of 0.8: 1, its result is, the space-time yield of diethy-aceto oxalate is 990 grams/(hour. rise), the selective of diethy-aceto oxalate is 98.1%.Afterwards, reaction temperature is improved 5 DEG C, and keep 90 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of diethy-aceto oxalate is 1110 grams/(hour. rise), the selective of diethy-aceto oxalate is 99.1%.
[embodiment 6]
0.8%Pd+0.003%Zr+0.25%Fe/ α-Al is consisted of according to the method that [embodiment 1] is identical is obtained
2o
3required catalyst.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, after constant temperature 6 hours, catalyst is 4000 hours at volume space velocity
-1, pressure is 0.4MPa, and temperature is 135 DEG C, and nitrous ether (ethyl nitrite) and CO mol ratio are react 1000 hours under the condition of 0.6: 1, and its result is, the space-time yield of diethy-aceto oxalate is 950 grams/(hour. rise), the selective of diethy-aceto oxalate is 97.9%.Afterwards, reaction temperature is improved 15 DEG C, and keep 60 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of diethy-aceto oxalate is 1000 grams/(hour. rise), the selective of diethy-aceto oxalate is 99.3%.
[embodiment 7]
0.6%Pd+0.08%Fe/ α-Al is consisted of according to the method that [embodiment 1] is identical is obtained
2o
3required catalyst.
Take above-mentioned obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 DEG C from room temperature with 3 DEG C/min, after constant temperature 6 hours, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.1MPa, and temperature is 125 DEG C, methyl nitrite and CO mol ratio are react after 1000 hours under the condition of 0.6: 1, its result is, the space-time yield of dimethyl oxalate is 910 grams/(hour. rise), the selective of dimethyl oxalate is 98.3%.Afterwards, reaction temperature is improved 10 DEG C, and keep 80 hours, then, then be cooled to former reaction temperature, now reaction result is: the space-time yield of dimethyl oxalate is 950 grams/(hour. rise), the selective of dimethyl oxalate is 98.8%.
[comparative example 1]
Adopt with [embodiment 7] identical catalyst and condition, take obtained catalyst 10 grams, loading diameter is in the tubular reactor of 18 millimeters, driving procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, is raised to 300 DEG C from room temperature with 3 DEG C/min, after constant temperature 6 hours, catalyst is 3000 hours at volume space velocity
-1, pressure is 0.1MPa, and temperature is 125 DEG C, methyl nitrite and CO mol ratio are react after 1000 hours under the condition of 0.6: 1, its result is, the space-time yield of dimethyl oxalate is 910 grams/(hour. rise), the selective of dimethyl oxalate is 98.3%.Afterwards, reaction condition is constant, and proceed reaction after 800 hours, now reaction result is: the space-time yield of dimethyl oxalate is 905 grams/(hour. rise), the selective of dimethyl oxalate is 98.0%.
Claims (3)
1. improving a CO producing oxalic ester catalyst activity method, to be greater than 0 and be less than or equal to the mist of 1.5 for raw material containing nitrites and CO mol ratio, is 500 ~ 10000 hours at volume space velocity
-1, pressure is-0.05 ~ 1.5MPa, and temperature is under 60 ~ 180 DEG C of conditions, adopt raising reaction temperature to exceed well-defined reaction temp 3 ~ 30 DEG C, and keep 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 containing oxalate; Wherein, at least one in the support selected from alumina of palladium-containing catalyst, silica, the content of palladium counts 0.02 ~ 0.6% with catalyst weight percent.
2. improve CO producing oxalic ester catalyst activity method according to claim 1, it is characterized in that volume space velocity is 1000 ~ 8000 hours
-1, pressure is 0 ~ 1.0MPa, and temperature is 80 ~ 160 DEG C; In raw material, nitrites and CO mol ratio are 0.1 ~ 1.0: 1; Adopt raising reaction temperature to exceed well-defined reaction temp 5 ~ 25 DEG C, and keep 1 ~ 80 hour.
3. improve CO producing oxalic ester catalyst activity method according to claim 2, it is characterized in that volume space velocity is 2000 ~ 6000 hours
-1, pressure is 0 ~ 0.8MPa, and temperature is 80 ~ 150 DEG C; In raw material, nitrites and CO mol ratio are 0.2 ~ 0.8: 1; Adopt raising reaction temperature to exceed well-defined reaction temp 10 ~ 25 DEG C, and keep 5 ~ 60 hours.
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| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 CN201110046446.4A patent/CN102649082B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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