CN105727956A - Catalyst for preparing ethylene glycol through dimethyl oxalate gas phase hydrogenation, and preparation method and application thereof - Google Patents
Catalyst for preparing ethylene glycol through dimethyl oxalate gas phase hydrogenation, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing ethylene glycol through dimethyl oxalate gas phase hydrogenation. The catalyst comprises the following components, by mass: 20-70 wt% of CuO, 25-79 wt% of SiO2, and 1.0-5.0wt% of oxide of a metal auxiliary agent. The catalyst has a specific surface area of 100-500m<2>/g, a pore volume of 0.3-1.5mL/g, and a pore size of 1.0-15.0nm. According to the invention, a pore-expanding agent and an environment-friendly auxiliary agent are added during a preparation process, such that the pore structure of the catalyst is effectively improved. When the prepared catalyst is used in a reaction for preparing ethylene glycol through oxalate gas phase hydrogenation, catalyst activity and ethylene glycol selectivity can be effectively improved; catalyst bed layer temperature can be stabilized; impurity generation can be significantly inhibited; no adverse influence is caused on the mechanical strength of the catalyst; and the wear resistance of the catalyst is improved. The service life of the catalyst can be longer than 1 year, such that the needs of industrial production can be satisfied.
Description
Technical field
The preparation method that the present invention relates to a kind of preparing ethanediol by hydrogenating dimethyl oxalate catalyst, belongs to field of catalyst preparation.
Background technology
Ethylene glycol has another name called glycol, is a kind of no color or smell, pleasantly sweet liquid, can dissolve each other with arbitrary proportion with water.Ethylene glycol is of many uses, it it is a kind of important organic chemical industry's synthesis material, mainly for the manufacture of polyester fiber, antifreezing agent, nonionic surfactant, ethanolamine and explosive etc., it is also used for preparation low-freezing coolant (electromotor is used), also can be directly used as solvent.It addition, also have extensive use in tobacco industry, textile industry and cosmetic industry.
At present, the method producing ethylene glycol both at home and abroad is mainly oil-ethylene-ethylene oxide route.Legal also referred to as pressure (hydraulic) water by oxirane direct hydration method, this process route has unsurmountable shortcoming, is mainly manifested in technological process long, and water ratio (mol ratio of water and oxirane) is big, and energy consumption is high, and ethylene glycol relative selectivity is poor.Due to China's oil resource-constrained, and natural gas, coal resource relative abundance, therefore, development is with natural gas, coal resource producing synthesis gas thus preparing ethylene glycol process route, and to reducing ethylene energy consumption, saving petroleum-based energy has very great meaning.Wherein, synthesis gas prepares ethylene glycol route because of its reaction condition gentleness through oxalate method, and glycol selectivity is high and becomes the current focus studied.Lot of domestic and international company and research institution, such as E.I.Du Pont Company, Xue Fulong company, ARCO company, the emerging product in space portion, UCC company of the U.S., domestic University Of Tianjin carbon one Chemical Engineering Laboratory, this project has all been studied by Fujian Chinese Academy of Sciences structure of matter institute and East China University of Science, and wherein, the exploitation of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen is the difficult point of project.
The patent of the catalyst relating to oxalic ester hydrogenation synthesizing of ethylene glycol or ethyl glycolate has been reported, such as patent EP46983A1, clear 57-122939, JP06135895A2, US4677234 etc., its primary response approach generally acknowledged is: oxalate methyl glycollate ethylene glycol, can generate the by-product such as ethanol, butanediol therebetween.Patents mainly formula reporting catalyst and preparation method thereof, but it is higher to there is reaction hydrogen ester, the shortcomings such as liquid hourly space velocity (LHSV) is relatively low, and selectivity of product is relatively low, and catalyst life is short.European patent 0060787 and for example reports a kind of copper Si catalyst containing Cr, within 1986, ARCO company of the U.S. adopts Cu-Cr catalyst, domestic Chinese Academy of Sciences Fujian thing structure develops Cu-Cr catalyst in the nineties, completes the 200mL mould examination research work of ethyl oxalate Hydrogenation ethylene glycol.But above catalyst is short for equal service life, and all employ the unfriendly type auxiliary agent Cr of environment.
To produce higher alcohols by-product in preparing glycol by hydrogenating oxalate process, even if such by-product content very low (0.1%wt) also can have a strong impact on product quality and separation difficulty, energy consumption is big.Reporting a kind of catalyst in European patent 0060787, it can control higher alcohols mass fraction in the product is about 1%, but its shortcoming is the Cr element and the control condition harshness that need to add severe toxicity in its catalyst.At present, result of study indicates, and higher alcohols by-product selectivity is relevant with catalyst reaction bed temperature skewness.US Patent No. 4649226 describes a kind of molding additive of such catalyst, improves the intensity of catalyst, but control higher alcohols by-product is not acted on to some extent after using this interpolation implant.
According to bibliographical information, for porous catalyst, its aperture is divided into four kinds of types by different sizes: 1) active component is prone to the gross porosity road of loss；2) aperture is suitable for, the duct that active component can effectively play；3) though reactant can enter, but intermediate compound or product are subject to space restriction, it is easy to the tubulus of coking；4) when active component content is higher, precipitated state active precursor primary stricture, make the tubulus that activity can not play.As can be seen here, in Catalyst Design and preparation process, it is desirable to Pore-size Distribution concentrates on the duct of the second type.Suitable catalyst structure, is possible not only to extend the service life of catalyst, and the generation of some impurity can be played inhibitory action.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, a kind of dimethyl oxalate. gas phase hydrogenation is provided to produce ethylene glycol catalyst and preparation method thereof, by adding expanding agent and environmentally friendly auxiliary agent in preparation process, it is effectively improved the pore structure of catalyst, the catalyst of preparation is made to produce in glycol reaction process being applied to oxalate gas phase hydrogenation, the activity of catalyst and the selectivity of ethylene glycol can be effectively improved, rugged catalyst bed temperature, significantly inhibit the generation of impurity, catalytic mechanical intensity is had no adverse effect, improve catalyst anti-wear performance, and the service life of catalyst can reach more than 1 year, disclosure satisfy that industrial needs.
The present invention is achieved by the following technical solutions:
A kind of dimethyl oxalate. gas phase hydrogenation produces ethylene glycol catalyst, including each component of following weight/mass percentage composition:
CuO20～70wt%；
SiO225～79wt%；
Oxide 1.0～the 5.0wt% of metal promoter；
Described metal promoter is selected from metallic element Li, Na, K, Cs, Ba, Mn, Ni, Al, Ag and Zn；
Preferably, described metal promoter is selected from metallic element Li, Na, K, Cs, Ba, Ni.
The specific surface area of described catalyst is 100～500m2/ g, pore volume is 0.3～1.5mL/g, and aperture is 1.0～15.0nm.
Preferably, the specific surface area of described catalyst is 300-500m2/ g, pore volume is 0.3-0.7mL/g, and aperture is 4-6nm.
Preferably, described dimethyl oxalate. gas phase hydrogenation produces ethylene glycol catalyst, including each component of following weight/mass percentage composition:
CuO35～60wt%；
SiO236～63wt%；
Oxide 2.0～the 4.0wt% of metal promoter；
The present invention further discloses the preparation method that described a kind of dimethyl oxalate. gas phase hydrogenation produces ethylene glycol catalyst, comprise the following steps:
(1) add water mixing in advance in Ludox, is subsequently adding precipitant and makes the mixed aqueous solution of Ludox and precipitant；
(2) mixed aqueous solution of the soluble-salt of preparation mantoquita and metal promoter；
(3) two kinds of aqueous solutions prepared by step (1) and step (2) are carried out Homogeneous phase mixing；
(4) being stirred reaction under water bath condition, reaction prepares colloidal solid through filtration, washing after terminating；
(5) colloidal solid prepared to step (4) adds organic expanding agent, stands after stirring；
(6) dry, roasting, playing sheet molding, the dimethyl oxalate. gas phase hydrogenation described in namely preparing produces ethylene glycol catalyst；Wherein,
Preferably, in step (1), SiO in described Ludox2Content is 25-30wt%.
Preferably, in step (1), described precipitant is selected from NaOH, Na2CO3、NaHCO3, ammonia and carbamide.
Preferably, in step (1), the pH regulating the mixed aqueous solution of described Ludox and precipitant is 1.0～7.0.It is more preferably 1.0～6.0.
Preferably, in step (1), in the mixed aqueous solution of described prepared Ludox and precipitant, SiO2Concentration be 5.0～12.5wt%, it is preferred to 8-12wt%.
Preferably, in step (1), the addition of described precipitant is with after ensureing step (1) and (2) two kinds of aqueous solution of step so that it is in copper precipitate completely and excessive slightly.
Preferably, in step (2), described mantoquita is copper nitrate, copper sulfate etc..
Preferably, in step (2), the soluble-salt of described metal promoter is selected from the nitrate of metal promoter, sulfate etc..
Preferably, in step (2), in the aqueous solution of the soluble-salt of described prepared mantoquita and metal promoter, the concentration of metallic copper is 7.5～12.6wt%；It is preferably 8-12wt%.
Preferably, in step (4), the temperature of described water-bath is 50～95 DEG C, and the time of described stirring reaction is 10～48 hours.
Preferably, in step (5), described organic expanding agent is selected from Polyethylene Glycol, and the degree of polymerization is 300～2000.
Preferably, in step (5), described organic expanding agent addition is SiO in described catalyst2The 1.0～8.0% of weight.
Preferably, in step (5), stand 1～3 hour after stirring.
Preferably, in step (6), described dry temperature is 80～120 DEG C, and the dry time is 10～24 hours.
Preferably, in step (6), the temperature of described roasting is 300～750 DEG C, and the time of roasting is 4～10 hours.
Preferably, before described catalyst uses, with the hydrogen nitrogen mixed gas reduction that hydrogen volume content is 5～100v%, reduction temperature is 120～300 DEG C.
Catalyst after reduction is applied to dimethyl oxalate. gas phase hydrogenation and produces ethylene glycol, hydrogenation technique parameter is: with dimethyl oxalate. for reaction raw materials, control reaction temperature 165～250 DEG C, reaction pressure 2.0～4.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) is 0.4～2.0g/mLcat.h, and the molecular proportion of hydrogen and oxalate is 50～200:1.
The present invention by adding expanding agent and environmentally friendly auxiliary agent in preparation process, it is effectively improved the pore structure of catalyst, make the catalyst of preparation in being applied to oxalic ester hydrogenation synthesizing of ethylene glycol course of reaction, the activity of catalyst and the selectivity of ethylene glycol can be effectively improved, rugged catalyst bed temperature, significantly inhibit the generation of impurity product, catalytic mechanical intensity there is not negative effect, improve catalyst anti-wear performance, and the service life of catalyst can reach more than 1 year, it is possible to meet industrial needs.Reaction temperature 165～230 DEG C, under reaction pressure 2.0～4.0MPa, ethylene glycol space-time yield is high, the conversion ratio of raw material DMO is close to 100%, target product selectivity is more than 95%, the impurity content that by-product especially affects ethylene glycol performance is low, reaction bed temperature is stable, and after catalyst uses 8266 hours, the reacted hydrogenation catalyst intensity obtained according to the passivation program set and granule integrity keep good.
Detailed description of the invention
Below by way of specific instantiation, technical scheme is described.Should be understood that one or more method steps that the present invention mentions do not repel before and after described combination step, there is also additive method step or additive method step can also be inserted between these steps specifically mentioned；Should also be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
Prepare dimethyl oxalate. gas phase hydrogenation and produce ethylene glycol catalyst, consist of CuO48wt%, SiO250wt% and NiO2.0wt%；Preparation process is as follows:
First weigh SiO2Content is the Ludox 5.0Kg of 25%, adds 4.8Kg deionized water, is sufficiently mixed, and weighs carbamide 2.7Kg and is dissolved in wherein, then is sufficiently mixed, and regulating pH value with concentrated nitric acid is 6.0.Weigh the copper nitrate solution 9.6Kg of 10.0wt%Cu again, weigh 194g solid nitric acid nickel and be dissolved in copper nitrate solution.Then by two solution mix homogeneously, and it is poured into together in reactor.By reactor heating in water bath, raise reaction temperature to 95 DEG C, mixing speed is transferred to 300 revs/min, reflux condensation mode 10 hours.Take out suspension after reaction, with Filter Press, then with the filter cake after the cleaned filter of deionized water, be colourless to cleaning mixture.Filter cake containing certain water yield is placed in stainless steel cask, add 56g Polyethylene Glycol (n=1000), stir, making filter cake is gel, place 2 hours, be then placed at 80 DEG C and dry 24 hours, 400 DEG C of roastings 10 hours, then play sheet molding, finally obtain oxalate gas phase hydrogenation catalyst.With BET test result such as table 1.
Using procatalyst hydrogen volume content is the hydrogen of 50v%, nitrogen mixture reduction, and reduction temperature is 300 DEG C.Being evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with oxalate for reaction raw materials, control reaction temperature 190 DEG C, reaction pressure 3.0MPa, oxalate liquid hourly space velocity (LHSV) is 0.7g/mLcat.h, and the molecular proportion of hydrogen and oxalate is 60.Evaluation result is in Table 1.
Embodiment 2
Prepare dimethyl oxalate. gas phase hydrogenation and produce ethylene glycol catalyst, consist of CuO20wt%, SiO279wt% and Na2O1.0wt%；Preparation process is as follows:
First weigh SiO2Content is the Ludox 6.6Kg of 30%, adds 9.3Kg deionized water, is sufficiently mixed, and weighs carbamide 1.2Kg and is dissolved in wherein, then is sufficiently mixed, and regulating pH value with concentrated nitric acid is 1.0.Weigh the copper nitrate solution 5.0Kg of 8.0wt%Cu again, weigh 34.3g solid nitric acid sodium and be dissolved in copper nitrate solution.Then by two solution mix homogeneously, and it is poured into together in reactor.By reactor heating in water bath, raise reaction temperature to 85 DEG C, mixing speed is transferred to 300 revs/min, reflux condensation mode 26 hours.Take out suspension after reaction, with Filter Press, then with the filter cake after the cleaned filter of deionized water, be colourless to cleaning mixture.Filter cake containing certain water yield is placed in stainless steel cask, add 128g Polyethylene Glycol (n=300), stir, making filter cake is gel, place 1 hour, be then placed at 100 DEG C and dry 15 hours, 600 DEG C of roastings 6 hours, then play sheet molding, finally obtain oxalate hydrogenation catalyst.With BET test result such as table 1.
Using the reduction of procatalyst 75v% hydrogen, nitrogen, reduction temperature is 210 DEG C.Being evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with oxalate for reaction raw materials, control reaction temperature 180 DEG C, reaction pressure 2.0MPa, oxalate liquid hourly space velocity (LHSV) is 0.4g/mLcat.h, and the molecular proportion of hydrogen and oxalate is 200.Evaluation result is in Table 1.
Embodiment 3
Prepare dimethyl oxalate. gas phase hydrogenation and produce ethylene glycol catalyst, consist of CuO70wt%, SiO225wt% and ZnO5.0wt%；Preparation process is as follows:
First weigh SiO2Content is the Ludox 2.5Kg of 25%, adds 4.5Kg deionized water, is sufficiently mixed, and weighs carbamide 3.9Kg and is dissolved in wherein, then is sufficiently mixed, and regulating pH value with concentrated nitric acid is 3.0.Weigh the copper nitrate solution 11.1Kg of 12.6wt%Cu again, weigh 458g solid nitric acid zinc and be dissolved in copper nitrate solution.Then by two solution mix homogeneously, and it is poured into together in reactor.By reactor heating in water bath, raise reaction temperature to 75 DEG C, mixing speed is transferred to 300 revs/min, reflux condensation mode 35 hours.Take out suspension after reaction, with Filter Press, then with the filter cake after the cleaned filter of deionized water, be colourless to cleaning mixture.Filter cake containing certain water yield is placed in stainless steel cask, add 8.9g Polyethylene Glycol (n=2000), stir, making filter cake is gel, place 3 hours, be then placed at 120 DEG C and dry 10 hours, 700 DEG C of roastings 4 hours, then play sheet molding, finally obtain oxalate hydrogenation catalyst.With BET test result such as table 1.
Using procatalyst 100v% hydrogen reducing, reduction temperature is 120 DEG C.Being evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with oxalate for reaction raw materials, control reaction temperature 230 DEG C, reaction pressure 4.0MPa, oxalate liquid hourly space velocity (LHSV) is 2.0g/mLcat.h, and the molecular proportion of hydrogen and oxalate is 50.Evaluation result is in Table 1.
In embodiment 1-3, precipitant carbamide can also use NaOH, Na2CO3、NaHCO3, ammonia etc. substitute, identical effect can be reached, the addition of precipitant is with after ensureing two kinds of aqueous solution so that it is in copper precipitate completely and excessive slightly.
Comparative example 1-1
Being not added with metal promoter, other preparation process and parameter, with embodiment 1, prepare hydrogenation of oxalate for preparing ethylene glycol catalyst.BET test result is in Table 1.
The in-service evaluation condition of catalyst is with embodiment 1, and evaluation result is in Table 1.
Comparative example 1-2
Being not added with expanding agent, other preparation process and parameter, with embodiment 1, prepare hydrogenation of oxalate for preparing ethylene glycol catalyst.BET test result is in Table 1.
The in-service evaluation condition of catalyst is with embodiment 1, and evaluation result is in Table 1.
Comparative example 2
Being not added with metal promoter and expanding agent, other preparation process and parameter, with embodiment 2, prepare hydrogenation of oxalate for preparing ethylene glycol catalyst.BET test result is in Table 1.
The in-service evaluation condition of catalyst is with embodiment 2, and evaluation result is in Table 1.
Comparative example 3
Being not added with metal promoter and expanding agent, other preparation process and parameter, with embodiment 3, prepare hydrogenation of oxalate for preparing ethylene glycol catalyst.BET test result is in Table 1.
The in-service evaluation condition of catalyst is with embodiment 3, and evaluation result is in Table 1.
Embodiment 7 is prepared dimethyl oxalate. gas phase hydrogenation and is produced ethylene glycol catalyst, consists of CuO48wt%, SiO250wt% and Li2O2.0wt%；Metal promoter soluble salt selects lithium sulfate；Preparation process step and other parameter reference embodiment 1；Catalyst in-service evaluation condition is with embodiment 1.BET test result and evaluation result are in Table 1.
Embodiment 5,6 and 8 is prepared respectively and is consisted of CuO70wt%, SiO225wt% and AgO5.0wt%；CuO70wt%, SiO225wt% and Al2O35.0wt% and CuO70wt%, SiO2The dimethyl oxalate. gas phase hydrogenation of 25wt% and BaO5.0wt% produces ethylene glycol catalyst；Embodiment 5 metal promoter soluble salt selects silver nitrate；Embodiment 6 metal promoter soluble salt selects aluminum sulfate；Embodiment 8 metal promoter soluble salt selects barium nitrate；Preparation process step and other parameter reference embodiment 3；Catalyst in-service evaluation condition is with embodiment 3.BET test result and evaluation result are in Table 1.
Embodiment 4,9 and 10 preparation forms respectively CuO20wt%, SiO279wt% and Mn2O1.0wt%；CuO20wt%, SiO279wt% and Cs2O1.0wt%；And CuO20wt%, SiO279wt% and K2The dimethyl oxalate. gas phase hydrogenation of O1.0wt% produces ethylene glycol catalyst；Embodiment 4 metal promoter soluble salt selects manganese nitrate；Embodiment 9 metal promoter soluble salt is selected from cesium sulfate；Embodiment 10 metal promoter soluble salt selects potassium nitrate；Preparation process step and other parameter reference embodiment 2；Catalyst in-service evaluation condition is with embodiment 2.BET test result and evaluation result are in Table 1.
Table 1 catalyst BET test result and evaluation result
Note: DMO is dimethyl oxalate., and EG is ethylene glycol, and MG is methyl glycollate, and BDO is 1,2-butanediol, and ET is ethanol；C represents conversion ratio, and S represents selectivity.
Catalyst is applied to dimethyl oxalate. gas phase hydrogenation and produces ethylene glycol process: DMO is hydrogenated with MG, repeated hydrogenation is to EG, EG crosses hydrogenation and generates ET and BDO, and the performance of a catalyst can not only see the conversion ratio of DMO and the selectivity of target product EG, also to see the selectivity of MG, BDO and ET.
Claims (10)
1. dimethyl oxalate. gas phase hydrogenation produces an ethylene glycol catalyst, including each component of following weight/mass percentage composition:
CuO20～70wt%；
SiO225～79wt%；
Oxide 1.0～the 5.0wt% of metal promoter；
Described metal promoter is selected from metallic element Li, Na, K, Cs, Ba, Mn, Ni, Al, Ag and Zn；
The specific surface area of described catalyst is 100～500m2/ g, pore volume is 0.3～1.5mL/g, and aperture is 1.0～15.0nm.
2. a kind of dimethyl oxalate. gas phase hydrogenation as claimed in claim 1 produces ethylene glycol catalyst, it is characterised in that include each component of following weight/mass percentage composition:
CuO35～60wt%；
SiO236～63wt%；
Oxide 2.0～the 4.0wt% of metal promoter.
3. the preparation method that a kind of dimethyl oxalate. gas phase hydrogenation as claimed in claim 1 or 2 produces ethylene glycol catalyst, comprises the following steps:
(1) add water mixing in advance in Ludox, is subsequently adding precipitant and makes the mixed aqueous solution of Ludox and precipitant；
(2) mixed aqueous solution of the soluble-salt of preparation mantoquita and metal promoter；
(3) two kinds of aqueous solutions prepared by step (1) and step (2) are carried out Homogeneous phase mixing；
(4) being stirred reaction under water bath condition, reaction prepares colloidal solid through filtration, washing after terminating；
(5) colloidal solid prepared to step (4) adds organic expanding agent, stands after stirring；
(6) dry, roasting, playing sheet molding, the dimethyl oxalate. gas phase hydrogenation described in namely preparing produces ethylene glycol catalyst.
4. preparation method as claimed in claim 3, it is characterised in that in step (1), also include any one in following characteristics or multinomial:
1. SiO in described Ludox2Content is 25-30wt%；
2. described precipitant is selected from NaOH, Na2CO3、NaHCO3, ammonia and carbamide；
3. the pH regulating the mixed aqueous solution of described Ludox and precipitant is 1.0～7.0；
4. in the mixed aqueous solution of described prepared Ludox and precipitant, SiO2Concentration be 5.0～12.5wt%.
5. preparation method as claimed in claim 3, it is characterised in that in step (2), also include any one in following characteristics or multinomial:
1. described mantoquita is selected from copper nitrate and copper sulfate；
2. the soluble-salt of described metal promoter is selected from nitrate and the sulfate of metal promoter；
3., in the aqueous solution of the soluble-salt of described prepared mantoquita and metal promoter, the concentration of metallic copper is 7.5～12.6wt%.
6. preparation method as claimed in claim 3, it is characterised in that in step (4), the temperature of described water-bath is 50～95 DEG C, and the time of described stirring reaction is 10～48 hours.
7. preparation method as claimed in claim 3, it is characterised in that in step (5), also includes any one of following characteristics or multinomial:
1. described organic expanding agent is selected from Polyethylene Glycol, and the degree of polymerization is 300～2000；
2. described organic expanding agent addition is SiO in described catalyst2The 1.0～8.0% of weight；
3. stand 1～3 hour after stirring.
8. preparation method as claimed in claim 3, it is characterised in that in step (5), also includes any one of following characteristics or multinomial:
1. described dry temperature is 80～120 DEG C, and the dry time is 10～24 hours；
2. the temperature of described roasting is 300～750 DEG C, and the time of roasting is 4～10 hours.
9. a kind of dimethyl oxalate. gas phase hydrogenation as claimed in claim 1 or 2 produces the application of ethylene glycol catalyst, it is characterised in that before described catalyst uses, and with the hydrogen nitrogen mixed gas reduction that hydrogen volume content is 5～100v%, reduction temperature is 120～300 DEG C.
10. a kind of dimethyl oxalate. gas phase hydrogenation as claimed in claim 9 produces the application of ethylene glycol catalyst, it is characterized in that, catalyst after reduction is applied to dimethyl oxalate. gas phase hydrogenation and produces ethylene glycol, hydrogenation technique parameter is: with dimethyl oxalate. for reaction raw materials, control reaction temperature 165～250 DEG C, reaction pressure 2.0～4.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) is 0.4～2.0g/mLcat.h, and the molecular proportion of hydrogen and oxalate is 50～200:1.
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| WO2018233497A1 (en) * | 2017-06-20 | 2018-12-27 | 高化学技术株式会社 | Copper-based catalyst and preparation method therefor, and method for preparing etherification-grade ethylene glycol by using catalyst |
| CN111689526A (en) * | 2020-06-02 | 2020-09-22 | 河北众迪远科技有限公司 | Preparation method of lithium battery cathode material lithium nickel manganese oxide |
| CN112871171A (en) * | 2021-01-06 | 2021-06-01 | 上海华谊能源化工有限公司 | Preparation method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation |
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