CN101954288A - Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof - Google Patents
Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof Download PDFInfo
- Publication number
- CN101954288A CN101954288A CN 201010293758 CN201010293758A CN101954288A CN 101954288 A CN101954288 A CN 101954288A CN 201010293758 CN201010293758 CN 201010293758 CN 201010293758 A CN201010293758 A CN 201010293758A CN 101954288 A CN101954288 A CN 101954288A
- Authority
- CN
- China
- Prior art keywords
- dimethyl oxalate
- catalyst
- hours
- urea
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, a preparation method and application thereof. The catalyst is prepared by using Cu as main active component and using one or more of Ag, Mg, Au, Ru, Rh, Pd, Pt, Re, Ni, Co, Cr, Zn and Zr as additive through a urea decomposition-homogeneous coprecipitation process, wherein the mass fraction of Cu is 0 to 30 percent, the mass fraction of the additive is 0 to 20 percent, and the rest is carrier silica. The method for preparing the catalyst is simple, and good in synthesis repetitiveness, and when being applied for hydrogenation of dimethyl oxalate to prepare methyl glycolate, the catalyst is high in activity and stability, and the selectivity of methyl glycolate is high.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application of prepared by dimethyl oxalate plus hydrogen methyl glycollate, particularly relate to described catalyst and be equipped with application in the methyl glycollate at prepared by dimethyl oxalate plus hydrogen.
Background technology
Methyl glycollate (MG) is a class important chemical product and an intermediate, is widely used in many fields such as chemical industry, medicine, agricultural chemicals, feed, dyestuff and spices, mainly comprises: 1) as the fine solvent in fiber, resin, rubber, the semiconductor production; 2) further hydrogenating reduction preparing ethylene glycol; 3) carbonylation system malonic acid (list) methyl esters; 4) ammonia is separated the system glycine; 5) oxidative dehydrogenation system glyoxalic acid methylester; 6) hydrolysis system glycolic etc.In all multipurposes of methyl glycollate, hydrolysis system glycolic has great exploitation value and vast market prospect.
The synthetic main employing of glycolic abroad is to be the carbonylation route of raw material with formaldehyde at present, corrosion-resistant and high pressure resistant the having relatively high expectations of equipment, and disposable having high input, large-scale production has difficulties; And domestic process route producing and ethanol in next life acid of also always continuing to use monoxone and soda lye hybrid reaction resterification, it is raw material that acetate is adopted in this chloroacetic production, sulphur is catalyst, the chlorine method is produced, though process is simple, but seriously corroded in the production process, pollute big, cost is high, thereby cause this method not use by heavy industrialization.Therefore need eco-friendly synthetic route of exploitation badly.
Along with the worsening shortages of petroleum resources, the C1 chemical industry of carrying out based on natural gas and coal-based raw material has important practical significance to China.Correlation technique has also obtained development fast in the nineties in last century.Wherein, CO and nitrites gas phase catalysis synthesizing dimethyl oxalate (DMO) are the important breakthrough of C1 route synthesis of chemicals.In the last few years, under the stable condition of the process upstream technology maturation of producing DMO, the product chain that further develops the DMO downstream had become the research focus and emphasis of this catalytic field.From DMO route preparation of ethanol by hydrogenating acid methyl esters, tally with the national condition, have the characteristics of economy, environmental protection.From existing report, Japan (JP06135895, US4440873) Cu-Ag/SiO that adopts the cuprammonium complexometry to prepare
2Catalyst can generate methyl glycollate by catalysis DMO highly selective; And domestic University Of Tianjin (CN101138730A) has also carried out the research of this reaction earlier, employing be improved silica dip loading copper silver catalyst, the yield of methyl glycollate can reach more than 68%.It is pointed out that for such catalyst and adopt the preparation of titration coprecipitation more, precipitating reagent is bigger to the catalytic performance influence, and great majority selection ammoniacal liquor is precipitating reagent, and high performance catalyst often needs accurately to control conditions such as ammonia still process temperature and pH value.At present, about preparing ethylene glycol by using dimethyl oxalate plus hydrogen, the industrialization practical exploration of particularly making methyl glycollate still major part concentrates on Study of Catalyst.
Summary of the invention
One of technical problem to be solved by this invention is to provide a kind of Catalysts and its preparation method and application of prepared by dimethyl oxalate plus hydrogen methyl glycollate.The present invention adopts urea decomposition-even coprecipitation to replace conventional titration coprecipitation, by progressively being decomposed at a certain temperature, urea discharges ammonia, control the settling velocity of Preparation of Catalyst precursor metal salts, make each component can homogeneous precipitation thereby reach; By this method Zhi Bei catalyst metal components mix, scattered, generation methyl glycollate that can catalysis dimethyl oxalate high selectivity, thus solved the problem that prior art exists effectively.
The present invention is achieved through the following technical solutions:
The catalyst of described prepared by dimethyl oxalate plus hydrogen methyl glycollate, with silica is carrier, with Cu is main active component, contain among Ag, Mg, Au, Ru, Rh, Pd, Pt, Re, Ni, Co, Cr, Zn, the Zr one or more simultaneously as auxiliary agent, wherein, the mass fraction of Cu is 0～30%, and the mass fraction of auxiliary agent is 0～20%, and all the other are carrier silica.
Preferably, the catalyst of described prepared by dimethyl oxalate plus hydrogen methyl glycollate, with silica is carrier, with Cu is main active component, contain among Ag, Ru, Pd, Re, Mg, Ni, Co, Cr, Zn or the Zr one or more simultaneously as auxiliary agent, wherein, the mass fraction of Cu is 0%～20%, the mass fraction of auxiliary agent is 0～15%, and all the other are carrier silica.
The Preparation of catalysts method of described prepared by dimethyl oxalate plus hydrogen methyl glycollate adopts urea to decompose-evenly coprecipitation preparation, specifically may further comprise the steps:
1) will contain the nitrate precursor deionized water dissolving of metal ions such as Cu, Ag, Mg, Au, Ru, Rh, Pd, Pt, Re, Ni, Co, Cr, Zn or Zr.
2) take by weighing urea and be mixed with the aqueous solution, urea liquid is added in the step 1) solution, stir into uniform solution, wherein, the concentration of metal ion is 0.5～3M, preferred 0.6～2M; The mol ratio of urea and nitrate ion is 0.1～6, preferred 0.5～4.
3) Ludox is added step 2) in the uniform solution that makes, and stir under placing 90～120 ℃ and carried out even co-precipitation in 10～15 hours, under 70～95 ℃ of temperature, wore out 10～30 hours then, wherein precipitation temperature is preferred 90～110 ℃, preferred 80～95 ℃ of aging temperature, preferred 10～20 hours of ageing time.
4) suction filtration is with deionized water or ethanol washing products obtained therefrom, then in 70～120 ℃ of dryings 24～36 hours; 300～800 ℃ of roastings 3～15 hours in Muffle furnace more promptly make described catalyst.Wherein, preferred 90～120 ℃ of baking temperature, preferred 18～36 hours of drying time; Preferred 300～600 ℃ of sintering temperature, preferred 4～12 hours of roasting time.
The application of described catalyst in the preparation methyl glycollate, promptly at first above-mentioned catalyst is packed into and reduce in the fixed bed continuous reactor, be cooled to 120～300 ℃ of reaction temperatures after the end, feeding mol ratio then is that 2: 1～100: 1 the hydrogen and the mixture of dimethyl oxalate react, and promptly gets the target product methyl glycollate.
Wherein, described catalyst adopts hydrogen reducing, and reducing condition is the air speed 100～1500h of Hydrogen Vapor Pressure 0.2～10.0MPa, hydrogen
-1, 150～400 ℃ of reduction temperatures, 2～36 hours recovery times.Preferred 140～250 ℃ of reaction temperature, preferred 5: 1～50: 1 of the mol ratio of hydrogen and dimethyl oxalate, the dimethyl oxalate liquid hourly space velocity (LHSV) is 0.01～5.0h
-1, be preferably 0.1～3.5h
-1Hydrogen Vapor Pressure is 0.2～10.0MPa, preferred 0.5～6.0MPa.
Method for preparing catalyst of the present invention is simple, synthetic good reproducibility, and when being applied to prepared by dimethyl oxalate plus hydrogen and being equipped with the methyl glycollate reaction, catalyst activity and stability are higher, the selectivity height of methyl glycollate.Wherein, the conversion ratio of methyl glycollate is up to 94.5%, and the selectivity of methyl glycollate is up to 92.5%.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail, but this embodiment does not limit protection scope of the present invention.
Embodiment 1
With copper nitrate or silver nitrate deionized water dissolving; According to the mol ratio of nitrate ion in urea and the metallic solution is to take by weighing urea and be mixed with the aqueous solution at 2.1: 1; Urea liquid is added in the mixed solution of copper nitrate and silver nitrate, stir; Add Ludox in above-mentioned mixed solution, and stir homogeneous precipitations in 10 hours under placing 100～105 ℃, decompose fully, wore out 20 hours in 95 ℃ again to guarantee urea; Suction filtration, after cleaning with deionized water with the gained sample in 90 ℃ of dryings 24 hours; 450 ℃ of roastings 5 hours in Muffle furnace again; The catalyst nonoxygen element of gained composition is shown 16%Cu-6%Ag/SiO with percentage table after the roasting
2
Pack into behind the catalyst compression molding that above-mentioned roasting is made in the fixed bed reactors, reduced 4 hours at 300 ℃ with hydrogen, reduction cools the temperature to reaction temperature after finishing, enter reactor reaction after dimethyl oxalate (DMO) and the hydrogen mixing preheating, reaction temperature is 185 ℃, and the dimethyl oxalate liquid hourly space velocity (LHSV) is 0.8h
-1, reaction pressure 2.0MPa, the mol ratio of hydrogen/DMO 40: 1, the product gas chromatographic analysis, the conversion ratio of dimethyl oxalate is 86.5%, the selectivity of methyl glycollate is 82.3%.
Embodiment 2～5
The composition of catalyst is identical with embodiment 1 among the embodiment 2～5, is 16%Cu-6%Ag/SiO
2
The Preparation of catalysts method is except that the mol ratio of urea and nitrate ion and embodiment 1 are different among the embodiment 2～5, and other is all identical with embodiment 1.
The reduction of catalyst is also identical with embodiment 1 with reaction condition among the embodiment 2～5.
Wherein, table 1 is the mole of a urea and nitrate ion reaction result when in the catalyst preparation process among the embodiment 2～5.
Table 1
| Embodiment | Urea and nitrate ion mol ratio | Dimethyl oxalate conversion ratio % | Methyl glycollate selectivity % |
| Embodiment 2 | 0.1? | 40.6? | 65.4? |
| Embodiment 3 | 0.5? | 51.5? | 72.1? |
| Embodiment 4 | 1.8? | 76.2? | 82.5? |
| Embodiment 5 | 2.5? | 87.5? | 89.8? |
Embodiment 6～18
The Preparation of catalysts method is identical with embodiment 1 among the embodiment 6～18, but the ratio of the ratio of selected metal ion and urea and metal ion, urea and nitrate ion is difference to some extent, thereby the composition of the catalyst that makes (the catalyst nonoxygen element is formed and represented with percentage) difference.
The reduction of catalyst is identical with embodiment 1 with reaction condition among the embodiment 6～18.
Table 2 is that the catalyst of embodiment 6～18 is formed and reaction result.
Table 2
| Embodiment | Catalyst is formed | Dimethyl oxalate conversion ratio % | Methyl glycollate selectivity % |
| Embodiment 6 | 25％Cu-6％Ag/SiO 2 | 90.2? | 81.5? |
| Embodiment 7 | 15％Cu-10％Ag/SiO 2 | 91.3? | 86.4? |
| Embodiment 8 | 20％Cu-15％Ag/SiO 2 | 89.5? | 88.6? |
| Embodiment 9 | 15Cu％-10％Ag-Zn5％/SiO 2 | 92.3? | 89.5? |
| Embodiment 10 | 18％Cu/SiO 2 | 85.6? | 84.7? |
| Embodiment 12 | 10％Cu-8％Ag-1％Mg/SiO 2 | 87.5? | 92.4? |
| Embodiment 13 | 15％Cu-10％Ag-3％Ni/SiO 2 | 88.9? | 93.5? |
| Embodiment 14 | 20％Cu-12％Ag-1.5％Cr/SiO 2 | 87.6? | 92.1? |
| Embodiment 15 | Cu15％-8％Ag-5％Zr/SiO 2 | 87.1? | 89.7? |
| Embodiment 16 | 15％Cu-10％Ag-2％Au/SiO 2 | 93.2? | 91.3? |
| Embodiment 17 | 20％Cu-12％Ag-0.2％Pt/SiO 2 | 94.5? | 91.2? |
| Embodiment 18 | 20％Cu-8％Ag-0.5％Ru/SiO 2 | 91.8? | 92.5? |
From above-mentioned table 1, table 2 as can be seen: catalyst of the present invention can be a methyl glycollate with the dimethyl oxalate hydro-conversion efficiently, and conversion ratio is up to 94.5%, and the selectivity of prepared methyl glycollate is up to 92.5%.
Should be noted that at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (8)
1. the catalyst of a prepared by dimethyl oxalate plus hydrogen methyl glycollate, it is characterized in that, described catalyst is carrier with silica, with Cu is main active component, contain among Ag, Mg, Au, Ru, Rh, Pd, Pt, Re, Ni, Co, Cr, Zn, the Zr one or more simultaneously as auxiliary agent, wherein, the mass fraction of Cu is 0～30%, the mass fraction of auxiliary agent is 0～20%, and all the other are carrier silica.
2. the catalyst of a prepared by dimethyl oxalate plus hydrogen methyl glycollate, it is characterized in that, described catalyst is carrier with silica, with Cu is main active component, contains among Ag, Ru, Pd, Re, Mg, Ni, Co, Cr, Zn or the Zr one or more simultaneously as auxiliary agent, wherein, the mass fraction of Cu is 0%～20%, the mass fraction of auxiliary agent is 0～15%,, all the other are carrier silica.
3. the Preparation of catalysts method of claim 1 or 2 described prepared by dimethyl oxalate plus hydrogen methyl glycollates is characterized in that, adopts urea to decompose-evenly coprecipitation preparation, specifically may further comprise the steps:
1) will contain the nitrate precursor deionized water dissolving of metal ion;
2) take by weighing urea and be mixed with the aqueous solution, urea liquid is added in the step 1) solution, stir into uniform solution, wherein, the concentration of metal ion is 0.5～3M, and the mol ratio of urea and nitrate ion is 0.1～6: 1;
3) Ludox is added step 2) in the uniform solution that makes, and place 90～120 ℃ to stir down and carried out even co-precipitation in 10～15 hours, under 70～95 ℃ of temperature aging 10～30 hours then;
4) suction filtration is with deionized water or ethanol washing products obtained therefrom, then in 70～120 ℃ of dryings 18～36 hours; 300～800 ℃ of roastings 3～15 hours in Muffle furnace more promptly make described catalyst.
4. preparation method according to claim 3 is characterized in that, described metal ion is selected from: Cu, Ag, Mg, Au, Ru, Rh, Pd, Pt, Re, Ni, Co, Cr, Zn, Zr.
5. the Preparation of catalysts method of claim 1 or 2 described prepared by dimethyl oxalate plus hydrogen methyl glycollates is characterized in that, adopts urea to decompose-evenly coprecipitation preparation, specifically may further comprise the steps:
1) will contain the nitrate precursor deionized water dissolving of metal ion;
2) take by weighing urea and be mixed with the aqueous solution, urea liquid is added in the step 1) solution, stir into uniform solution, wherein, the concentration of metal ion is 0.6～2M, and the mol ratio of urea and nitrate ion is 0.5～4: 1;
3) Ludox is added step 2) in the uniform solution that makes, and place 90～110 ℃ to stir down and carried out even co-precipitation in 10～15 hours, under 80～95 ℃ of temperature aging 10～20 hours then;
4) suction filtration is with deionized water or ethanol washing products obtained therefrom, then in 90～120 ℃ of dryings 24～36 hours; 300～600 ℃ of roastings 4～12 hours in Muffle furnace more promptly make described catalyst.
6. claim 1 or the 2 described catalyst application in the preparation methyl glycollate, it is characterized in that, at first claim 1 or 2 described catalyst are packed into and reduce in the fixed bed continuous reactor, be cooled to 120～300 ℃ of reaction temperatures after the end, feeding mol ratio then is 2: 1～100: 1 the hydrogen and the mixture of dimethyl oxalate, reacts, and promptly gets methyl glycollate, wherein, the hourly space velocity of dimethyl oxalate liquid is 0.01～5.0h
-1Hydrogen Vapor Pressure is 0.2～10.0MPa.
7. application according to claim 6 is characterized in that described catalyst need adopt hydrogen reducing before use, and reducing condition is the air speed 100～1500h of Hydrogen Vapor Pressure 0.2～10.0MPa, hydrogen
-1, 150～400 ℃ of reduction temperatures, 2～36 hours recovery times.
8. application according to claim 6 is characterized in that, preferred 140～250 ℃ of reaction temperature, preferred 5: 1～50: 1 of the mol ratio of hydrogen and dimethyl oxalate, the preferred 0.1～3.5h of dimethyl oxalate liquid hourly space velocity (LHSV)
-1, the preferred 0.5～6.0MPa of Hydrogen Vapor Pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010293758 CN101954288B (en) | 2010-09-27 | 2010-09-27 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010293758 CN101954288B (en) | 2010-09-27 | 2010-09-27 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101954288A true CN101954288A (en) | 2011-01-26 |
| CN101954288B CN101954288B (en) | 2013-01-23 |
Family
ID=43482021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010293758 Active CN101954288B (en) | 2010-09-27 | 2010-09-27 | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101954288B (en) |
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| CN102327774A (en) * | 2011-07-06 | 2012-01-25 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
| CN102553615A (en) * | 2012-01-18 | 2012-07-11 | 厦门大学 | Oxalate hydrogenation copper-gold dual-metal catalyst and preparation method thereof |
| CN102641735A (en) * | 2012-04-25 | 2012-08-22 | 厦门大学 | Oxalate hydrogenated Au-Ag bimetallic catalyst and preparation method thereof |
| CN102649747A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction |
| CN102649745A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing glycolate through oxalate gas phase hydrogenation |
| CN102649746A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
| CN102649074A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Preparation method of fluid catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation |
| CN102649744A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Production method for glycolic acid ester |
| CN102649072A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Fluidized bed catalyst of glycolate catalyzed from oxalic ester |
| CN102649743A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for synthesizing glycollic acid ester |
| CN102649062A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN102989490A (en) * | 2012-12-04 | 2013-03-27 | 复旦大学 | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof |
| CN103007961A (en) * | 2012-12-13 | 2013-04-03 | 北京化工大学常州先进材料研究院 | Catalyst for eliminating CO in hydrogen source of fuel cell and preparation method of catalyst |
| CN103157490A (en) * | 2011-12-13 | 2013-06-19 | 西南化工研究设计院 | Catalyst for producing ethanol by hydrogenation of acetic ester, and preparation method thereof |
| CN103301843A (en) * | 2012-03-15 | 2013-09-18 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
| CN103785408A (en) * | 2014-02-12 | 2014-05-14 | 常州大学 | Catalyst for preparing methyl glycolate through dimethyl oxalate hydrogenation and synthetic method of catalyst |
| CN103801303A (en) * | 2014-02-20 | 2014-05-21 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, as well as preparation method and application of catalyst |
| CN104109093A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for synthesizing glycolate through hydrogenating oxalate |
| CN105618057A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst for preparation of beta-diol from beta-diketone by fixed bed hydrogenation |
| CN105618056A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst for hydrogenation of beta-diketone |
| CN106944065A (en) * | 2017-03-27 | 2017-07-14 | 江苏金聚合金材料有限公司 | The preparation method and application of graphene-supported nickel hydrogenation catalyst |
| CN107321352A (en) * | 2017-07-19 | 2017-11-07 | 武汉凯迪工程技术研究总院有限公司 | Ni-based reforming catalyst of recirculating fluidized bed and its preparation method and application |
| CN107837809A (en) * | 2017-09-27 | 2018-03-27 | 上海华谊能源化工有限公司 | It is a kind of to prepare catalyst of normal propyl alcohol and its production and use for dimethyl malenate catalytic hydrogenation |
| CN108325532A (en) * | 2018-03-13 | 2018-07-27 | 浙江师范大学 | Catalyst in the building-up process of methyl glycollate and preparation method thereof, application |
| CN108499564A (en) * | 2018-03-13 | 2018-09-07 | 浙江师范大学 | Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application |
| CN109550506A (en) * | 2018-12-07 | 2019-04-02 | 徐州伯利恒生物科技有限公司 | A kind of low-corrosiveness catalyst |
| CN109569655A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Hydrogenation of oxalate for preparing for ethyl glycolate method |
| CN109731581A (en) * | 2018-12-28 | 2019-05-10 | 万华化学集团股份有限公司 | Modified load-type copper rhenium bimetallic catalyst and its preparation method and application |
| CN109926056A (en) * | 2019-01-25 | 2019-06-25 | 浙江师范大学 | It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application |
| CN109954500A (en) * | 2017-12-25 | 2019-07-02 | 沈阳三聚凯特催化剂有限公司 | A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application |
| CN109999812A (en) * | 2019-05-22 | 2019-07-12 | 兰州理工大学 | A kind of preparation method and applications of the core-shell structure bimetallic copper-based catalysts of high stability |
| CN110871071A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
| CN111229247A (en) * | 2020-02-28 | 2020-06-05 | 浙江师范大学 | Catalyst for preparing ethanol by hydrogenation of oxalate and preparation method and application thereof |
| CN111495373A (en) * | 2020-04-22 | 2020-08-07 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing glycine methyl ester and glycine from methyl glycolate by using double-metal glass wire layered eutectic |
| CN111715226A (en) * | 2020-07-20 | 2020-09-29 | 大连瑞克科技有限公司 | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof |
| CN111774050A (en) * | 2020-07-17 | 2020-10-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
| CN111992209A (en) * | 2020-09-02 | 2020-11-27 | 山东阿斯德科技有限公司 | Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof |
| CN113461524A (en) * | 2021-06-15 | 2021-10-01 | 中石化南京化工研究院有限公司 | Method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
| CN113893853A (en) * | 2021-09-28 | 2022-01-07 | 江苏金聚合金材料有限公司 | Composite carrier bimetallic ester hydrogenation catalyst and preparation method and application thereof |
| CN114054041A (en) * | 2021-09-29 | 2022-02-18 | 中触媒新材料股份有限公司 | Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof |
| CN115069299A (en) * | 2022-06-08 | 2022-09-20 | 浙江联盛化学股份有限公司 | Super-hydrophobic Ni-Cu catalyst and preparation method, application and use method thereof |
| CN116459846A (en) * | 2023-05-09 | 2023-07-21 | 中国科学院兰州化学物理研究所 | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof |
| CN114054041B (en) * | 2021-09-29 | 2024-06-11 | 中触媒新材料股份有限公司 | Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607205A (en) * | 2009-07-24 | 2009-12-23 | 华烁科技股份有限公司 | A kind of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen and preparation method thereof |
| CN101700496A (en) * | 2009-10-21 | 2010-05-05 | 江苏丹化醋酐有限公司 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
-
2010
- 2010-09-27 CN CN 201010293758 patent/CN101954288B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607205A (en) * | 2009-07-24 | 2009-12-23 | 华烁科技股份有限公司 | A kind of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen and preparation method thereof |
| CN101700496A (en) * | 2009-10-21 | 2010-05-05 | 江苏丹化醋酐有限公司 | Catalyst for synthesizing methyl glycolate through hydrogenation by dimethyl oxalate and preparation method thereof |
Cited By (71)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151568B (en) * | 2011-01-30 | 2013-07-31 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| CN102649744A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Production method for glycolic acid ester |
| CN102649072A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Fluidized bed catalyst of glycolate catalyzed from oxalic ester |
| CN102649747A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction |
| CN102649747B (en) * | 2011-02-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester by oxalic ester through fluidized bed reaction |
| CN102649746A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
| CN102649074A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Preparation method of fluid catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation |
| CN102649744B (en) * | 2011-02-25 | 2015-01-07 | 中国石油化工股份有限公司 | Production method for glycolic acid ester |
| CN102649743B (en) * | 2011-02-25 | 2014-10-15 | 中国石油化工股份有限公司 | Method for synthesizing glycollic acid ester |
| CN102649743A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for synthesizing glycollic acid ester |
| CN102649062A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation |
| CN102649745B (en) * | 2011-02-25 | 2014-08-13 | 中国石油化工股份有限公司 | Method for preparing glycolate through oxalate gas phase hydrogenation |
| CN102649072B (en) * | 2011-02-25 | 2014-05-28 | 中国石油化工股份有限公司 | Fluidized bed catalyst of glycolate catalyzed from oxalic ester |
| CN102649745A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing glycolate through oxalate gas phase hydrogenation |
| CN102327774A (en) * | 2011-07-06 | 2012-01-25 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
| CN102327774B (en) * | 2011-07-06 | 2014-05-28 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
| CN103157490A (en) * | 2011-12-13 | 2013-06-19 | 西南化工研究设计院 | Catalyst for producing ethanol by hydrogenation of acetic ester, and preparation method thereof |
| CN102553615B (en) * | 2012-01-18 | 2014-07-02 | 厦门大学 | Oxalate hydrogenation copper-gold dual-metal catalyst and preparation method thereof |
| CN102553615A (en) * | 2012-01-18 | 2012-07-11 | 厦门大学 | Oxalate hydrogenation copper-gold dual-metal catalyst and preparation method thereof |
| CN103301843A (en) * | 2012-03-15 | 2013-09-18 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
| CN103301843B (en) * | 2012-03-15 | 2014-12-03 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
| CN102641735A (en) * | 2012-04-25 | 2012-08-22 | 厦门大学 | Oxalate hydrogenated Au-Ag bimetallic catalyst and preparation method thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN102989490B (en) * | 2012-12-04 | 2015-06-17 | 复旦大学 | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof |
| CN102989490A (en) * | 2012-12-04 | 2013-03-27 | 复旦大学 | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof |
| CN103007961A (en) * | 2012-12-13 | 2013-04-03 | 北京化工大学常州先进材料研究院 | Catalyst for eliminating CO in hydrogen source of fuel cell and preparation method of catalyst |
| CN104109093B (en) * | 2013-04-16 | 2016-04-13 | 中国石油化工股份有限公司 | The method of oxalic ester hydrogenation synthesizing of glycolate |
| CN104109093A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for synthesizing glycolate through hydrogenating oxalate |
| CN103785408A (en) * | 2014-02-12 | 2014-05-14 | 常州大学 | Catalyst for preparing methyl glycolate through dimethyl oxalate hydrogenation and synthetic method of catalyst |
| CN103785408B (en) * | 2014-02-12 | 2016-05-04 | 常州大学 | A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate |
| CN103801303A (en) * | 2014-02-20 | 2014-05-21 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, as well as preparation method and application of catalyst |
| CN105618057B (en) * | 2014-11-04 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of catalyst preparing beta-diol for beta-diketon fixed bed hydrogenation |
| CN105618057A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst for preparation of beta-diol from beta-diketone by fixed bed hydrogenation |
| CN105618056A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst for hydrogenation of beta-diketone |
| CN106944065A (en) * | 2017-03-27 | 2017-07-14 | 江苏金聚合金材料有限公司 | The preparation method and application of graphene-supported nickel hydrogenation catalyst |
| CN106944065B (en) * | 2017-03-27 | 2019-12-17 | 江苏金聚合金材料有限公司 | Preparation method and application of graphene-supported nickel hydrogenation catalyst |
| CN107321352A (en) * | 2017-07-19 | 2017-11-07 | 武汉凯迪工程技术研究总院有限公司 | Ni-based reforming catalyst of recirculating fluidized bed and its preparation method and application |
| CN107837809B (en) * | 2017-09-27 | 2021-08-10 | 上海华谊能源化工有限公司 | Catalyst for preparing n-propanol by catalytic hydrogenation of dimethyl malonate and preparation method and application thereof |
| CN107837809A (en) * | 2017-09-27 | 2018-03-27 | 上海华谊能源化工有限公司 | It is a kind of to prepare catalyst of normal propyl alcohol and its production and use for dimethyl malenate catalytic hydrogenation |
| CN109569655A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Hydrogenation of oxalate for preparing for ethyl glycolate method |
| CN109954500A (en) * | 2017-12-25 | 2019-07-02 | 沈阳三聚凯特催化剂有限公司 | A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application |
| CN109954500B (en) * | 2017-12-25 | 2023-05-05 | 沈阳三聚凯特催化剂有限公司 | Copper-based skeleton composite membrane type hydrogenation catalyst, and preparation method and application thereof |
| CN108499564A (en) * | 2018-03-13 | 2018-09-07 | 浙江师范大学 | Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application |
| CN108325532A (en) * | 2018-03-13 | 2018-07-27 | 浙江师范大学 | Catalyst in the building-up process of methyl glycollate and preparation method thereof, application |
| CN108499564B (en) * | 2018-03-13 | 2020-11-03 | 浙江师范大学 | Catalyst in synthesis process of methyl glycolate and preparation method and application thereof |
| CN110871071A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
| CN109550506A (en) * | 2018-12-07 | 2019-04-02 | 徐州伯利恒生物科技有限公司 | A kind of low-corrosiveness catalyst |
| CN109731581A (en) * | 2018-12-28 | 2019-05-10 | 万华化学集团股份有限公司 | Modified load-type copper rhenium bimetallic catalyst and its preparation method and application |
| CN109731581B (en) * | 2018-12-28 | 2022-01-07 | 万华化学集团股份有限公司 | Modified supported copper-rhenium bimetallic catalyst and preparation method and application thereof |
| CN109926056A (en) * | 2019-01-25 | 2019-06-25 | 浙江师范大学 | It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application |
| CN109999812A (en) * | 2019-05-22 | 2019-07-12 | 兰州理工大学 | A kind of preparation method and applications of the core-shell structure bimetallic copper-based catalysts of high stability |
| CN109999812B (en) * | 2019-05-22 | 2020-02-14 | 兰州理工大学 | Preparation method and application of high-stability core-shell structure bimetallic copper-based catalyst |
| CN111229247B (en) * | 2020-02-28 | 2023-06-13 | 浙江师范大学 | Catalyst for preparing ethanol by oxalate hydrogenation and preparation method and application thereof |
| CN111229247A (en) * | 2020-02-28 | 2020-06-05 | 浙江师范大学 | Catalyst for preparing ethanol by hydrogenation of oxalate and preparation method and application thereof |
| CN111495373A (en) * | 2020-04-22 | 2020-08-07 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing glycine methyl ester and glycine from methyl glycolate by using double-metal glass wire layered eutectic |
| CN111495373B (en) * | 2020-04-22 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing glycine methyl ester and glycine from methyl glycolate by using double-metal glass wire layered eutectic |
| CN111774050A (en) * | 2020-07-17 | 2020-10-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
| CN111774050B (en) * | 2020-07-17 | 2023-05-09 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing hydrogenation of dimethyl oxalate |
| CN111715226A (en) * | 2020-07-20 | 2020-09-29 | 大连瑞克科技有限公司 | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof |
| CN111992209A (en) * | 2020-09-02 | 2020-11-27 | 山东阿斯德科技有限公司 | Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof |
| CN113461524A (en) * | 2021-06-15 | 2021-10-01 | 中石化南京化工研究院有限公司 | Method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate |
| CN113893853B (en) * | 2021-09-28 | 2023-11-03 | 江苏金聚合金材料有限公司 | Composite carrier bimetallic ester hydrogenation catalyst and preparation method and application thereof |
| CN113893853A (en) * | 2021-09-28 | 2022-01-07 | 江苏金聚合金材料有限公司 | Composite carrier bimetallic ester hydrogenation catalyst and preparation method and application thereof |
| CN114054041A (en) * | 2021-09-29 | 2022-02-18 | 中触媒新材料股份有限公司 | Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof |
| CN114054041B (en) * | 2021-09-29 | 2024-06-11 | 中触媒新材料股份有限公司 | Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
| CN115069299A (en) * | 2022-06-08 | 2022-09-20 | 浙江联盛化学股份有限公司 | Super-hydrophobic Ni-Cu catalyst and preparation method, application and use method thereof |
| CN115069299B (en) * | 2022-06-08 | 2024-04-12 | 浙江联盛化学股份有限公司 | Super-hydrophobic Ni-Cu catalyst and preparation method, application and use method thereof |
| CN116459846A (en) * | 2023-05-09 | 2023-07-21 | 中国科学院兰州化学物理研究所 | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof |
| CN116459846B (en) * | 2023-05-09 | 2024-03-26 | 中国科学院兰州化学物理研究所 | Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101954288B (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101954288B (en) | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof | |
| CN102001944B (en) | Method for preparing glycolate by catalyzing oxalate under action of hydrogenation | |
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN101927168B (en) | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof | |
| CN106365995A (en) | Methyl acetate production method | |
| CN106582652A (en) | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof | |
| CN102091624B (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| CN101596455A (en) | A kind of Catalysts and its preparation method of synthesis of oxalate | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN102500381A (en) | Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis | |
| CN110947382B (en) | Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN103372453A (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN101099934A (en) | Aromatic saturated hydrogenation catalyst and its preparing process | |
| CN106890668A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN104109093B (en) | The method of oxalic ester hydrogenation synthesizing of glycolate | |
| CN103769095A (en) | Glycol catalyst obtained through hydrogenation reaction of dimethyl oxalate and preparation method of glycol catalyst | |
| CN102744085A (en) | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation | |
| CN102211036B (en) | A kind of modified molecular sieve catalyst and its precursor and preparation method thereof | |
| CN103801321B (en) | A kind of catalyst for the preparation of BDO and preparation method | |
| CN109772291B (en) | Selective hydrogenation and dealkynization catalyst and preparation method and application thereof | |
| CN102229587B (en) | Method for generating succinic anhydride through maleic anhydride hydrogenation catalyzed by Nano-Ni | |
| CN102430421B (en) | Catalytic agent for synthesizing oxalic ester and preparing method thereof | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN102319562A (en) | The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method | |
| CN103191732A (en) | Method for preparing cyclohexene catalyst through partial hydrogenation of benzene, and method for producing cyclohexene through using cyclohexene catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |