CN104888778A - Glucose hydrogenolysis catalysis Cu/MgO catalyst and preparation method thereof - Google Patents
Glucose hydrogenolysis catalysis Cu/MgO catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104888778A CN104888778A CN201510209248.3A CN201510209248A CN104888778A CN 104888778 A CN104888778 A CN 104888778A CN 201510209248 A CN201510209248 A CN 201510209248A CN 104888778 A CN104888778 A CN 104888778A
- Authority
- CN
- China
- Prior art keywords
- copper
- mgo
- hexafluoroacetylacetone
- glucose
- catalyst
- 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
Abstract
The invention discloses a glucose hydrogenolysis catalysis Cu/MgO catalyst and a preparation method thereof, and belongs to the technical field of heterogeneous catalysis. In anhydrous anaerobic conditions, by filtering, vacuum distillation and sublimation and purification of a liquid obtained by reaction of cuprous oxide, 1, 5-cyclooctadiene, and hexafluoro-acetylacetone, metal organic precursor hexafluoro-acetylacetone-cyclooctadiene copper and hexafluoro-acetylacetone copper relatively stable to air is produced. Petal shaped Mg (OH) 2 is synthesized by solvothermal method from magnesium acetate tetrahydrate as a raw material by use of a mixture of ethanol and deionized water solution as solvent, and the petal shaped Mg (OH) 2 is calcined to obtain an alkaline mesoporous MgO carrier with high specific surface area. By MOCVD (metal organic chemical vapor deposition) method, the two metal organic precursors are supported onto the MgO carrier for hydrogen reduction to obtain the copper base catalyst Cu/MgO used for glucose hydrogenolysis reaction. The glucose hydrogenolysis catalysis Cu/MgO catalyst has the advantages of simple operation process, mild reaction condition, good catalyst activity and stability, and good prospects of industrial application.
Description
Technical field
The invention belongs to heterogeneous catalysis technology field, relate to a kind of Cu/MgO catalyst and preparation method of catalysis glucose hydrogenolysis high valuable chemicals.
Background technology
Along with the worsening shortages of fossil fuel, being on the increase of world population quantity, the demand of the mankind to the energy constantly increases again simultaneously, makes to research and develop catalyst renewable resource (living beings) being converted into high valuable chemicals and has great importance.Biomass source is extensive, cheap, and wherein, glucose is the widest and most important a kind of monose of occurring in nature distribution, and be a kind of polyhydroxy aldehyde, the glucose that native form exists belongs to D configuration, the pyrans formula that the is mainly configuration existed in the aqueous solution.At present, what glucose catalytic hydrogenolysis produced the reaction great majority employing of low-carbon polyol is all noble metal catalyst, production cost is high, and often need to add alkaline matter as promoter, according to hydrogenolysis mechanism, under the condition of alkali-free, hydrogenation and isomerization reaction can be there is in glucose, produce sorbierite and sweet mellow wine, and in the basic conditions, can hydrogenolysis be there is in glucose, produce low-carbon polyol, as 1, 2-PD, glycerine, ethylene glycol etc., they are all important chemicals and Organic Chemicals, such as, 1, unsaturated polyester (UP) produced by 2-propane diols, the important source material of epoxy resin, at coating, medicine, cosmetics, be widely used in the industries such as chemical industry.
Chinese patent, publication number: CN101781167A, introduce the method that glucose catalytic hydrogenolysis prepares dihydroxylic alcohols and polyalcohol, and it adopts and adds alkaline matter and regulate solution
ph carrys out promoting catalyst catalysis C-C bond fission and prevents the loss because producing the catalyst that the accessory substances such as organic acid cause.Reaction pressure needed for this technique is high, and not high to the single selective of product.Chinese patent, publication number: CN101921174A, introduce the method that carbon nano-fiber load ruthenium catalyzing sorbitol hydrogenolysis prepares 1,2-PD and EG, its catalyst used is noble metal catalyst, expensive, need add NaOH to regulate solution
ph is 11 ~ 13, and the conversion ratio of sorbierite and product is selective not high.The people such as B.C.Miranda (Appl.Catal.B:Environ., 2015,166 – 167,166 – 180) describe the bimetallic catalyst prepared by equi-volume impregnating is used in the hydrogenolysis of glycerine, carrier surface is distributed in by load component when make use of preparation catalyst, utilization rate high, be prepared into a kind of decentralization better, specific area is large, active catalyst preferably, but in this preparation process, the reduction temperature of catalyst is high, produce waste gas during precursors decompose, cause environmental pollution.Chinese patent, publication number: CN102924233A, describes the catalyst prepared with coprecipitation and prepares in propane diols for hydrogenolysis of glycerin, the preparation process of catalyst is more, and influence factor is complicated, if operating condition control is improper, active component local concentration may be made too high, produce and reunite.The nickel catalyse cellulose hydrogenolysis that the people such as X.C.Wang (Green Chem., 2012,14,758-765) describe load changes into the method for 1,2-alkane glycol, in this technique, adopts less (the about 20m of specific surface area of catalyst prepared by coprecipitation
2g
-1), and the product species that hydrogenolysis is produced is more, single selective is poor.
The Catalyst Production cost used for glucose hydrogenolysis is high, reaction solution often need add alkaline matter as promoter and the problem such as production efficiency is low, we successfully have developed and adopt MOCVD method to prepare alkaline oxygenated magnesium-supported copper-based catalysts, and it is better dispersed, and specific area is larger, catalytic activity is high, be applied in glucose hydrogenolysis, without the need to adding alkaline accelerator, and glucose can transform completely, be 60% ~ 72% to the selective of 1,2-PD.
Summary of the invention
The invention provides a kind of Cu/MgO catalyst and preparation method of catalysis glucose hydrogenolysis high valuable chemicals.
The present invention synthesizes petal-shaped Mg (OH) with solvent-thermal method in Hydrothermal Synthesis still
2, after calcining, obtain alkaline mesoporous MgO carrier, remain Mg (OH)
2appearance structure and there is larger specific area; Synthesize the metastable two kinds of metallorganic precursors hexafluoroacetylacetones-cyclo-octadiene copper (I) of air and hexafluoroacetylacetone copper under anhydrous and oxygen-free condition; Adopt the method synthesized high-performance Cu/MgO catalysis material of metal organic chemical vapor deposition (MOCVD), hydrogen reducing; And be solvent with Green Water, in high-pressure hydrogenation reactor, carry out glucose hydrogenolysis (concentration of glucose is 5-20wt%), hydrogenolysis adopts segmentation constant voltage operation, first paragraph reaction temperature 120-140 DEG C, reaction pressure 4-8MPa; Second segment reaction temperature 200-250 DEG C, reaction pressure 4-8MPa.Invention increases the selective of 1,2-PD and additionally do not add alkali in the hydrogenolysis solution of glucose as promoter, operating procedure is simple, and environmental friendliness, catalytic activity is high, and the single selective of product is fine.
Technical scheme of the present invention is as follows:
A Cu/MgO Catalysts and its preparation method for catalysis glucose hydrogenolysis, by Magnesium acetate (Mg(OAc)2) tetrahydrate, ethanol and deionized water carry out stirring reaction, afterwards solution are injected stainless steel autoclave, are placed in the baking oven of 180 DEG C and react; Take out autoclave and be cooled to room temperature, reactant liquor carried out centrifugation, washs, be drying to obtain white solid powder magnesium hydroxide; Magnesium hydroxide is carried out calcining under the atmosphere of argon gas and oxygen and namely obtains MgO carrier.Under anhydrous and oxygen-free condition, by cuprous oxide, 1,5-cyclo-octadiene, hexafluoroacetylacetone, oxolane stirring reaction, the solution obtained is carried out decompression distillation to remove desolventizing, afterwards the pressed powder obtained is carried out sublimation purification, obtain air metastable metallorganic precursors hexafluoroacetylacetone-cyclo-octadiene copper (I) and hexafluoroacetylacetone copper; Fully being mixed with carrier magnesia respectively by these the two kinds of precursors obtained loads in Shi Lanke bottle, respectively in uniform temperature, carries out vapour deposition under the condition of vacuum.Taking out post-depositional pressed powder is placed in reduction tube, at argon gas, carry out under the atmosphere of hydrogen reducing namely obtaining catalysis material Cu/MgO, it is joined in autoclave together with 5-20wt% glucose solution and carries out hydrogenolysis, reaction pressure 4-8MPa, first paragraph reaction temperature 120-140 DEG C, second segment reaction temperature 200-250 DEG C, mixing speed 800r/min, naturally cools to room temperature after having reacted.Filter the product after reaction, and reclaim catalyst.Jointly product is characterized by gas phase and liquid chromatogram, calculate the conversion ratio of glucose and the selective of product.
Prepared according to the methods of the invention supported non-noble metal catalysis material can be applicable to the aspects such as hydrogenation, dehydrogenation, oxidation, alkylation, cyclisation, removal organic pollution, automobile exhaust pollution thing and embodies excellent catalytic performance, and the present invention is simple to operate, environmental friendliness, has wide prospects for commercial application.Be used for glucose hydrogenolysis by metal supported catalyst of the present invention, glucose transforms completely, reaches more than 70% to the selective of 1,2-PD, solves the problems such as glucose hydroformylation product solution single selective is not good.
Accompanying drawing explanation
The stereoscan photograph of Fig. 1 carrier MgO.
Fig. 2 (a) loading is the transmission electron microscope photo of 5%Cu/MgO (I).
Fig. 2 (b) loading is the transmission electron microscope photo of 5%Cu/MgO (II).
Fig. 2 (c) loading is the transmission electron microscope photo of 15%Cu/MgO (I).
Fig. 2 (d) loading is the transmission electron microscope photo of 15%Cu/MgO (II).
Detailed description of the invention
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1 ~ 3
(volume ratio is respectively: 2:1 Magnesium acetate (Mg(OAc)2) tetrahydrate to be joined respectively the mixed solution of the deionized water of 60ML and absolute ethyl alcohol, 1:1, stirring reaction 1:2), then solution is joined in stainless steel autoclave respectively, be placed in 180 DEG C of baking ovens and continue reaction, respectively centrifugation is carried out to reactant liquor afterwards, with deionized water and the absolute ethanol washing of corresponding proportion, finally be put in baking oven and carry out drying, namely obtain Mg (OH)
2, and be placed in tube type resistance furnace, at 500 DEG C, calcine under the atmosphere of argon gas and oxygen, namely obtain MgO carrier.Consider the pattern of MgO and productive rate, choose deionized water that volume ratio is 1:2 and absolute ethyl alcohol reacts.The stereoscan photograph of gained sample is shown in Fig. 1.
| Magnesium acetate (Mg(OAc)2) tetrahydrate/g | V Deionized water：V Absolute ethyl alcohol | Magnesium hydroxide/g | |
| Example 1 | 1.29 | 2:1 | 0.009 |
| Example 2 | 1.29 | 1:1 | 0.032 |
| Example 3 | 1.29 | 1:2 | 0.100 |
Embodiment 4
By Cu
2o joins in three mouthfuls of round-bottomed flasks, adds 1,5-cyclo-octadiene and THF stirring reaction under the atmosphere of argon gas, then within half an hour, injects 1 by constant voltage separatory funnel, 1,1,5,5,5-hexafluoro-2,4-pentanedione and THF continue stirring reaction, and reaction terminates the unreacted Cu of rear filtration
2o, the filtrate obtained is carried out decompression distillation with except desolventizing, afterwards sublimation purification is carried out to pressed powder, obtain corresponding metallorganic precursors hexafluoroacetylacetone-cyclo-octadiene copper (I), learnt by thermogravimetric analysis, the temperature that supports of monovalence copper precursors elects 100 DEG C as.
Embodiment 5
Substantially the same manner as Example 4, only do not add 1,5-cyclo-octadiene, corresponding metallorganic precursors hexafluoroacetylacetone copper can be obtained.Learnt by thermogravimetric analysis, the temperature that supports of cupric precursor elects 60 DEG C as.
Embodiment 6 ~ 7
Monovalence copper precursors and cupric precursor are placed on respectively the side in two chemical vapor deposition unit Y-pieces, carrier is placed on opposite side, respectively at 100 DEG C and 60 DEG C, under vacuum condition, carry out vapour deposition, the supported copper catalyst (embodiment 6) that loading is 5wt% can be obtained.
Monovalence copper precursors and cupric precursor are placed in agate mortar with carrier respectively and grind, it is made fully to mix, then mixture is respectively charged in Shi Lanke bottle, under other condition is identical, carries out vapour deposition, the supported copper catalyst (embodiment 7) that loading is 5wt% can be obtained respectively.Embodiment 6,7 support device and operation is compared, be easier to support together with carrier is ground with precursor, namely obtain the supported copper catalyst that loading is 10wt%, 15wt%.By monovalence copper precursors, the catalyst that cupric precursor obtains is labeled as Cu/MgO (I), Cu/MgO (II) respectively.
Embodiment 8 ~ 9
The pressed powder supported is placed in reduction tube, at 200 DEG C, argon gas (flow is 20mL/min), reductase 12 h (embodiment 8) under the atmosphere of hydrogen (20mL/min), when finding that gas flow is large, the precursor supported is caused to be taken away by gas.Therefore modulation hydrogen and argon gas flow and be all 10mL/min (embodiment 9), other conditions are constant, can obtain the supported copper catalyst of the different loadings reduced.Fig. 2 (a)-(d) be shown in by the transmission electron microscope photo of gained sample.
Embodiment 10 ~ 12
Taking glucose is dissolved in deionized water, be made into the solution that 3 parts of mass concentrations are 5wt%, it is joined in reactor respectively, add the supported copper catalyst Cu/MgO (I) that the good loading of prereduction is 5wt%, 10wt%, 15wt% afterwards respectively, capping still, adopt segmentation constant voltage heating operation, at 6Mpa, stirring reaction 2h under the condition of 140 DEG C, mixing speed is set to 800r/min, then under the condition of 220 DEG C, reacts 3h.Filter the product after reaction, carry out gas phase and liquid-phase chromatographic analysis, and reclaim catalyst.The conversion ratio obtaining glucose is 100%.
Embodiment 13 ~ 15
Taking glucose is dissolved in deionized water, be made into the solution that 3 parts of mass concentrations are 5wt%, it is joined in reactor respectively, add the supported copper catalyst Cu/MgO (II) that the good loading of prereduction is 5wt%, 10wt%, 15wt% afterwards respectively, capping still, adopt segmentation constant voltage heating operation, at 6Mpa, stirring reaction 2h under the condition of 140 DEG C, mixing speed is set to 800r/min, then under the condition of 220 DEG C, reacts 3h.Filter the product after reaction, carry out gas phase and liquid-phase chromatographic analysis, and reclaim catalyst.The conversion ratio obtaining glucose is 100%.
Embodiment 16
In order to compare the glucose hydrogenolysis performance of the catalyst prepared without method, taking glucose is dissolved in deionized water, be made into the solution that mass concentration is 5wt%, joined in reactor, add the supported copper catalyst Cu/MgO adopting co-precipitation to prepare afterwards, capping still, adopt segmentation constant voltage heating operation, at 6Mpa, stirring reaction 2h under the condition of 140 DEG C, mixing speed is set to 800r/min, then under the condition of 220 DEG C, reacts 3h.Filter the product after reaction, carry out gas phase and liquid-phase chromatographic analysis, and reclaim catalyst.The conversion ratio obtaining glucose is 71.9%.
Claims (3)
1. a preparation method for the Cu/MgO catalyst of catalysis glucose hydrogenolysis, is characterized in that:
In Hydrothermal Synthesis still, petal-shaped Mg (OH) is synthesized with solvent-thermal method
2, after calcining, obtain alkaline mesoporous MgO carrier; Synthesize the metastable two kinds of metallorganic precursors hexafluoroacetylacetones-cyclo-octadiene copper (I) of air and hexafluoroacetylacetone copper under anhydrous and oxygen-free condition; Adopt the method synthesized high-performance Cu/MgO catalysis material of metal organic chemical vapor deposition, hydrogen reducing; Take water as solvent, in high-pressure hydrogenation reactor, carry out glucose hydrogenolysis, concentration of glucose is 5-20wt%;
Hydrogenolysis adopts segmentation constant voltage operation:
First paragraph reaction temperature 120-140 DEG C, reaction pressure 4-8MPa;
Second segment reaction temperature 200-250 DEG C, reaction pressure 4-8Mpa.
2. preparation method according to claim 1, is characterized in that:
(1) Magnesium acetate (Mg(OAc)2) tetrahydrate, ethanol and deionized water are carried out stirring reaction, the solution obtained injects stainless steel autoclave, is placed in the baking oven of 180 DEG C and reacts; Take out autoclave and be cooled to room temperature, reactant liquor carried out centrifugation, washs, be drying to obtain white solid powder magnesium hydroxide;
(2) magnesium hydroxide is carried out calcining under the atmosphere of argon gas and oxygen both obtain MgO carrier;
(3) under anhydrous and oxygen-free condition, by cuprous oxide, 1,5-cyclo-octadiene, hexafluoroacetylacetone and oxolane stirring reaction, the solution obtained is carried out decompression distillation to remove desolventizing, afterwards the pressed powder obtained is carried out sublimation purification, obtain air metastable metallorganic precursors hexafluoroacetylacetone-cyclo-octadiene copper (I) and hexafluoroacetylacetone copper;
(4) two kinds of precursors that step (3) obtains fully are mixed with MgO carrier respectively, carry out vapour deposition; Taking out post-depositional pressed powder is placed in reduction tube, at argon gas, carries out reducing namely obtaining catalysis material Cu/MgO under the atmosphere of hydrogen;
(5) itself and 5-20wt% glucose solution are joined segmentation constant voltage hydrogenolysis in autoclave, after having reacted, naturally cool to room temperature; Filter the product after reaction, and reclaim catalyst.
3. preparation method according to claim 1 and 2, is characterized in that: described metal organic copper precursor comprises hexafluoroacetylacetone-vinyltrimethoxy silane copper (I), acetylacetone copper, hexafluoroacetylacetone-haloflex copper (I), hexafluoroacetylacetone-trimethyl-phosphine copper (I), hexafluoroacetylacetone-cyclo-octadiene copper (I), hexafluoroacetylacetone copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510209248.3A CN104888778B (en) | 2015-04-27 | 2015-04-27 | A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510209248.3A CN104888778B (en) | 2015-04-27 | 2015-04-27 | A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104888778A true CN104888778A (en) | 2015-09-09 |
| CN104888778B CN104888778B (en) | 2017-03-29 |
Family
ID=54021982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510209248.3A Active CN104888778B (en) | 2015-04-27 | 2015-04-27 | A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104888778B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111599970A (en) * | 2020-06-01 | 2020-08-28 | 北京化工大学 | Magnesium oxide/iron composite material modified diaphragm and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD295096A5 (en) * | 1990-06-13 | 1991-10-24 | Deutsches Hydrierwerk Rodleben,De | PROCESS FOR PREPARING A CATALYST FOR GLUCOSE HYDROGENATION |
| CN102153446A (en) * | 2011-03-10 | 2011-08-17 | 江苏大学 | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis |
| CN103240102A (en) * | 2013-05-15 | 2013-08-14 | 常州工学院 | Preparation method of copper-metallic oxide and method for preparing 1, 2-propylene glycol by hydrogenating glycerol |
-
2015
- 2015-04-27 CN CN201510209248.3A patent/CN104888778B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD295096A5 (en) * | 1990-06-13 | 1991-10-24 | Deutsches Hydrierwerk Rodleben,De | PROCESS FOR PREPARING A CATALYST FOR GLUCOSE HYDROGENATION |
| CN102153446A (en) * | 2011-03-10 | 2011-08-17 | 江苏大学 | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis |
| CN103240102A (en) * | 2013-05-15 | 2013-08-14 | 常州工学院 | Preparation method of copper-metallic oxide and method for preparing 1, 2-propylene glycol by hydrogenating glycerol |
Non-Patent Citations (2)
| Title |
|---|
| XINGUO CHEN ET AL.: "Hydrogenolysis of biomass-derived sorbitol to glycols and glycerol over Ni-MgO catalysts", 《CATALYSIS COMMUNICATIONS》 * |
| 张建利等: "Cu/Mg0催化剂CO加氢低温甲醇合成研究", 《煤炭转化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111599970A (en) * | 2020-06-01 | 2020-08-28 | 北京化工大学 | Magnesium oxide/iron composite material modified diaphragm and preparation method thereof |
| CN111599970B (en) * | 2020-06-01 | 2021-06-01 | 北京化工大学 | Magnesium oxide/iron composite material modified diaphragm and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104888778B (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101985103B (en) | Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof | |
| Liu et al. | Simultaneous production of lactic acid and propylene glycol from glycerol using solid catalysts without external hydrogen | |
| CN105712840A (en) | Method for producing high-carbon primary alcohols by catalytic conversion of ethanol | |
| CN109796428B (en) | Application of copper-based catalyst in hydrogenation of 5-hydroxymethylfurfural | |
| CN102924233B (en) | Method for preparing propylene glycol by glycerin hydrogenolysis | |
| CN102728380B (en) | Application of catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis | |
| CN107398276B (en) | Catalyst for preparing 2, 5-dimethylfuran by catalyzing selective hydrodeoxygenation of 5-hydroxymethylfurfural and preparation method | |
| CN108325532A (en) | Catalyst in the building-up process of methyl glycollate and preparation method thereof, application | |
| CN105315130A (en) | Method used for preparing 1,3-dihydric alcohol via Prins condensation reaction | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN101747152B (en) | Citral liquid-phase hydrogenation method for synthesizing unsaturated alcohols | |
| CN103170338B (en) | A kind of catalyst for being used for 1,2 propane diols and preparation method thereof | |
| CN103240095A (en) | Methyl acetate hydrogenation catalyst and preparation method thereof | |
| CN107398264B (en) | Mg-Zr-Zn composite metal oxide catalyst and preparation method and application thereof | |
| CN102173977B (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN112191253A (en) | Supported nano metal catalyst, preparation method and application thereof | |
| CN109851473B (en) | Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution | |
| CN102153444B (en) | Method for preparing 1,3-diols | |
| CN111054339B (en) | Catalyst composition for preparing ethylene glycol | |
| CN104888778A (en) | Glucose hydrogenolysis catalysis Cu/MgO catalyst and preparation method thereof | |
| CN103130625A (en) | Method for preparing acetaldehyde and co-producing acetal by using ethanol | |
| KR20130017250A (en) | Method for preparing high-yield biofuel from guaiacol | |
| CN108404919A (en) | Copper C catalyst and preparation method thereof for esters liquid-phase hydrogenatin synthetic fatty alcohol | |
| CN102886269B (en) | Catalyst for synthesizing crotyl alcohol by crotonic aldehyde through gas phase selective hydrogenating and preparation method | |
| CN108940341B (en) | Catalyst for preparing alkane by catalytic hydrogenation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 124221 Liaoning city of Panjin Province in the Liaodong Bay Area Road No. 2 Applicant after: Dalian University of Technology Applicant after: Towngas Environmental Protection Energy Research Institute Co.,Ltd. Address before: The Liaodong Bay area large 124221 Dalian Road, Liaoning city of Panjin province No. 2 Applicant before: Dalian University of Technology Applicant before: Towngas Environmental Protection Energy Research Institute Co.,Ltd. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |