CN103028403A - Body type copper-based ester hydrogenation catalyst and preparation method and application thereof - Google Patents
Body type copper-based ester hydrogenation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN103028403A CN103028403A CN2011102982400A CN201110298240A CN103028403A CN 103028403 A CN103028403 A CN 103028403A CN 2011102982400 A CN2011102982400 A CN 2011102982400A CN 201110298240 A CN201110298240 A CN 201110298240A CN 103028403 A CN103028403 A CN 103028403A
- Authority
- CN
- China
- Prior art keywords
- copper
- molar concentration
- catalyst
- mixed
- preparation
- 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
Images
Abstract
The invention provides a preparation method of a high dispersion body type copper-based metal catalyst. The copper-based metal catalyst is prepared by the following steps of: baking in an air atmosphere at a high temperature by taking Cu/Mg/Al laminar double-metal hydroxide particles as a precursor to obtain a Cu/Mg/Al compound metal oxide; and reducing in a hydrogen atmosphere to obtain a catalyst through which nanometer metal copper is highly dispersed into a magnesium-aluminum compound metal oxide substrate. The catalyst has the characteristics of high dispersion and high activity, and the specific surface area is 100-200 m<2>/g. The catalyst is applied to hydrogenation of 1,4-cyclohexanedicarboxylate for preparing 1,4-cyclohexanedimethanol, the reaction transformation ratio can be up to 90-99 percent, and the selectivity of 1,4-cyclohexanedimethanol is up to 90-98 percent.
Description
Technical field
The present invention relates to catalyst preparation technical field, be specifically related to high dispersive, high activity body formula copper base hydrogenation catalyst and preparation method thereof, this catalyst is mainly used in the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation.
Background technology
Isosorbide-5-Nitrae-cyclohexanedimethanol (CHDM) industrial be a kind of important production of polyester raw material, synthetic unsaturated polyester (UP) can be used as colloid coating, lamination and notes film resin, its product has good chemical resistance and environment.CHDM is used for the production of polyester fiber, not only have more the characteristics such as low-density, high-melting-point, and its hydrolytic stability and electric property are also more excellent, and the high symmetry that is specially adapted to make electric equipment CHDM also can make the crystallinity of mylar improve glass transition temperature; Because the primary hydroxyl of CHDM does not have sterically hindered, so preparation just approaches with the raw material acid molecule during mylar easily, secondly when crosslinking curing, easily and crosslinking agent approaching, its result can generate polymer at short notice, can obtain in addition the polymer of hardening at subcritical temerature type or short time constrictive type.
In industrial production, CHDM can be got by Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid dimethyl ester (DMCD) Hydrogenation.The catalyst that adopts mainly is Cu-Cr catalyst, and (GB 98801211965 for Eastman Kodak Co.Production of1,4-cyclohexanedimethanol.US such as copper chromite; Huels Aktiengesellschaft.Method of producing aliphatic and cycloaliphatic diols by catalytic hydrogenation of dicarboxylic acid esters.DE, US5030771.1989), the alkaline-earth metal such as baric are copper chromite catalyst (the Towa Kasei Kogyo KK.Production of 1 of co-catalyst, 4-cyclohexanedimethanol.JP 6192146.1992), and the Cu-Cr catalyst (Arakawa Chem Ind Co Ltd.Production of Isosorbide-5-Nitrae-cyclohexanedimethanol.JP 6228028.1993) that contains manganese.But such catalyst also has certain shortcoming, and crushing strength is low, and is active unstable, and in the life-span short (catalyst regeneration is frequent), carrying out ester through hydrogenation, to react needed reaction pressure very high, usually more than 20MPa, is unfavorable for suitability for industrialized production.In addition, because preparation method's restriction is in a kind of at random unordered non-homogeneous state as the dispersion in structure between the various metallic elements of active constituent and other doped chemical, this dispersity can only be finely tuned within the specific limits on the impact of catalytic active center distribution, activated centre power and number, can't fundamentally break through and control, and then have a strong impact on the performance of cooperative effect between catalytic activity and the active component.Layered double hydroxide (LDHs) is the novel nano inorganic functional material that a class has layer structure, and its chemical composition can be expressed as [M
2+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+Be Mg
2+, Ni
2+, Co
2+, Mg
2+, Cu
2+, Mn
2+Deng divalent metal; M
3+Be Al
3+, Cr
3+, Fe
3+, Sc
3+Deng trivalent metal cation; A
N-Be anion, such as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6H
4(COO)
2 2-Etc. inorganic, organic ion and complex ion.In the LDHs crystal structure, owing to be subjected to the impact of the minimum effect of lattice energy and lattice orientation effect thereof, so that metal ion evenly distributes on laminate in a certain way, namely on laminate in each small construction unit, its chemical composition and structure is constant.Because the chemical composition and structure of LDHs has Modulatory character and whole uniformity at microcosmic, itself is again the two-dimensional nano material, can introduce potential catalytic active species to its laminate by design, prepare active stratiform presoma.
Summary of the invention
The purpose of this invention is to provide a kind of high dispersive, high activity body formula copper base ester through hydrogenation Catalysts and its preparation method, and this catalyst is applied to the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation.
The present invention forms the characteristics of adjustable sex change according to layered double hydroxide (LDHs) structure designability and laminate, the high dispersive effect that utilizes the colloid mill High Rotation Speed to produce, obtain first Cu/Mg/Al type LDHs nanoparticle sol, hydrothermal crystallizing generates the LDHs nano particle of stratiform compound with regular structure again, prepares high dispersive, high activity, copper base hydrogenation catalyst cheaply by Roasting Decomposition and reduction at last.
This high dispersive, high activity body formula copper base ester through hydrogenation catalyst are that nano-metallic copper is dispersed in the Al-Mg composite metal oxide matrix, and its specific area is at 100～200m
2Between/the g.Because self special microstructure of lamellar precursor can make active component be dispersed in catalyst surface, active component and carrier act synergistically mutually simultaneously, therefore this catalyst is applied to 1,4-dimethyl hexahydrophthalate Hydrogenation standby 1, the 4-cyclohexanedimethanol has excellent catalytic activity and selective.
This method for preparing catalyst is:
A. with corresponding solubility nitrate and deionized water preparation mixed nitrate solution, the metal ion in the mixed nitrate solution is Cu
2+, Mg
2+And Al
3+, wherein the mol ratio of bivalent metal ion and trivalent metal ion is 2-4: 1, and the mol ratio of copper ion and magnesium ion is 0.3-2: 1; Cu wherein
2+Molar concentration be 0.1～0.4mol/L, Mg
2+Molar concentration be 0.1～0.4mol/L, Al
3+Molar concentration be 0.1～0.4mol/L.
B. NaOH and solubility inorganic sodium are dissolved in preparation mixed-alkali solution in the deionized water, wherein the NaOH molar concentration is 1.6 times of molar concentration of all metal ions in the mixed nitrate solution of steps A, and the molar concentration of sodium salt is 2 times of aluminium ion molar concentration in the mixed solution; Described solubility inorganic sodium is that nitric acid is received, a kind of in sodium sulphate or the sodium chloride.
C. pour into simultaneously above-mentioned mixing salt solution and mixed-alkali solution equal-volume in the colloid mill, stirred 2-10 minute with 1000-2500 rev/min rotating speed, isolate sediment, with deionized water centrifuge washing 5 times, to pH to 6.5-7.5, then the ratio that adds 20-30ml water in every gram sediment adds deionized water, in 60～80 ℃ of crystallization 6～48 hours, naturally cools to room temperature; Centrifugation obtained copper magnalium laminar double-metal hydroxide precursor in 8～24 hours in 60～80 ℃ of lower dryings;
D. the copper magnalium laminar double-metal hydroxide precursor that step C is obtained places Muffle furnace, is warming up to 500-700 ℃ with the speed of 2～10 ℃/min, and insulation 3～12h naturally cools to room temperature, obtains copper based composite metal oxidate;
E, the copper based composite metal oxidate that obtains among the step D is placed tube-type atmosphere furnace, under hydrogen atmosphere, be warming up to 200～400 ℃ and be incubated 3～5h with the heating rate of 5～10 ℃/min, after naturally cooling to room temperature, obtain monolithic devices copper base hydrogenation catalyst.Monolithic devices copper base hydrogenation catalyst is passed into the H of 8MPa under 220 ℃
2, to carry out Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalytic hydrogenation and prepare the 1,4-CHDM reaction, reaction conversion ratio can reach 90～99%, and it selectively can reach 90～98% to 1,4-CHDM.
The body formula copper base hydrogenation catalyst that obtains is characterized, the results are shown in Figure 1-3.
Fig. 1 is the x-ray diffraction pattern (XRD) of embodiment 2 laminate precursors, can see the characteristic diffraction peak of layered double hydroxide, proves the LDHs precursor that has generated pure cupric.Fig. 2 can find out the characteristic diffraction peak that MgO, Cu simple substance and composite metal oxide have occurred for implementing the x-ray diffraction pattern (XRD) of product of roasting in 2, has synthesized the copper-based catalysts of high dispersive.Fig. 3 can find out the particle diameter distribution uniform of metallic copper nano particle for implementing the projection Electronic Speculum figure (TEM) of 2 copper-based catalysts.
The present invention has following remarkable result: but adopt the layered duplex metal hydroxide nanometer particle that a process for preparing to have the characteristics of metallic element high degree of dispersion, structure homogeneous, the Nomenclature Composition and Structure of Complexes modulation, and the copper base metal hydrogenation catalyst that therefore obtains with nano particle roasting and reduction has the active component high degree of dispersion and is evenly distributed.The catalyst raw material that has overcome the prior art preparation mixes the shortcomings such as inhomogeneous, active low and active component easy stripping loss.Without corrosiveness, non-environmental-pollution is fit to suitability for industrialized production to technical process of the present invention to production equipment.
Description of drawings
Fig. 1 is the XRD figure of embodiment 2 laminate precursors
Fig. 2 is the XRD figure of copper base metal hydrogenation catalyst among the embodiment 2
Fig. 3 is the TEM of copper base hydrogenation catalyst among the embodiment 2.
The specific embodiment
Embodiment 1
By the accurate weighing Cu of stoichiometric proportion (NO
3)
26H
2O, Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O is mixed with mixing salt solution with deionized water, Cu in the solution
2+Molar concentration for for 0.3mol/L, Mg
2+Molar concentration be 0.3mol/L, Al
3+Molar concentration be 0.15mol/L.NaOH and sodium sulphate are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 1.2mol/L, and the sodium salt molar concentration is 0.3mol/L.Pour into simultaneously isopyknic 100ml mixing salt solution and mixed-alkali solution in the colloid mill, 3000 rev/mins rotating speed stirred 2 minutes, then use the deionized water centrifuge washing 5 times, to pH to 7, then join in the 500ml there-necked flask 60 ℃ of crystallization 6 hours with 250ml water, naturally cool to afterwards room temperature.After filtration, washing, 60 ℃ obtained the CuMgAl-LDH nano particle in lower dry 12 hours, then the LDHs precursor for preparing were placed Muffle furnace, were warming up to 600 ℃ with the speed of 5 ℃/min, insulation 5h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate that obtains is placed tube-type atmosphere furnace, be warming up to 300 ℃ and be incubated 5h and obtain body formula copper base hydrogenation catalyst with the heating rate of 5 ℃/min under hydrogen atmosphere, specific area is 150m
2/ g.
Take by weighing the 2.0g catalyst and utilize the high-pressure hydrogenation reaction to carry out the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation, reaction conversion ratio can reach 99.0%, and can reach 96.0% to the conversion ratio of goal response thing 1,4-CHDM.
Embodiment 2
By the accurate weighing Cu of stoichiometric proportion (NO
3)
26H2O, Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O is mixed with mixing salt solution with deionized water, Cu in the solution
2+Molar concentration for for 0.2mol/L, Mg
2+Molar concentration be 0.2mol/L, Al
3+Molar concentration be 0.2mol/L.NaOH and sodium chloride are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 0.96mol/L, and the sodium chloride molar concentration is 0.4mol/L.Pour into simultaneously isopyknic 100ml mixing salt solution and mixed-alkali solution in the colloid mill, 5000 rev/mins rotating speed stirred 5 minutes, then use the deionized water centrifuge washing 5 times, to pH to 7, then join in the 500ml there-necked flask 80 ℃ of crystallization 24 hours with 250ml water, naturally cool to afterwards room temperature.After filtration, washing, 80 ℃ obtained the CuMgAl-LDH nano particle in lower dry 24 hours, then the LDHs precursor for preparing were placed Muffle furnace, were warming up to 600 ℃ with the speed of 2 ℃/min, insulation 10h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate that obtains is placed tube-type atmosphere furnace, be warming up to 270 ℃ and be incubated 3h and obtain body formula copper base hydrogenation catalyst with the heating rate of 10 ℃/min under hydrogen atmosphere, specific area is 177m
2/ g.
Take by weighing the 2.0g catalyst and utilize high-pressure hydrogenation reaction to carry out the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation, reaction conversion ratio can reach 99.0%, can reach 98.0% to the conversion ratio of goal response thing 1,4-CHDM.
Embodiment 3
By the accurate weighing Cu of stoichiometric proportion (NO
3)
26H
2O, Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O is mixed with mixing salt solution with deionized water, Cu in the solution
2+Molar concentration be 0.3mol/L, Mg
2+Molar concentration be 0.3mol/L, Al
3+Molar concentration be 0.4mol/L.NaOH and sodium chloride are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 1.6mol/L, and the sodium chloride molar concentration is 0.8mol/L.Pour into simultaneously isopyknic 100ml mixing salt solution and mixed-alkali solution in the colloid mill, 6000 rev/mins rotating speed stirred 10 minutes, then use the deionized water centrifuge washing 5 times, to pH to 7, then join in the 500ml there-necked flask 80 ℃ of crystallization 24 hours with 250ml water, naturally cool to afterwards room temperature.After filtration, washing, 70 ℃ obtained the CuMgAl-LDH nano particle in lower dry 12 hours, then the LDHs precursor for preparing were placed Muffle furnace, were warming up to 550 ℃ with the speed of 10 ℃/min, insulation 8h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate that obtains is placed tube-type atmosphere furnace, be warming up to 300 ℃ and be incubated 3h and obtain body formula copper base hydrogenation catalyst with the heating rate of 10 ℃/min under hydrogen atmosphere, specific area is 190m
2/ g.
Take by weighing the 2.0g catalyst and utilize high-pressure hydrogenation reaction to carry out the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation, reaction conversion ratio can reach 98.0%, can reach 94.0% to the conversion ratio of goal response thing 1,4-CHDM.
Embodiment 4
By the accurate weighing Cu of stoichiometric proportion (NO
3)
26H
2O, Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O is mixed with mixing salt solution with deionized water, Cu in the solution
2+Molar concentration be 0.2mol/L, Mg
2+Molar concentration be 0.1mol/L, Al
3+Molar concentration be 0.2mol/L.NaOH and sodium chloride are dissolved in preparation mixed-alkali solution in the deionized water, and wherein the NaOH molar concentration is 1.0mol/L, and the sodium chloride molar concentration is 0.4mol/L.Pour into simultaneously isopyknic 100ml mixing salt solution and mixed-alkali solution in the colloid mill, 6000 rev/mins rotating speed stirred 5 minutes, then use the deionized water centrifuge washing 5 times, to pH to 7, then join in the 500ml there-necked flask 60 ℃ of crystallization 24 hours with 250ml water, naturally cool to afterwards room temperature.After filtration, washing, 70 ℃ obtained the CuMgAl-LDH nano particle in lower dry 24 hours, then the LDHs precursor for preparing were placed Muffle furnace, were warming up to 650 ℃ with the speed of 5 ℃/min, insulation 10h obtains copper base copper based composite metal oxidate.The copper based composite metal oxidate that obtains is placed tube-type atmosphere furnace, be warming up to 250 ℃ and be incubated 5h and obtain body formula copper base hydrogenation catalyst with the heating rate of 5 ℃/min under hydrogen atmosphere, specific area is 172m
2/ g.
Take by weighing the 2.0g catalyst and utilize high-pressure hydrogenation reaction to carry out the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation, reaction conversion ratio can reach 96.0%, can reach 93.0% to the conversion ratio of goal response thing 1,4-CHDM.
Claims (3)
1. the preparation method of a body formula copper base ester through hydrogenation catalyst, concrete steps are as follows:
A. with corresponding solubility nitrate and deionized water preparation mixed nitrate solution, the metal ion in the mixed nitrate solution is Cu
2+, Mg
2+And Al
3+, wherein the mol ratio of bivalent metal ion and trivalent metal ion is 2-4: 1, and the mol ratio of copper ion and magnesium ion is 0.3-2: 1; Cu wherein
2+Molar concentration be 0.1～0.4mol/L, Mg
2+Molar concentration be 0.1～0.4mol/L, Al
3+Molar concentration be 0.1～0.4mol/L;
B. NaOH and solubility inorganic sodium are dissolved in preparation mixed-alkali solution in the deionized water, wherein the NaOH molar concentration is 1.6 times of molar concentration of all metal ions in the mixed nitrate solution of steps A, and the molar concentration of sodium salt is 2 times of aluminium ion molar concentration in the mixed solution; Described solubility inorganic sodium is that nitric acid is received, a kind of in sodium sulphate or the sodium chloride;
C. pour into simultaneously above-mentioned mixing salt solution and mixed-alkali solution equal-volume in the colloid mill, stirred 2-10 minute with 1000-2500 rev/min rotating speed, isolate sediment, with deionized water centrifuge washing 5 times, to pH to 6.5-7.5, then the ratio that adds 20-30ml water in every gram sediment adds deionized water, in 60～80 ℃ of crystallization 6～48 hours, naturally cools to room temperature; Centrifugation obtained copper magnalium laminar double-metal hydroxide precursor in 8～24 hours in 60～80 ℃ of lower dryings;
D. the copper magnalium laminar double-metal hydroxide precursor that step C is obtained places Muffle furnace, is warming up to 500-700 ℃ with the speed of 2～10 ℃/min, and insulation 3～12h naturally cools to room temperature, obtains copper based composite metal oxidate;
E, the copper based composite metal oxidate that obtains among the step D is placed tube-type atmosphere furnace, be warming up to 200～400 ℃ and be incubated 3～5h with the heating rate of 5～10 ℃/min under hydrogen atmosphere, room temperature to be naturally cooled to obtains monolithic devices copper base hydrogenation catalyst.
2. the body formula copper base ester through hydrogenation catalyst of a method preparation according to claim 1 is that nano-metallic copper is dispersed in the Al-Mg composite metal oxide matrix, and its specific area is at 100～200m
2Between/the g.
3. the application of a body formula copper base ester through hydrogenation catalyst claimed in claim 2, this catalyst are applied to the standby 1,4-CHDM of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Hydrogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110298240.0A CN103028403B (en) | 2011-09-30 | 2011-09-30 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110298240.0A CN103028403B (en) | 2011-09-30 | 2011-09-30 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103028403A true CN103028403A (en) | 2013-04-10 |
| CN103028403B CN103028403B (en) | 2014-11-05 |
Family
ID=48016095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110298240.0A Expired - Fee Related CN103028403B (en) | 2011-09-30 | 2011-09-30 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103028403B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841436A (en) * | 2015-05-07 | 2015-08-19 | 北京化工大学 | Simple preparation method for one-piece high load copper base catalyst |
| CN109513444A (en) * | 2018-12-10 | 2019-03-26 | 上海应用技术大学 | A kind of preparation method of new copper magnesium bi-metal oxide catalyst |
| CN111545202A (en) * | 2020-04-28 | 2020-08-18 | 东南大学 | Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof |
| CN111790390A (en) * | 2020-06-18 | 2020-10-20 | 北京化工大学 | Preparation method and application of copper-based catalyst with interface synergistic effect |
| CN114032076A (en) * | 2021-12-27 | 2022-02-11 | 涉县津东经贸有限责任公司 | Hydrogenated terphenyl heat conduction oil synthesis process |
| CN114588904A (en) * | 2022-03-08 | 2022-06-07 | 中国科学院青岛生物能源与过程研究所 | Cu-based metal oxide catalyst, preparation method thereof and synthesis method of 2,3-butanediol using same |
| CN115155581A (en) * | 2022-08-02 | 2022-10-11 | 北京航空航天大学 | Copper-based composite catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
| CN101474571A (en) * | 2009-02-06 | 2009-07-08 | 北京理工大学 | Solid base catalyst for preparing biodiesel |
| CN102000572A (en) * | 2010-10-15 | 2011-04-06 | 大连理工大学 | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide |
-
2011
- 2011-09-30 CN CN201110298240.0A patent/CN103028403B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
| CN101474571A (en) * | 2009-02-06 | 2009-07-08 | 北京理工大学 | Solid base catalyst for preparing biodiesel |
| CN102000572A (en) * | 2010-10-15 | 2011-04-06 | 大连理工大学 | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841436A (en) * | 2015-05-07 | 2015-08-19 | 北京化工大学 | Simple preparation method for one-piece high load copper base catalyst |
| CN109513444A (en) * | 2018-12-10 | 2019-03-26 | 上海应用技术大学 | A kind of preparation method of new copper magnesium bi-metal oxide catalyst |
| CN111545202A (en) * | 2020-04-28 | 2020-08-18 | 东南大学 | Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof |
| CN111790390A (en) * | 2020-06-18 | 2020-10-20 | 北京化工大学 | Preparation method and application of copper-based catalyst with interface synergistic effect |
| CN114032076A (en) * | 2021-12-27 | 2022-02-11 | 涉县津东经贸有限责任公司 | Hydrogenated terphenyl heat conduction oil synthesis process |
| CN114588904A (en) * | 2022-03-08 | 2022-06-07 | 中国科学院青岛生物能源与过程研究所 | Cu-based metal oxide catalyst, preparation method thereof and synthesis method of 2,3-butanediol using same |
| CN115155581A (en) * | 2022-08-02 | 2022-10-11 | 北京航空航天大学 | Copper-based composite catalyst and preparation method and application thereof |
| CN115155581B (en) * | 2022-08-02 | 2024-04-12 | 北京航空航天大学 | Copper-based composite catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103028403B (en) | 2014-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103028403B (en) | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof | |
| Zhao et al. | From solid-state metal alkoxides to nanostructured oxides: a precursor-directed synthetic route to functional inorganic nanomaterials | |
| CN101711971B (en) | Zinc-containing multielement metallic oxide/carbon nanotube complex as well as preparation method and application thereof | |
| CN103028409A (en) | Supported copper-based metal catalyst with high dispersion as well as preparation method and application thereof | |
| CN103440997A (en) | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof | |
| CN102553581A (en) | Active component morphology controllable loaded noble metal catalyst and preparation method thereof | |
| CN102163713A (en) | Method for preparing high-voltage spinel anode material of lithium-ion secondary battery | |
| CN104841436A (en) | Simple preparation method for one-piece high load copper base catalyst | |
| CN101664676B (en) | Preparation method of composite metal oxide/carbon nanotube type visible light catalyst | |
| CN111250148A (en) | Catalyst for preparing cyclohexylbenzene by benzene hydroalkylation and preparation method and application thereof | |
| Guo et al. | Preparation of Ni–B amorphous alloy catalyst from nickel hydrazine complex with ultrasonic assistance | |
| CN101554596A (en) | Method for preparing solid base catalyst with high specific surface by hybrid composite precursors | |
| CN101279262B (en) | Preparation of highly selective epoxidized nano composite oxides for catalyzing olefin hydrocarbon and air | |
| CN103223345A (en) | Loaded nickel-indium (Ni-In) intermetallic compound catalyst and preparation method thereof | |
| CN102139914A (en) | Method for preparing calcium titanate nanoparticles | |
| Luo et al. | A single-ligand-protected Eu 60− n Gd (Tb) n cluster: a reasonable new approach to expand lanthanide aggregations | |
| CN102764654A (en) | FexOy-based inorganic nanocomposite and preparation method thereof | |
| CN109046355A (en) | A kind of copper-based houghite catalyzes and synthesizes 3,3 ', 5,5 '-tetramethyls -4,4 '-biphenyl diquinone method | |
| CN102380392A (en) | Catalyst for preparing 1, 4-cyclohexanedimethanol | |
| CN101037231A (en) | Simple method for ozone oxidation preparation of alpha-FeOOH, beta-MnO2 and Co3O4 nano material | |
| Starowicz | Electrochemical synthesis of copper oxide particles with controlled oxidation state, shape and size | |
| CN104841430A (en) | Low load-capacity hydrotalcite catalyst used for hydroxylation reaction of phenol and preparation method thereof | |
| CN114789050A (en) | Bimetal titanium niobium oxide, preparation method thereof and application of bimetal titanium niobium oxide as catalyst of hydrogen storage material | |
| CN106492862B (en) | A kind of catalyst and preparation method thereof being used to prepare cis-butenedioic anhydride | |
| Najafpour et al. | A very simple and high-yield method to synthesize nanolayered Mn oxide |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141105 Termination date: 20180930 |