CN103657633A - Preparation method and application of eggshell type molybdenum carbide catalyst - Google Patents
Preparation method and application of eggshell type molybdenum carbide catalyst Download PDFInfo
- Publication number
- CN103657633A CN103657633A CN201310589889.7A CN201310589889A CN103657633A CN 103657633 A CN103657633 A CN 103657633A CN 201310589889 A CN201310589889 A CN 201310589889A CN 103657633 A CN103657633 A CN 103657633A
- Authority
- CN
- China
- Prior art keywords
- molybdenum carbide
- preparation
- eggshell type
- carbide catalyst
- molybdenum
- 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 discloses a fast reaction film formation method to prepare an eggshell type molybdenum carbide catalyst and belongs to the technical field of industrial catalysis. The method comprises the following steps: a carrier with a molybdenum oxide perssad adsorbed on the surface is added into a melamine solution, a film composed of a molybdenum carbide precursor is rapidly generated on the surface of the carrier through the fast reaction of melamine and the molybdenum oxide perssad, and the eggshell type molybdenum carbide catalyst is formed via pyrolysis of the film. According to the invention, the technology is simple, the thickness of the shell layer can be controlled, the energy consumption during the process is low, and the utilization rate and the stability of the active components in the prepared eggshell type molybdenum carbide catalyst are high and excellent. The eggshell type molybdenum carbide catalyst has excellent industrial application prospect and can be used for alkene-alkyne selective hydrogenation reaction and other reactions represented by phenylacetylene selective hydrogenation.
Description
Technical field
The invention belongs to Industrial Catalysis technical field, relate to a kind of preparation method and application of eggshell type molybdenum carbide catalyst.
Background technology
Molybdenum carbide has the catalytic performance that is similar to noble metal, in Industrial Catalysis field, has a wide range of applications.For poisonous substance common in the raw material of industry, as carbon monoxide, sulphur, nitrogen etc., molybdenum carbide has the incomparable anti-poisoning capability of noble metal.Therefore, in many industry, relate to hydrogen process, for example, in hydrodenitrogeneration, hydrofinishing, hydroisomerizing, molybdenum carbide has shown excellent catalytic performance and higher stability, is a kind of noble metal catalyst substitute of cheapness.Molybdenum carbide is limited by the particle sintering in high temperature preparation process, often have very little specific area and very low active component degrees of exposure, therefore conventionally utilize decentralization and the anti-caking power that improves molybdenum carbide particles with the combination of carrier, thereby improve the Activity and stabill of molybdenum carbide catalyst.A large amount of studies show that, the distribution of active component on carrier is an important parameter that determines catalyst performance.For differential responses reasonable layout active component, can effectively improve the utilization rate of active phase, improve the activity of catalyst, in the life-span of extending catalyst, for the intermediate product in successive reaction, have very high selective simultaneously.The distribution of typical active component on carrier can be divided into eggshell type, protein type, yolk type and even type.Wherein the distribution of active component eggshell type is that activity is concentrated to the outer surface that is distributed in carrier mutually, thereby egg-shell catalyst has shown superior catalytic performance in the reaction of numerous surperficial fast reactions and DIFFUSION CONTROLLED.In addition, egg-shell catalyst is conducive to reaction species from the quick desorption of carrier surface, can effectively reduce the catalytic active center causing at surface aggregation because of species and poison effect, has improved the stability of catalyst.Meanwhile, the quick desorption of product has avoided it further to react, therefore can be used for improving object product in the middle of consecutive reaction selective (Ind.Eng.Chem.Prod.Res.Dev., 1981,20,439-450).
The load type molybdenum carbide catalyst that load type molybdenum carbide catalyst, especially active component are non-uniform Distribution has very large Industrial Catalysis application potential.The noble metal substitute that it can be used as a kind of cheapness is used to typical consecutive reaction if the purifying of alkene (substituting precious metals pd), prepared from benzene and hydrogen are for cyclohexene (substituting noble metal Ru) etc.With respect to traditional load type molybdenum carbide catalyst (being more common in the even type of active component distributes), eggshell type molybdenum carbide catalyst is mass transfer enhancement effectively, when keeping catalyst to have greater activity, obtains the high selectivity to intermediate product.At present, yet there are no eggshell type molybdenum carbide catalyst preparation method's pertinent literature report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of succinctly effectively preparing eggshell type molybdenum carbide catalyst, and gained eggshell type molybdenum carbide catalyst has demonstrated higher catalytic activity and selective to take alkene-alkynes selective hydrogenation that phenylacetylene selective hydrogenation is representative.
The preparation method of eggshell type molybdenum carbide catalyst of the present invention, technical scheme is as follows:
(1) preparation contains the molybdenum oxide group aqueous solution: the molybdenum source containing molybdenum oxide group is water-soluble, obtain the required aqueous solution containing molybdenum oxide group.Wherein, the molybdenum source containing molybdenum oxide group is ammonium paramolybdate, phosphomolybdic acid or silicomolybdic acid etc.
(2) dipping: oxide carrier is joined to containing in the aqueous solution of molybdenum oxide group of (1) gained, flood under normal pressure and temperature.Oxide carrier used is Al
2o
3, SiO
2or SiO
2-Al
2o
3.
(3) preparation melamine solution: melamine is dissolved in solvent, is heated to melamine and dissolves completely.Solvent for use is water, ethylene glycol, glycerine or formalin etc.
(4) prepare load molybdenum carbide presoma carrier: the oxide carrier after dipping in (2) is joined in the melamine solution of (3) gained, and the molybdenum oxide group fast reaction of melamine and Oxide-supports absorption generates molybdenum carbide presoma.
(5) pyrolysis: wash the load molybdenum carbide presoma carrier that (4) obtain with water, carry out pyrolysis after being dried under inert atmosphere, pyrolysis temperature is 600-750 ℃, and the time is 60-120min, obtains eggshell type molybdenum carbide catalyst.Wherein, inert atmosphere can be the inert atmospheres such as argon gas or helium.
Eggshell type molybdenum carbide catalyst prepared by said method is for alkene-alkynes selective hydrogenation.
Molybdenum carbide catalyst of the present invention is a kind of catalyst of active component non-uniform Distribution, the quality percentage composition of Mo is between 5-15%, it forms at carrier surface the dense film that one deck consists of molybdenum carbide presoma by the fast reaction of molybdenum oxide group and melamine, stoped the continuation diffusion of the melamine molecule in solution to carrier inside, therefore the eggshell type of having realized active component distributes, and has improved the utilization rate of active component.The method is simple to operate, and raw material is easy to get, and preparation process energy consumption is low, and catalyst performance is excellent, is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is the eggshell type molybdenum carbide catalyst hatching scanning EPMA result figure of embodiment 1 gained.
Fig. 2 (a) is the eggshell type molybdenum carbide catalyst section digital photograph of embodiment 8 gained.
Fig. 2 (b) is the eggshell type molybdenum carbide catalyst section digital photograph of embodiment 9 gained.
Fig. 2 (c) is the eggshell type molybdenum carbide catalyst section digital photograph of embodiment 10 gained.
Fig. 2 (d) is the eggshell type molybdenum carbide catalyst section digital photograph of embodiment 11 gained.
Fig. 2 (e) is the eggshell type molybdenum carbide catalyst section digital photograph of embodiment 1 gained.
Fig. 3 is molybdenum carbide particles transmission electron microscope photo in the eggshell type molybdenum carbide catalyst of embodiment 1 gained.
The specific embodiment
Below in conjunction with technical scheme, describe specific embodiments of the invention in detail.
Embodiment 1
Take 0.23g ammonium paramolybdate and put into beaker, measure 25 ml deionized water, treat to add 5 Al after ammonium paramolybdate dissolves completely
2o
3bead, standing 24 hours.Take 0.23g melamine and put into another clean beaker, measure 25 ml deionized water, be heated to 80 ℃, treat that melamine dissolves completely, maintains 80 ℃ by solution temperature.Al after the immersion that filtration is obtained
2o
3bead is put into melamine solution, reacts 5 minutes.Filtration obtains Al
2o
3bead, with deionized water rinsing, dries and is placed in argon gas atmosphere, with the programming rate of 5 ℃/min, is warming up to 650 ℃, and constant temperature 90 minutes, is down to room temperature, obtains eggshell type molybdenum carbide catalyst.
ICP result shows that the quality percentage composition of metal M o is 9.3%.As shown in Figure 1, the transmission electron microscope photo of molybdenum carbide particles as shown in Figure 3 for the EPMA characterization result of gained eggshell type molybdenum carbide catalyst.
Embodiment 2
Take 0.2g phosphomolybdic acid and put into beaker, all the other steps are identical with embodiment 1.
Embodiment 3
Take 0.2g silicomolybdic acid and put into beaker, all the other steps are identical with embodiment 1.
Embodiment 4
Measure 25 milliliters of ethylene glycol, be heated to 80 ℃ and dissolve melamine, all the other steps are identical with embodiment 1.
Embodiment 5
Measure 25 milliliters of glycerine, be heated to 80 ℃ and dissolve melamine, all the other steps are identical with embodiment 1.
Embodiment 6
Pyrolysis temperature is 600 ℃, constant temperature 120 minutes, and all the other steps are identical with embodiment 1.
Pyrolysis temperature is 750 ℃, constant temperature 60 minutes, and all the other steps are identical with embodiment 1.
Embodiment 8
Until melamine, be dissolved in completely after water, solution temperature is down to 0 ℃ and constant temperature.Al after the immersion that filtration is obtained
2o
3bead is put into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 9
Until melamine, be dissolved in completely after water, solution temperature is down to 20 ℃ and constant temperature.Al after the immersion that filtration is obtained
2o
3bead is put into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 10
Until melamine, be dissolved in completely after water, solution temperature is down to 40 ℃ and constant temperature.Al after the immersion that filtration is obtained
2o
3bead is put into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 11
Until melamine, be dissolved in completely after water, solution temperature is down to 60 ℃ and constant temperature.Al after the immersion that filtration is obtained
2o
3bead is put into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Get 1 embodiment, 1 gained eggshell type molybdenum carbide catalyst, be placed on the constant temperature zone of fixed bed reactors.Within 90 minutes, to remove the oxidation film on top layer, prereduction condition is hydrogen pressure: 0.5MPa in catalyst prereduction, hydrogen flow rate: 50mL/min, reduction temperature: 400 ℃.After prereduction finishes, fixed bed reaction actuator temperature is down to 240 ℃, hydrogen pressure rises to 2MPa.With the charging of high pressure liquid phase feed pump, raw material: the phenylacetylene that quality percentage composition is 1% is dissolved in solvent cyclohexane.Mass space velocity is 20h
-1, the mol ratio of hydrogen and phenylacetylene is 204.Product carries out gas chromatographic analysis, phenylacetylene conversion ratio 92.3% under optimal conditions, and cinnamic is selectively 98.2%.
Claims (10)
1. a preparation method for eggshell type molybdenum carbide catalyst, is characterized in that, comprises the steps:
(1) preparation contains the molybdenum oxide group aqueous solution: the molybdenum source containing molybdenum oxide group is water-soluble, obtain the aqueous solution containing molybdenum oxide group;
(2) dipping: oxide carrier is joined to containing in the aqueous solution of molybdenum oxide group of step (1) gained, flood under normal pressure and temperature;
(3) preparation melamine solution: melamine is dissolved in solvent, is heated to melamine and dissolves completely;
(4) prepare load molybdenum carbide presoma carrier: the oxide carrier after dipping in step (2) is joined in the melamine solution that step (3) obtains, obtain load molybdenum carbide presoma carrier;
(5) pyrolysis: wash the load molybdenum carbide presoma carrier that step (4) obtains with water, carry out pyrolysis after being dried under inert atmosphere, pyrolysis temperature is 600-750 ℃, and the time is 60-120min, obtains eggshell type molybdenum carbide catalyst.
2. preparation method according to claim 1, is characterized in that, the described molybdenum source containing molybdenum oxide group is ammonium paramolybdate, phosphomolybdic acid or silicomolybdic acid.
3. preparation method according to claim 1 and 2, is characterized in that, described oxide carrier is Al
2o
3, SiO
2or SiO
2-Al
2o
3.
4. preparation method according to claim 1 and 2, is characterized in that described solvent is water, ethylene glycol, glycerine or formalin.
5. preparation method according to claim 3, is characterized in that described solvent is water, ethylene glycol, glycerine or formalin.
6. according to the preparation method described in claim 1,2 or 5, it is characterized in that described inert atmosphere is argon gas or helium.
7. preparation method according to claim 3, is characterized in that described inert atmosphere is argon gas or helium.
8. preparation method according to claim 4, is characterized in that described inert atmosphere is argon gas or helium.
9. the application of the eggshell type molybdenum carbide catalyst that described in claim 1,2,5,7 or 8 prepared by preparation method, is characterized in that, described eggshell type molybdenum carbide catalyst is for alkene-alkynes selective hydrogenation.
10. the application of the eggshell type molybdenum carbide catalyst that described in claim 6 prepared by preparation method, is characterized in that, described eggshell type molybdenum carbide catalyst is for alkene-alkynes selective hydrogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310589889.7A CN103657633B (en) | 2013-11-19 | 2013-11-19 | The preparation method of eggshell type molybdenum carbide catalyst and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310589889.7A CN103657633B (en) | 2013-11-19 | 2013-11-19 | The preparation method of eggshell type molybdenum carbide catalyst and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103657633A true CN103657633A (en) | 2014-03-26 |
| CN103657633B CN103657633B (en) | 2015-10-28 |
Family
ID=50297118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310589889.7A Active CN103657633B (en) | 2013-11-19 | 2013-11-19 | The preparation method of eggshell type molybdenum carbide catalyst and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103657633B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669347A (en) * | 2015-12-31 | 2016-06-15 | 浙江工业大学 | Method for reducing content of unsaturated hydrocarbons in linear alkylbenzene |
| CN109794279A (en) * | 2019-02-22 | 2019-05-24 | 中国林业科学研究院林产化学工业研究所 | A kind of MoC/CN catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
| CN111111730A (en) * | 2019-12-19 | 2020-05-08 | 浙江师范大学 | Molybdenum carbide catalyst, preparation method and application thereof |
| CN111517906A (en) * | 2019-02-04 | 2020-08-11 | 国家能源投资集团有限责任公司 | Hydrocarbon conversion process using metal carbide nanomaterial catalyst |
| CN112916019A (en) * | 2021-01-26 | 2021-06-08 | 西南化工研究设计院有限公司 | Ferromolybdenum catalyst with core-shell structure, preparation and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2285837A (en) * | 1940-11-23 | 1942-06-09 | Norton Co | Method of producing the abrasive metal carbides |
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
| CN103204504A (en) * | 2013-03-07 | 2013-07-17 | 大连理工大学 | Method for manufacturing molybdenum carbide material containing non-stoichiometric carbon |
-
2013
- 2013-11-19 CN CN201310589889.7A patent/CN103657633B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2285837A (en) * | 1940-11-23 | 1942-06-09 | Norton Co | Method of producing the abrasive metal carbides |
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
| CN103204504A (en) * | 2013-03-07 | 2013-07-17 | 大连理工大学 | Method for manufacturing molybdenum carbide material containing non-stoichiometric carbon |
Non-Patent Citations (1)
| Title |
|---|
| MIN PANG ET AL: ""Mo(VI)-Melamine Hybrid As Single-Source Precursor to Pure Phaseβ-Mo2C for the Selective Hydrogenation of Naphthalene to Tetralin"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, 7 March 2013 (2013-03-07), pages 4564 - 4571 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669347A (en) * | 2015-12-31 | 2016-06-15 | 浙江工业大学 | Method for reducing content of unsaturated hydrocarbons in linear alkylbenzene |
| CN105669347B (en) * | 2015-12-31 | 2017-11-07 | 浙江工业大学 | A kind of method for reducing linear alkylbenzene (LAB) unsaturated hydrocarbons content |
| CN111517906A (en) * | 2019-02-04 | 2020-08-11 | 国家能源投资集团有限责任公司 | Hydrocarbon conversion process using metal carbide nanomaterial catalyst |
| WO2020160706A1 (en) * | 2019-02-04 | 2020-08-13 | China Energy Investment Corporation Limited | Hydrocarbon conversion processes using metal carbide nanomaterial catalysts |
| US11517884B2 (en) | 2019-02-04 | 2022-12-06 | China Energy Investment Corporation Limited | Metal carbide nanomaterial catalysts and production method thereof |
| CN111517906B (en) * | 2019-02-04 | 2023-04-21 | 国家能源投资集团有限责任公司 | Hydrocarbon conversion process using metal carbide nanomaterial catalyst |
| CN109794279A (en) * | 2019-02-22 | 2019-05-24 | 中国林业科学研究院林产化学工业研究所 | A kind of MoC/CN catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
| CN109794279B (en) * | 2019-02-22 | 2022-04-05 | 中国林业科学研究院林产化学工业研究所 | MoC/CN catalyst, preparation method thereof and application thereof in oleic acid hydrodeoxygenation reaction |
| CN111111730A (en) * | 2019-12-19 | 2020-05-08 | 浙江师范大学 | Molybdenum carbide catalyst, preparation method and application thereof |
| CN111111730B (en) * | 2019-12-19 | 2023-03-28 | 浙江师范大学 | Molybdenum carbide catalyst, preparation method and application thereof |
| CN112916019A (en) * | 2021-01-26 | 2021-06-08 | 西南化工研究设计院有限公司 | Ferromolybdenum catalyst with core-shell structure, preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103657633B (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106179440B (en) | N doping multi-stage porous charcoal and its preparation method and application | |
| CN103657633B (en) | The preparation method of eggshell type molybdenum carbide catalyst and application | |
| CN103949286B (en) | A kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage | |
| CN1083736C (en) | An activated raney metal fixed-bed catalyst and a process for its preparation | |
| CN106944065B (en) | Preparation method and application of graphene-supported nickel hydrogenation catalyst | |
| CN108816233A (en) | A kind of preparation method of the copper-cobalt composite oxide catalysts for benzene catalysis oxidation | |
| CN105618095B (en) | Porous nano carborundum load platinum catalyst and preparation and the application in alpha, beta-unsaturated aldehyde selective hydrogenation reaction | |
| Yin et al. | Ag/Ag2O confined visible-light driven catalyst for highly efficient selective hydrogenation of nitroarenes in pure water medium at room temperature | |
| CN107349956B (en) | Catalyst for hydrogen production by reforming ethanol steam and preparation method thereof | |
| CN110841684B (en) | Catalyst for methanol steam reforming hydrogen production and application of catalyst in methanol steam reforming hydrogen production | |
| CN102633581A (en) | Application of nano titanium oxide mesoporous composite loaded platinum catalyst to catalytic hydrogenation | |
| CN104276951A (en) | Method for using water phase to catalytically oxidize lactates for preparing pyruvates | |
| CN107999081A (en) | A kind of carbon coating structure nano iron-base fischer-tropsch synthesis catalyst and its preparation method and application | |
| CN113058596B (en) | High-stability CO 2 Preparation and application of catalyst for preparing ethanol by hydrogenation | |
| CN110665546A (en) | Noble metal/amino MOFs selective hydrogenation catalyst, preparation method and application thereof | |
| CN109851473B (en) | Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution | |
| CN111389398A (en) | Preparation method of hierarchical hollow silica confinement cuprous oxide visible-light-driven photocatalyst | |
| CN108855158B (en) | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN101157677B (en) | Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst | |
| CN106964356B (en) | Semiconductor catalyst for light auxiliary catalysis methanol and carbon dioxide Synthesis of dimethyl carbonate | |
| CN110433850B (en) | Bimetallic catalyst for catalyzing hydrogenation deoxidation of veratryl alcohol and preparation method and application thereof | |
| CN113398929A (en) | For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst and preparation method thereof | |
| CN101139332A (en) | Method for catalytic preparation of gamma-butyrolactone by using supported nano-gold catalyst | |
| CN109876821B (en) | Preparation method of copper-manganese bimetallic catalyst for p-nitrophenol hydrogenation | |
| CN103599777B (en) | Gold-based catalyst for room-temperature carbon monoxide removal and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |