CN103657633B - The preparation method of eggshell type molybdenum carbide catalyst and application - Google Patents
The preparation method of eggshell type molybdenum carbide catalyst and application Download PDFInfo
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- CN103657633B CN103657633B CN201310589889.7A CN201310589889A CN103657633B CN 103657633 B CN103657633 B CN 103657633B CN 201310589889 A CN201310589889 A CN 201310589889A CN 103657633 B CN103657633 B CN 103657633B
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- molybdenum carbide
- molybdenum
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- melamine
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Abstract
The invention discloses a kind of fast reaction membrane formation process and prepare eggshell type molybdenum carbide catalyst, belong to Industrial Catalysis technical field.The method is had by adsorption the carrier of molybdenum oxide group to join in melamine solution, generate rapidly by the fast reaction of melamine and molybdenum oxide group the film be made up of molybdenum carbide presoma at carrier surface, after pyrolysis, form eggshell type molybdenum carbide catalyst.Present invention process is simple, and shell thickness is controlled, and process energy consumption is low, and in the eggshell type molybdenum carbide catalyst of preparation, active component utilization rate is high, good stability, has good prospects for commercial application.This eggshell type molybdenum carbide catalyst can be used for reactions such as the phenylacetylene selective hydrogenation alkene-alkynes selective hydrogenations that is representative.
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 being similar to noble metal, has a wide range of applications in Industrial Catalysis field.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, relate to hydrogen process in many industry, such as, in hydrodenitrogeneration, hydrofinishing, hydroisomerizing, molybdenum carbide shows 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 usually utilize and improve the decentralization of molybdenum carbide particles and anti-caking power with the combination of carrier, thus improve the Activity and stabill of molybdenum carbide catalyst.Large quantifier elimination display, the distribution of active component on carrier is the important parameter determining catalyst performance.Effectively can improve the utilization rate of active phase for differential responses reasonable layout active component, improve the activity of catalyst, the life-span of extending catalyst, the intermediate product in successive reaction be had 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 by active phase integrated distribution in the outer surface of carrier, and thus in the reaction of numerous surperficial fast reaction with diffusion control, egg-shell catalyst shows superior catalytic performance.In addition, egg-shell catalyst is conducive to the quick desorption of reaction species from carrier surface, effectively can reduce the catalytic active center caused at surface aggregation because of species and poison effect, improve the stability of catalyst.Meanwhile, the quick desorption of product avoids it and reacts further, therefore can be used for selective (Ind.Eng.Chem.Prod.Res.Dev., 1981,20, the 439-450) that improve object product in the middle of consecutive reaction.
Load type molybdenum carbide catalyst, especially active component are that the load type molybdenum carbide catalyst of non-uniform Distribution has very large Industrial Catalysis application potential.It can be used to typical consecutive reaction if the purifying (substitute precious metals pd) of alkene, prepared from benzene and hydrogen are for cyclohexene (substituting noble metal Ru) etc. as a kind of noble metal substitute of cheapness.Relative to traditional load type molybdenum carbide catalyst (being more common in the even type distribution of active component), eggshell type molybdenum carbide catalyst can effective mass transfer enhancement, obtains the high selectivity to intermediate product while maintenance catalyst has greater activity.At present, yet there are no the pertinent literature report of eggshell type molybdenum carbide catalyst preparation method.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of succinct method effectively preparing eggshell type molybdenum carbide catalyst, and gained eggshell type molybdenum carbide catalyst shows higher catalytic activity and selective to the alkene being representative with phenylacetylene selective hydrogenation-alkynes selective hydrogenation.
The preparation method of eggshell type molybdenum carbide catalyst of the present invention, technical scheme is as follows:
(1) preparation is containing the molybdenum oxide group aqueous solution: by water-soluble for the molybdenum source containing molybdenum oxide group, obtains 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) flood: oxide carrier is joined 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) melamine solution is prepared: be dissolved in by melamine in solvent, be heated to melamine and dissolve completely.Solvent for use is water, ethylene glycol, glycerine or formalin etc.
(4) load molybdenum carbide presoma carrier is prepared: join in the melamine solution of (3) gained by the oxide carrier after dipping in (2), the molybdenum oxide group fast reaction that melamine and Oxide-supports adsorb generates molybdenum carbide presoma.
(5) pyrolysis: wash the load molybdenum carbide presoma carrier that (4) obtain with water, carry out pyrolysis under an inert atmosphere after drying, pyrolysis temperature is 600-750 DEG C, and the time is 60-120min, obtains eggshell type molybdenum carbide catalyst.Wherein, inert atmosphere can be the inert atmosphere 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 mass percentage of Mo is between 5-15%, it forms at carrier surface the dense film that one deck is made up of molybdenum carbide presoma by the fast reaction of molybdenum oxide group and melamine, the melamine molecule in solution is prevented to spread to the continuation of carrier inside, therefore achieve the eggshell type distribution of active component, improve 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.
The eggshell type molybdenum carbide catalyst section digital photograph that Fig. 2 (a) is embodiment 8 gained.
The eggshell type molybdenum carbide catalyst section digital photograph that Fig. 2 (b) is embodiment 9 gained.
The eggshell type molybdenum carbide catalyst section digital photograph that Fig. 2 (c) is embodiment 10 gained.
The eggshell type molybdenum carbide catalyst section digital photograph that Fig. 2 (d) is embodiment 11 gained.
The eggshell type molybdenum carbide catalyst section digital photograph that Fig. 2 (e) is embodiment 1 gained.
Fig. 3 is molybdenum carbide particles transmission electron microscope photo in the eggshell type molybdenum carbide catalyst of embodiment 1 gained.
Detailed description of the invention
Specific embodiments of the invention are described in detail below in conjunction with technical scheme.
Embodiment 1
Take 0.23g ammonium paramolybdate and put into beaker, measure 25 ml deionized water, treat that ammonium paramolybdate dissolves completely and add 5 Al
2o
3bead, leaves standstill 24 hours.Take 0.23g melamine and put into another clean beaker, measure 25 ml deionized water, be heated to 80 DEG C, treat that melamine goes is complete, solution temperature is maintained 80 DEG C.Al after the immersion that filtration is obtained
2o
3bead puts into melamine solution, reacts 5 minutes.Filtration obtains Al
2o
3bead, with deionized water rinsing, dry and be placed in argon gas atmosphere, be warming up to 650 DEG C with the programming rate of 5 DEG C/min, constant temperature 90 minutes, is down to room temperature, obtains eggshell type molybdenum carbide catalyst.
The mass percentage of ICP result display 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 DEG C and dissolve melamine, all the other steps are identical with embodiment 1.
Embodiment 5
Measure 25 milliliters of glycerine, be heated to 80 DEG C and dissolve melamine, all the other steps are identical with embodiment 1.
Embodiment 6
Pyrolysis temperature is 600 DEG C, and constant temperature 120 minutes, all the other steps are identical with embodiment 1.
Embodiment 7
Pyrolysis temperature is 750 DEG C, and constant temperature 60 minutes, all the other steps are identical with embodiment 1.
Embodiment 8
After melamine is dissolved in water completely, solution temperature is down to 0 DEG C and constant temperature.Al after the immersion that filtration is obtained
2o
3bead puts into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 9
After melamine is dissolved in water completely, solution temperature is down to 20 DEG C and constant temperature.Al after the immersion that filtration is obtained
2o
3bead puts into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 10
After melamine is dissolved in water completely, solution temperature is down to 40 DEG C and constant temperature.Al after the immersion that filtration is obtained
2o
3bead puts into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 11
After melamine is dissolved in water completely, solution temperature is down to 60 DEG C and constant temperature.Al after the immersion that filtration is obtained
2o
3bead puts into melamine solution, reacts 5 minutes.All the other steps are identical with embodiment 1.
Embodiment 12
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, hydrogen flow rate: 50mL/min, reduction temperature: 400 DEG C in catalyst prereduction.After prereduction terminates, fixed bed reaction actuator temperature is down to 240 DEG C, hydrogen pressure rises to 2MPa.With the charging of high pressure liquid phase feed pump, raw material: mass percentage be 1% phenylacetylene be 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 92.3% under optimal conditions, cinnamic selective be 98.2%.
Claims (3)
1. a preparation method for eggshell type molybdenum carbide catalyst, is characterized in that, comprises the steps:
(1) preparation is containing the molybdenum oxide group aqueous solution: by water-soluble for the molybdenum source containing molybdenum oxide group, obtain the aqueous solution containing molybdenum oxide group;
(2) flood: oxide carrier is joined containing in the aqueous solution of molybdenum oxide group of step (1) gained, flood under normal pressure and temperature;
(3) melamine solution is prepared: be dissolved in by melamine in solvent, be heated to melamine and dissolve completely;
(4) load molybdenum carbide presoma carrier is prepared: joined by the oxide carrier after dipping in step (2) in the melamine solution that step (3) obtains, namely obtain load molybdenum carbide presoma carrier;
(5) pyrolysis: wash the load molybdenum carbide presoma carrier that step (4) obtains with water, carry out pyrolysis under an inert atmosphere after drying, pyrolysis temperature is 600-750
oc, the time is 60-120min, obtains eggshell type molybdenum carbide catalyst;
The described molybdenum source containing molybdenum oxide group is ammonium paramolybdate, phosphomolybdic acid or silicomolybdic acid;
Described oxide carrier is Al
2o
3, SiO
2or SiO
2-Al
2o
3;
Described solvent is water, ethylene glycol, glycerine or formalin.
2. preparation method according to claim 1, is characterized in that described inert atmosphere is argon gas or helium.
3. the application of eggshell type molybdenum carbide catalyst prepared of preparation method described in claim 1 or 2, it is characterized in that, described eggshell type molybdenum carbide catalyst is used for alkene-alkynes selective hydrogenation.
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| 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 |
| US20200246783A1 (en) * | 2019-02-04 | 2020-08-06 | China Energy Investment Corporation Limited | Hydrocarbon conversion processes using metal carbide nanomaterial catalysts |
| 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 |
| CN111111730B (en) * | 2019-12-19 | 2023-03-28 | 浙江师范大学 | Molybdenum carbide catalyst, preparation method and application thereof |
| CN112916019B (en) * | 2021-01-26 | 2022-02-11 | 西南化工研究设计院有限公司 | Ferromolybdenum catalyst with core-shell structure, preparation and application |
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| 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 |
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2013
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| 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 |
|---|
| "Mo(VI)-Melamine Hybrid As Single-Source Precursor to Pure Phaseβ-Mo2C for the Selective Hydrogenation of Naphthalene to Tetralin";Min Pang et al;《Industrial & Engineering Chemistry Research》;20130307;第4564-4571页 * |
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