CN101658804B - Preparation method of high-performance supported metal silicide catalyst and application thereof - Google Patents
Preparation method of high-performance supported metal silicide catalyst and application thereof Download PDFInfo
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- CN101658804B CN101658804B CN2009103071224A CN200910307122A CN101658804B CN 101658804 B CN101658804 B CN 101658804B CN 2009103071224 A CN2009103071224 A CN 2009103071224A CN 200910307122 A CN200910307122 A CN 200910307122A CN 101658804 B CN101658804 B CN 101658804B
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Abstract
The invention discloses a preparation method of a high-performance supported metal silicide catalyst and application thereof, and belongs to the field of catalytic science and technology. In the catalyst, silicon atoms enter metal lattices, and cause the metal lattices to be expanded and metallic bond length to be increased, and structural changes, physical property changes and the like provide metal silicides with special catalytic properties. The preparation method comprises the following steps: a carbonyl compound and an organic silicon compound are used as raw materials, and a metal organic silicide precursor is obtained after low temperature reaction and purification by sublimation; and the metal organic silicide precursor is sublimated to a carrier in a fluidized bed reactor for metal organic chemical vapor deposition, thus obtaining the high-performance supported metal silicide catalyst. The catalyst can be applied to multi-phase hydrogen-related catalytic reactions such as naphthalene hydrogenation, selective hydrogenation of alkyne or diene, hydrodesulfurization and hydrodenitrogenation reactions. The preparation method solves the problem of low surface area of metal silicides prepared by traditional methods, and has advantages of simple operation and easy control.
Description
Technical field
The invention belongs to catalytic science and technical field, relate to a kind of high-performance supported metal silicide catalyst, preparation method and application thereof.
Background technology
Catalysis is the key and one of core technology during chemical is produced, ammonia synthesizing industry, petroleum refining and chemical industry, fine chemicals synthesize and the preparation and the environmental protection technical field of macromolecular material all have irreplaceable important function.According to statistics, about chemical process more than 80% relates to catalysis technique, and the development of catalysis technique and major progress all depend on the discovery and the developing of new catalytic material.
Metal silicide is that silicon atom gets into behind the metal lattice and a type of forming has the special physics and the compound of chemical property; Have low-resistivity and excellent high temperature resistant, resistance to oxidation and performance such as corrosion-resistant; Fields such as pottery, electronics and coating have been widely used in.The lattice that nonmetal silicon atom gets into metal causes the expansion of metal lattice and metal bond distance's increase; Thereby make metal can be with the contraction and near the density of states of fermi level to increase; Given this type of metal silicide special catalytic performance in the variation of aspects such as structure and physical property, especially the catalytic property of type noble metal.Yet discover in a large number in the hydrogenation reaction of noble metal in the presence of sulfur-containing compound because the formation of sulfide causes activity to decline to a great extent.Yet thermodynamic data also shows metal silicide and in the presence of hydrogen sulfide, has higher stability than noble metal, thereby possibly have stronger sulfur tolerance, and can be applicable to a large amount of catalytic reactions of sulfur-containing compound under existing.
Traditional metal silicide adopts metallurgical method to prepare usually, and its specific surface is actively low (to be generally less than 10m
2/ g).At microelectronics technology, the method for synthetic metal silicide is main with physical method, also uses methods such as reaction diffusion and high temperature sintering; Metal silicide with the preparation of these technical methods mainly exists with the form of film, and its shortcoming is that the specific area of silicide material of preparation is less, and preparation condition is harsh, process is complicated, be difficult to control, is not suitable for catalytic reaction.
Metal silicide is studied and is used as a kind of novel catalysis material, also rarely has report both at home and abroad.But the catalytic property of metal silicide is existing report in basic research.Like research Cu/SiO such as Van den Oetelaar
2Find during the metal-support interaction of model catalyst that high temperature hydrogen treatment causes SiO
2The formation of copper silicide particle on the carrier.Schl? Pt/SiO studies in gl seminar under UHV condition
2Found during the model catalyst system and catalyzing to have formed platinum silicide at the metallic carrier interface.Research platinum such as Somorjai have also been found the generation of platinum silicide in the silica surface deposition process, yet these researchs only limit to the Surface Science research of model system, do not relate to silicide catalytic performance and surface size.Juszczyk etc. study Pd/SiO
2Find during catalyst after high temperature hydrogen treatment, to have formed palladium silicide, and the formation of palladium silicide improved 2, the isomerized activity of 2-dimethylbutane has reduced by 2, the activation energy that the 2-dimethylbutane transforms, and the size and the palladium-billon of activation energy are suitable.During silicon tetrachloride hydrogenation-dechlorination reaction on Roewer etc. research metallic nickel and the copper catalyst, find nickle silicide and copper silicide be very effective catalyst activity mutually.Yet the report that does not also have synthesized high-performance high-dispersion load silicide catalysis material so far.
Summary of the invention
The technical problem that the present invention will solve provides a kind of high-performance supported metal silicide catalyst, preparation method and application thereof; Overcome the problem that the traditional metal making method for silicide exists; And be applied to the heterogeneous hydrogen catalysis reaction that relates to, like selection hydrogenation, hydrodesulfurization, the hydrodenitrogeneration reaction of naphthalene hydrogenation, alkynes or diene.
Technical scheme of the present invention is following:
A kind of high-performance supported metal silicide catalyst is that the lattice of silicon atom entering metal causes the expansion of metal lattice and metal bond distance's increase, has given metal silicide special catalytic performance in the variation of aspects such as structure and physical property.
Make raw material with carbonyls and organo-silicon compound, the organic silicide presoma of metal that after low-temp reaction and distillation are purified, obtains.The organic silicide presoma of metal is sublimate into the enterprising row metal organic chemical vapor deposition of carrier in the fluidized-bed reactor, prepares high performance supported metal silicide catalyst.Concrete steps are following:
Carbonyls and organo-silicon compound mol ratio 1: 2 to 1: 10, the temperature that carbonyls and organo-silicon compound react is at-70 to-20 ℃.The carbonyls raw material comprises carbonyl cobalt, carbonyl iron, manganese carbonyl, molybdenum carbonyl or tungsten carbonyl; Organo-silicon compound comprise trichlorosilane, silane or its alkyl-substituted derivatives.
Metal organic chemical vapor deposition carries out on fluidized-bed reactor; Can adopt carrier gas that the organic silicide presoma of metal of distillation directly is written into fluidized-bed reactor; Load on the carrier through single metal organic chemistry gas-phase reaction deposition, obtain high performance supported metal silicide catalyst; Also can adopt earlier and the organic silicide presoma of metal that distils is written into fluidized-bed reactor, metal organic precursor deposition is adsorbed onto on the carrier, make high performance supported metal silicide catalyst with hydrogen reducing again with inert gas.Described carrier is oxide, composite oxides, molecular sieve or raw material of wood-charcoal material.
Granularity and the distribution thereof of metal silicide on carrier can be controlled through preparation parameters such as adjustment sublimation temperature, flow rate of carrier gas, decomposition temperatures among the present invention, and the composition of metal silicide can be adjusted through the composition of adjustment metal silicide presoma.
A kind of high-performance supported metal silicide catalyst of the present invention can be applicable to the heterogeneous hydrogen catalysis reaction that relates to, like selection hydrogenation, hydrodesulfurization, the hydrodenitrogeneration reaction of naphthalene hydrogenation, alkynes or diene.
Effect of the present invention and benefit are the problems that has overcome the low surface area of conventional method existence; Simple to operate; Control easily, the high-performance supported metal silicide catalyst of preparation has excellent catalytic activity and selectivity in naphthalene hydrogenation, selective acetylene hydrocarbon hydrogenation, hydrodesulfurization, hydrodenitrogeneration reaction.
Description of drawings
Fig. 1 is the Co (CO) of embodiment 1 gained
4SiCl
3IR figure.
Fig. 2 is the Co (CO) of embodiment 1 gained
4SiCl
3 13C NMR figure.
Fig. 3 is the Co (CO) of embodiment 1 gained
4SiCl
3 29Si NMR figure.
Fig. 4 is the CoSi/SiO of embodiment 3 gained
2XRD figure.
Fig. 5 is the CoSi/SiO of embodiment 3 gained
2The transmission electron microscope photo sketch map.
Fig. 6 is the CoSi/SiO of embodiment 3 gained
2The high-resolution photo sketch map of transmission electron microscope photo.
Fig. 7 is the products distribution figure of embodiment 6 gained.
Fig. 8 is the selectivity of product figure of embodiment 6 gained.
The specific embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme.
Take by weighing 3.0gCo
2(CO)
8Join in the vial, get 13.5gSiHCl
3Be added in the vial and mix, stirring reaction is two hours under the low temperature, and removing the product that excessive organo-silicon compound obtain after the room temperature is greyish brown powder; It is moved in the distillation device; Heating sublimation can see having yellow acicular crystal to generate, and takes out the 3.65g that weighs; Yield is 70%, and sealing is preserved.
Take by weighing 1.0gFe
3(CO)
12And 13.5gSiHCl
3, at N
2In the following adding autoclave of protection.Put into oil bath pan to autoclave, be heated to 120 ℃, constant temperature 36 hours.Removing the product that excessive organo-silicon compound obtain then is yellow powder, it is moved in the distillation device heating sublimation; Can see that flaxen acicular crystal is arranged, continue distillation and then obtain absinthe-green granular crystal generation, take out the 0.3g that weighs; Yield is 60%, and sealing is preserved.
Take by weighing 0.5g 500 ℃ of pretreated SiO in Muffle furnace
2Carrier places fluidized-bed reactor, the organic cobalt and silicon compound presoma of weighing metal 0.15g, and argon gas is done carrier gas, 40 ℃ of distillations down, presoma loads on SiO
2On, 500 ℃ of thermal decompositions obtain the load type metal cobalt silicide.
Take by weighing 0.8g 500 ℃ of pretreated SBA-15 carriers in Muffle furnace, place fluidized-bed reactor, the organic cobalt and silicon compound presoma of weighing metal 0.25g; Argon gas is done carrier gas; 40 ℃ of distillations down load on the SBA-15 presoma, and 500 ℃ of thermal decompositions obtain high activity loading type metal silication cobalt.
Take by weighing 0.5g 500 ℃ of pretreated SiO in Muffle furnace
2Carrier places fluidized-bed reactor, the organic iron silicon compound precursor of weighing metal body 0.2g, and hydrogen is done carrier gas, 40 ℃ of distillations down, direct 500 ℃ of thermal decompositions obtain the load type metal iron suicide.
Reactor is a fixed bed, and naphthalene, decane and undecanoic mixture are through bed, and wherein naphthalene is a reactant, and concentration is 5mol%; Decane is made solvent; Hendecane is made internal standard compound, and concentration is 1mol%.Beds is the metal silicide catalyst 0.2g of embodiment 3,4 or 5 preparations.Reaction temperature is 340 ℃, and reaction pressure is 4MPa, uses the gas chromatographic analysis product.The result shows that the conversion ratio of naphthalene is 20-80%, and the selectivity of product naphthane is near 100%.Above-mentionedly show that metal silicide catalyst of the present invention has very high activity and selectivity for naphthalene hydrogenation tetrahydrobiopterin synthesis naphthalene.
Adopt the cobalt silicide catalyst of embodiment 3 preparations to be used for cracking ethylene C 9 fraction selection hydrogenation, remove colloid and dienes compound in the C 9 fraction.At reactive hydrogen dividing potential drop 4.0MPa, 90 ℃ of reaction temperatures, volume space velocity 21.0h
-1, under 500: 1 the process conditions of hydrogen to oil volume ratio, carry out hydropyrolysis experiment.The result shows that alkadienes reduces to 0.80g/100g by 5.01g/100g, generates oily diene and descends significantly, and significant change does not all take place for sulphur, nitrogen, arene content.This presentation of results cobalt silicide catalyst of the present invention in cracking ethylene C 9 fraction one-stage selective hydrogenation, have alkadienes saturability and selective hydrogenation performance preferably.
Take by weighing phenylacetylene 0.6069g, be dissolved in 10mL ethanol, put into the 50mL autoclave, add embodiment 3 gained catalyst 0.2g again, at 80 ℃ in 2.0MPa H
2Under the condition reaction 3 hours, product carries out gas chromatographic analysis, phenylacetylene conversion ratio 80%, to cinnamic selectivity greater than 99%.This presentation of results cobalt silicide catalyst of the present invention in the alkynes selective hydrogenation, have excellent selection hydrogenation performance.
Claims (1)
1. the application of a high-performance supported metal silicide catalyst is characterized in that, catalyst adopts the following steps preparation:
Carbonyls and organo-silicon compound mol ratio 1: 2 to 1: 10, the temperature that carbonyls and organo-silicon compound react is at-70 to-20 ℃; The carbonyl compound raw material is selected from carbonyl cobalt, carbonyl iron, manganese carbonyl, molybdenum carbonyl or tungsten carbonyl; Organo-silicon compound are selected from silane or its alkyl-substituted derivatives;
Metal organic chemical vapor deposition carries out on fluidized-bed reactor; Adopt carrier gas that the organic silicide presoma of metal of distillation directly is written into fluidized-bed reactor, load on the carrier, obtain high performance supported metal silicide catalyst through single metal organic chemistry gas-phase reaction deposition; Or adopt elder generation the organic silicide presoma of metal that distils to be written into fluidized-bed reactor with inert gas, and metal organic precursor deposition is adsorbed onto on the carrier, make high performance supported metal silicide catalyst with hydrogen reducing again;
Described carrier is composite oxides, molecular sieve or raw material of wood-charcoal material;
The supported metal silicide catalyst of method for preparing is applicable to the selection hydrogenation of alkynes or alkadienes.
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| CN102408916B (en) * | 2010-09-21 | 2014-05-28 | 中国石油化工股份有限公司 | Method for removing alkine and dialkene from pyrolysis gas through selective hydrogenation |
| CN102327769A (en) * | 2011-06-13 | 2012-01-25 | 大连理工大学 | Methanation catalyst and application thereof |
| CN102302929A (en) * | 2011-07-12 | 2012-01-04 | 神华集团有限责任公司 | Sulfur-resisting high-temperature methanation catalyst and preparation method thereof |
| KR101580171B1 (en) * | 2014-01-23 | 2015-12-24 | 한국화학연구원 | Method for modifying surface of metal siliside, method for producing trichlorosilane using surface modified metal siliside and apparatus for producing the same |
| CN104801305B (en) * | 2015-03-12 | 2017-11-07 | 大连理工大学 | A kind of height is than table body phase transition metal silicide hydrogenation deoxidation catalyst, preparation method and applications |
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