CN102600877A - High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof - Google Patents
High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-selectivity carbide catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and a quick microwave preparation method thereof, belonging to the technical field of catalyst material application and preparation. The method comprises the steps of: fully grinding complex compounds containing relevant metals and carriers, or supporting the complex compounds containing the relevant metals onto the surfaces of carriers through a solution impregnation method and conducting microwave pyrolysis in inert gas to form the supported carbide catalyst. The invention provides the high-efficiency carbide catalyst with 100 percent selectivity aiming at the naphthalene hydrogenation reaction for preparing the tetrahydronaphthalene and a simple, convenient, quick, environmental-friendly and energy-saving preparation method thereof. The prepared carbide particles are evenly dispersed on the carriers, so that the situation of surface carbon deposition is avoided. The contradiction between high catalyst selectivity and high cost is successfully avoided, and therefore the high-selectivity carbide catalyst and the preparation method thereof have promising industrial application prospect.
Description
Technical field
The invention belongs to catalysis material uses and preparing technical field; Relate to a kind of the reaction and have carbides catalytic material of high selectivity and preparation method thereof to naphthalene hydrogenation preparing naphthane; Specially refer to a kind of rapid microwave preparation method of carbides catalytic material, and the carbides catalytic material of preparation is used for reactions such as naphthalene hydrogenation preparing naphthane.
Background technology
The probe that the naphthalene hydrogenation reaction often is used as the aromatic hydrogenation serial reaction is studied the mechanism of reaction, in the petroleum refinement field, has important theory to be worth and directive significance.Simultaneously, two kinds of products of naphthalene hydrogenation reaction: naphthane and decahydronaphthalene itself are exactly the abundant industrial products of practical value.Naphthane is a kind of high boiling organic solvent of excellence, is widely used in industries such as coating, medicine.Nearest research shows that in fuel cell, naphthane is a kind of good hydrogen atom donor, and its ability of supplying with hydrogen atom fast is that decahydronaphthalene is incomparable, therefore very likely becomes cheapness, the high efficient energy sources of a new generation.Go on foot the hydrogenation preparing naphthane through one of naphthalene in the industry; But because the naphthalene hydrogenation is a consecutive reaction: one step of naphthalene hydrogenation obtains naphthane; The further hydrogenation of naphthane generates decahydronaphthalene; The product of hydrogenation reaction is the mixture of naphthane and decahydronaphthalene normally, needs an additional step distillation operation that two kinds of materials are come into operation after separately, and complex operation complicacy and operating cost are high.Noble metal is made catalyst (Catal.Today; 1996; 31,93-104) in naphthalene hydrogenation preparing naphthane reaction, show good selectivity (＞80%), but noble metal is rare, to pollutants such as sulphur, carbon monoxide sensitivity; In catalytic reaction, be prone to poisoning and deactivation, so precious metal catalyst naphthalene hydrogenation reaction is not the approach of a desirable suitability for industrialized production naphthane.Transition metal and transient metal sulfide, silicide (Catal.Today have appearred subsequently in succession; 2007; 128, the 63-73) application example of catalysis naphthalene hydrogenation reaction is though they have stronger anti-poisoning capability and self cheap than noble metal; But the catalytic activity that shows and to the selectivity very low (＜80%) of naphthane can not satisfy production requirement.Therefore, the naphthalene hydrogenation reaction catalysis material of developing a kind of cheapness, stable, high activity, high selectivity is being contained abundant industrial value.
Carbide has shown the catalytic performance that is similar to noble metal in many hydrogen-involved reactions (selective hydrogenation etc.), and because it is cheap, anti-poisoning capability is extensively regarded as the substitute of noble metal by force.But because preparation method's limitation, the carbide specific area that obtains is little, particle surface has serious carbon distribution, and catalytic activity that shows and selectivity are very low, and the catalytic performance of type noble metal is not fully represented.At present, the preparation method of carbide can be classified as two types: the presoma and the hydrocarbon gas that contain respective metal at high temperature react, and the presoma and the carbon that contain respective metal at high temperature react.Two kinds of preparation methods use the carbon source of carbonaceous material as carburizing process inevitably, have caused high temperature to be coated one deck carbon (area carbon) in the surface of the carbide particle of generation down, and the catalytic active site on surface is covered.The single-source precursor one of having researched and proposed afterwards goes on foot the method that pyrolysis prepares molybdenum carbide; The molecule that this method is bigger with phosphorus content in advance combines through chemical reaction with the molybdenum source; Make pyrolytic process need not external carbon source; The dispersal direction of carbon atom is extremely outside mutually from traditional being phase-changed into by granule by outside to granule, and carbon is with gas form (CO, CO
2) overflow, avoided carbon to form area carbon in particle surface gathering, cracking.Present most popular single-source precursor is molybdenum-hexamethylenetetramine complex compound; There is the research report to use traditional this precursor of temperature-programmed pyrolysis can prepare molybdenum carbide (Chem.Mater., 2007,19; 1801-1807); But in the preparation process,, also need add a large amount of hexamethylenetetramines, by the pyrogenous origin CH of hexamethylenetetramine except molybdenum-hexamethylenetetramine complex compound
4Carbon source as carburizing process; Therefore see from microcosmic angle; This process is not one step of a single-source precursor pyrolysismethod truly, and carbon atom is not changed by the dispersal direction of outside to granule phase, and the molybdenum carbide particles for preparing also has area carbon to a certain degree.Therefore, the class precious metal catalyst performance of carbide is fully used is to solve the effective way that noble metal can not satisfy this contradiction of commercial production for research high-specific surface area or high dispersive and the preparation method that do not have a carbides catalytic material of area carbon.
Summary of the invention
The invention provides a kind of carbides catalytic material and rapid microwave preparation method thereof that react to naphthalene hydrogenation preparing naphthane with high selectivity.This preparation method contains the single-source precursor of respective metal through the microwave fast pyrogenation, and a step obtains carbide, has shortened pyrolytic process substantially, has prevented carbide particle polymerization sintering at high temperature.Owing to comprising a large amount of carbon in the single-source precursor that contains respective metal, pyrolytic process can avoid the use of external carbon source simultaneously, and the carbide particle that therefore prepares does not have the area carbon phenomenon.Use carbides catalytic material that this method prepares in the reaction of naphthalene hydrogenation preparing naphthane, to show good catalytic activity and to the high selectivity of naphthane.
Technical scheme of the present invention comprises the steps:
A kind of high-selectivity catalyst that is used for the reaction of naphthalene hydrogenation preparing naphthane; It comprises one or more combinations in molybdenum carbide catalyst, tungsten carbide catalyst, metal modification molybdenum carbide catalyst, the metal modification tungsten carbide catalyst, and wherein metal comprises nickel or/and metals such as cobalts.
Above-mentioned catalyst, following method is adopted in its preparation:
To contain the single-source precursor of respective metal and the presoma that the carrier mixed grinding obtains carbide; The single-source precursor that perhaps adopts the method for solution impregnation will contain respective metal supports on the carrier, boils off solvent, and oven dry obtains the presoma of carbide.
Single-source precursor, slaine and the carrier mixed grinding that will contain respective metal obtain the presoma that metal is modified carbide; The single-source precursor, the slaine that perhaps adopt the method for solution impregnation will contain respective metal support on the carrier, boil off solvent, and oven dry obtains the presoma that metal is modified carbide.The percentage by weight of metal is in the 5-50% scope.Wherein slaine comprises nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride, cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride.
The presoma that the presoma and the metal of carbide are modified carbide places microwave reactor respectively; Microwave-heating 10-30min in inert gas; In inert gas, naturally cool to room temperature after pyrolysis finishes, obtain carbide catalyst, metal modification carbide catalyst.Described inert gas is argon gas or helium, and gas flow rate is the 30-130 ml/min.
The described single-source precursor that contains respective metal is molybdenum-hexamethylenetetramine complex compound, tungsten carbonyl.Molybdenum-hexamethylenetetramine complex compound, adopt following method preparation:
With the aqueous solution of the aqueous solution and the hexamethylenetetramine of ammonium heptamolybdate, separate out white crystal, to filter and obtain white solid, oven dry promptly obtains molybdenum-hexamethylenetetramine complex compound; The concentration of the aqueous solution does not have influence to the preparation of molybdenum-hexamethylenetetramine complex compound.
Described carrier can be divided three classes: raw material of wood-charcoal material carrier, oxide carrier, molecular sieve carrier.Raw material of wood-charcoal material carrier comprises carbon black, active carbon, CNT, carbon nano-fiber.Oxide carrier comprises alundum (Al, silica, titanium dioxide.Molecular sieve comprises MCM series, ZSM series, SBA is serial or faujasite.
Carbides catalytic material prepared in accordance with the present invention can also be applied to fuel battery negative pole oxygen reduction reaction, ammonia decomposition reaction, transformation of glycerol reaction etc. except that being applied to the reaction of naphthalene hydrogenation preparing naphthane.
Effect of the present invention and benefit have provided a kind ofly has 100% optionally efficient carbides catalytic material to naphthalene hydrogenation preparing naphthane reaction, with and easy fast, the preparation method of environmental friendliness, energy efficient.Should contain the single-source precursor of respective metal through the microwave fast pyrogenation, a step obtains carbide, has shortened pyrolytic process substantially, has prevented carbide particle polymerization sintering at high temperature.Owing to comprising a large amount of carbon in the single-source precursor that contains respective metal, pyrolytic process can avoid the use of external carbon source simultaneously, has therefore broken through the limitation of the necessary carbon containing of carrier, has enlarged the selection face of carrier.The no carbon distribution in carbide catalyst surface for preparing has very high decentralization on carrier.This catalyst like never before brings up to 100% with the selectivity of naphthalene hydrogenation preparing naphthane reaction, has successfully avoided the corresponding expensive contradiction of catalyst high selectivity, therefore has wide prospect in industrial application.
Description of drawings
Fig. 1 is for the molybdenum loading is 20%, the microwave-heating time is the XRD spectra of 30 minutes activated carbon supported molybdenum carbide.
Fig. 2 is for the molybdenum loading is 20%, the microwave-heating time is the transmission electron microscope photo of 30 minutes activated carbon supported molybdenum carbide.
Fig. 3 is the activated carbon supported molybdenum carbide catalysis material of the present invention preparation conversion ratio and the selectivity sketch map to the naphthalene hydrogenation reaction.
The specific embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
The preparation of embodiment 1 activated carbon supported molybdenum carbide catalysis material
It is 15% ammoniacal liquor that a certain amount of molybdenum-hexamethylenetetramine complex compound is added 1 ml concn, treat fully dissolving after, take by weighing the 0.1g active carbon and add solution, boil off solvent under the room temperature naturally, 80 ℃ of dryings are 3 hours in the vacuum drying chamber, obtain the presoma of molybdenum carbide.Change molybdenum-hexamethylenetetramine complex compound addition, can make the molybdenum carbide presoma of different molybdenum loadings.Presoma is placed microwave reactor, fed argon purge 2 hours, under argon atmosphere, open microwave 800W heating 30min, sample cools off after X-ray powder diffraction is accredited as Mo
2C.
The preparation of the molybdenum carbide catalysis material that embodiment 2SBA-15 nickel-loaded is modified
It is 15% ammoniacal liquor that a certain amount of molybdenum-hexamethylenetetramine complex compound is added 1 ml concn, adds 1 ml concn and be 15% ammoniacal liquor.After treating fully dissolving, take by weighing the 0.1g active carbon and add solution, boil off solvent under the room temperature naturally, 80 ℃ of dryings are 3 hours in the vacuum drying chamber, obtain the molybdenum carbide presoma that nickel is modified.Change the addition of molybdenum-hexamethylenetetramine complex compound and Nickelous nitrate hexahydrate, can make the molybdenum carbide presoma of the nickel modification of different molybdenums, nickel loading.Because the molybdenum carbide presoma that the SBA-15 nickel-loaded is modified does not absorb microwave; Can't under microwave action, make and self be heated; Therefore the 0.05g zirconia is mixed being placed on (zirconia is used to absorb microwave indirect presoma) in the microwave reactor with presoma, fed argon purge 2 hours, under argon atmosphere, open microwave 800W heating 30min; Sample cooling is after sulfuric acid flush away zirconia, and X-ray powder diffraction is accredited as Mo
2C and nickel oxide.
The preparation of the molybdenum carbide catalysis material that embodiment 3 silicon dioxide carried cobalts are modified
It is 15% ammoniacal liquor that a certain amount of molybdenum-hexamethylenetetramine complex compound is added 1 ml concn, adds 1 ml concn and be 15% ammoniacal liquor.After treating fully dissolving, take by weighing 0.1g silica and add solution, boil off solvent under the room temperature naturally, 80 ℃ of dryings are 3 hours in the vacuum drying chamber, obtain the molybdenum carbide presoma that cobalt is modified.Change the addition of molybdenum-hexamethylenetetramine complex compound and cobalt chloride hexahydrate, can make the molybdenum carbide presoma of the cobalt modification of different molybdenums, cobalt loading.Because the molybdenum carbide presoma that silicon dioxide carried cobalt is modified does not absorb microwave; Can't under microwave action, make and self be heated; Therefore the 0.05g zirconia is mixed being placed on (zirconia is used to absorb microwave indirect presoma) in the microwave reactor with presoma, fed argon purge 2 hours, under argon atmosphere, open microwave 800W heating 30min; Sample cooling is after sulfuric acid flush away zirconia, and X-ray powder diffraction is accredited as Mo
2C and cobalt oxide.
The preparation of embodiment 4 alundum (Al load tungsten carbide catalysis materials
Take by weighing the 0.1g alundum (Al, a certain amount of tungsten carbonyl is put in the mortar, grinds 15min, obtains the presoma of tungsten carbide, the addition that changes tungsten carbonyl can obtain the tungsten carbide presoma of different tungsten loadings.Because alundum (Al load tungsten carbide presoma does not absorb microwave; Can't under microwave action, make and self be heated; Therefore the 0.05g zirconia is mixed being placed on (zirconia is used to absorb microwave indirect presoma) in the microwave reactor with presoma, fed argon purge 2 hours, under argon atmosphere, open microwave 800W heating 30min; Sample cooling is after sulfuric acid flush away zirconia, and X-ray powder diffraction is accredited as WC.
The preparation of the tungsten carbide catalysis material that embodiment 5MCM-41 load cobalt is modified
Take by weighing 0.1g MCM-41 and a certain amount of tungsten carbonyl, cobalt chloride hexahydrate are put in the mortar; Grind 15min; Obtain the tungsten carbide presoma that cobalt is modified, the addition that changes tungsten carbonyl, cobalt chloride hexahydrate can obtain the tungsten carbide presoma of the cobalt modification of different cobalt, tungsten loading.Because the tungsten carbide presoma that MCM-41 load cobalt is modified does not absorb microwave; Can't under microwave action, make and self be heated; Therefore the 0.05g zirconia is mixed being placed on (zirconia is used to absorb microwave indirect presoma) in the microwave reactor with presoma, fed argon purge 2 hours, under argon atmosphere, open microwave 800W heating 30min; Sample cooling is after sulfuric acid flush away zirconia, and X-ray powder diffraction is accredited as WC and cobalt oxide.
The preparation of the tungsten carbide catalysis material that embodiment 6 carbon black loadings nickel are modified
Take by weighing 0.1g XC-72R and a certain amount of tungsten carbonyl, nickel acetate are put in the mortar; Grind 15min; Obtain the tungsten carbide presoma that nickel is modified, the addition that changes tungsten carbonyl and nickel acetate can obtain the tungsten carbide presoma of the nickel modification of different nickel, tungsten loading.Presoma is placed microwave reactor, fed argon purge 2 hours, under argon atmosphere, open microwave 800W heating 30min, sample cools off after X-ray powder diffraction is accredited as WC and nickel oxide.
Embodiment 7 activated carbon supported molybdenum carbide catalysis materials are to the catalytic performance of naphthalene hydrogenation reaction
Taking by weighing 0.1g is that 20% activated carbon supported molybdenum carbide catalyst is loaded the constant temperature zone in reaction tube by the molybdenum loading of embodiment 1 preparation, all fills with quartz sand up and down.Catalyst is 1MPa at Hydrogen Vapor Pressure, temperature be under 400 ℃ the condition activation 2 hours to remove surface passivation layer.Being reflected at Hydrogen Vapor Pressure is 4MPa, and temperature is to carry out under 340 ℃ the condition.The catalytic activity of naphthalene hydrogenation reaction is seen Fig. 3.The conversion ratio of naphthalene is 95%, and the selectivity of naphthane is 100%, and in 60 hours, keeps the selectivity to naphthane 100%.
Claims (10)
1. a high-selectivity catalyst that is used for the reaction of naphthalene hydrogenation preparing naphthane is characterized in that, it comprises one or more combinations in molybdenum carbide catalyst, tungsten carbide catalyst, metal modification molybdenum carbide catalyst, the metal modification tungsten carbide catalyst.
2. high-selectivity catalyst according to claim 1 is characterized in that, the metal that metal is modified in molybdenum carbide catalyst, the metal modification tungsten carbide catalyst comprises nickel or/and cobalt.
3. preparation method who is used for the high-selectivity catalyst of naphthalene hydrogenation preparing naphthane reaction is characterized in that following steps:
To contain the single-source precursor of respective metal and the presoma that the carrier mixed grinding obtains carbide; The single-source precursor that perhaps adopts the method for solution impregnation will contain respective metal supports on the carrier, boils off solvent, and oven dry obtains the presoma of carbide; The percentage by weight of metal is in the 5-50% scope;
Single-source precursor, slaine and the carrier mixed grinding that will contain respective metal obtain the presoma that metal is modified carbide; The single-source precursor, the slaine that perhaps adopt the method for solution impregnation will contain respective metal support on the carrier, boil off solvent, and oven dry obtains the presoma that metal is modified carbide; The percentage by weight of metal is in the 5-50% scope;
The presoma that the presoma and the metal of carbide are modified carbide places microwave reactor respectively; Microwave-heating 10-30min in inert gas; In inert gas, naturally cool to room temperature after pyrolysis finishes, obtain carbide catalyst, metal modification carbide catalyst;
The described single-source precursor that contains respective metal is molybdenum-hexamethylenetetramine complex compound, tungsten carbonyl.
4. preparation method according to claim 3 is characterized in that, the described single-source precursor that contains respective metal is molybdenum-hexamethylenetetramine complex compound, tungsten carbonyl.
5. preparation method according to claim 3 is characterized in that described slaine comprises nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride, cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride.
6. preparation method according to claim 3; It is characterized in that described molybdenum-hexamethylenetetramine complex compound is prepared by following method:, separate out white crystal with the aqueous solution of the aqueous solution and the hexamethylenetetramine of ammonium heptamolybdate; Filtration obtains white solid, oven dry.
7. preparation method according to claim 3 is characterized in that described carrier is raw material of wood-charcoal material carrier, oxide carrier, molecular sieve carrier.
8. preparation method according to claim 7 is characterized in that, raw material of wood-charcoal material carrier comprises carbon black, active carbon, CNT, carbon nano-fiber; Oxide carrier comprises alundum (Al, silica, titanium dioxide; Molecular sieve comprises MCM series, ZSM series, SBA is serial or faujasite.
9. preparation method according to claim 3 is characterized in that described inert gas is argon gas or helium, and gas flow rate is the 30-130 ml/min.
10. preparation method according to claim 3 is characterized in that, the carbides catalytic material of preparation is applied to fuel battery negative pole oxygen reduction reaction, ammonia decomposition reaction, transformation of glycerol reaction.
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| CN114426490A (en) * | 2020-10-12 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic hydrogenation of unsaturated compounds |
| CN114505089B (en) * | 2020-11-16 | 2023-06-13 | 南开大学 | Preparation method and application method of catalyst for preparing decalin by naphthalene hydrogenation |
| CN114505089A (en) * | 2020-11-16 | 2022-05-17 | 南开大学 | Preparation method and use method of catalyst for preparing decahydronaphthalene through naphthalene hydrogenation |
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| CN114011428B (en) * | 2021-12-07 | 2024-05-03 | 太原理工大学 | Catalyst for preparing decalin by naphthalene one-step hydrogenation and preparation method thereof |
| CN114805225B (en) * | 2022-07-04 | 2022-09-23 | 苏州中车氢能动力技术有限公司 | Hydrogenation method of methyl quinoxaline |
| CN114805225A (en) * | 2022-07-04 | 2022-07-29 | 苏州中车氢能动力技术有限公司 | Hydrogenation method of methyl quinoxaline |
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