CN109647517A - One kind being used for nitro benzene and its derivative hydrogenation catalyst preparation method - Google Patents
One kind being used for nitro benzene and its derivative hydrogenation catalyst preparation method Download PDFInfo
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- CN109647517A CN109647517A CN201710940720.XA CN201710940720A CN109647517A CN 109647517 A CN109647517 A CN 109647517A CN 201710940720 A CN201710940720 A CN 201710940720A CN 109647517 A CN109647517 A CN 109647517A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
Abstract
The present invention relates to one kind to be used for nitro benzene and its derivative hydrogenation catalyst preparation method.By supporting noble metal after carbon material is carried out functional modification with high molecular polymer.Method for preparing catalyst include: (1) by carbon material and high molecular polymer in certain density salting liquid, 0.5~6h of ultrasonic treatment is carried out under certain temperature, obtain the carbon material of functionalization；(2) salting liquid of noble metal is prepared to the noble metal granule of certain size distribution under the action of protective agent and reducing agent；(3) it obtains supporting noble metal catalyst on the carbon material that the aqueous solution of resulting noble metal granule or organic solution support modified with functional group after ultrasonic 10min, 2~12h of stirring；The method for preparing catalyst is simple and effective, environmentally protective, after reducing agent restores, obtains with certain size distribution, finely dispersed noble metal supported catalyst.And the catalyst has broad application prospects in the catalytic field of nitro benzene and its derivative.
Description
Technical field
The invention belongs to technical field of organic synthesis, and the present invention relates to one kind to be used for nitro benzene and its derivative hydrogenation catalyst
The preparation method of agent.
Background technique
Nitrobenzene aminated compounds is widely used in dyestuff, medicine, pesticide, rubber chemicals as a kind of organic intermediate
And the production of fine-chemical intermediate.For example, ortho-nitraniline be mainly used as dyestuff intermediate, micro iodide measurement,
The production etc. of pesticide carbendazim；2- Amino-5-nitrophenol is for producing neutral pink BL, manufacture premetallized dye, activity
Black, leather coating red GL, leather coating black RL, solvent red BL, solvent red KL etc..Currently, nitrobenzene aminated compounds is mainly
It is obtained by nitro compound selective reduction, including iron powder reducing method, sodium sulfide reducing method and catalytic hydrogenation method etc..First two is closed
At method and process long flow path, the three wastes are more, and post-processing is complicated, and environmental pollution is serious, and catalytic hydrogenation method reaction equation is C6H5NO2+
3H2=C6H5NH2+2H2The advantages that O, reaction is simple and environmentally friendly, product quality height and good reaction selectivity, in laboratory research
Very extensive with applying in industrial production, therefore, catalytic hydrogenating reduction technology is increasingly taken seriously and develops.
Nitrobenzene and its derivatives catalysis add the core of hydrogen production aniline process to be efficient catalyst, therefore study nitro
The catalyst that benzene hydrogenation synthesizes aniline has important theoretical value and realistic meaning.In recent years, catalyst with metal nanoparticles has
There are high catalytic activity and selectivity, becomes the research hotspot of Catalytic Hydrogenation of Nitrobenzene catalyst.Wherein, noble metal nano grain
Son such as gold (Au), platinum (Pt), the catalyst such as ruthenium (Ru) and rhodium (Rh) can come into full contact with substrate, to show excellent work
Property, add in hydrogen in nitrobenzene and its derivatives catalysis and is widely used.Publication number [CN201210366356.8] disclose it is a kind of with
The carried noble metal of 30-70 DEG C of sulfide removal is catalyst, using halogenated nitrobenzene as raw material, and high-selective and hydrogenating synthesizes halogen
For the method for aniline, the catalyst prepared in this method can effectively inhibit hydrodehalogenation side reaction, and the selectivity of product is high；But
The limited and higher cost and metal nanoparticle of Precious Metals Resources because of specific surface energy height, grow up by heated easy reunion, into
And surface-active site is caused to reduce, it is always the difficulty for restricting precious metal nano-particle catalyst application the problem of catalyst inactivation
Topic.Therefore, if can be immobilized on these metals, specific surface area is larger, it is compound to be prepared on cheap carrier with certain duct
Material then the metal after load can avoid being lost to a certain extent, while facilitating the recycling of catalyst and repeating benefit
With.Skeleton of the carrier as supported catalyst active component, so can be increased after nano-metal particle is loaded using one side
The specific surface area for adding catalyst improves the dispersion degree of active component and improves the catalytic efficiency of unit mass active component；It is another
Aspect, carrier can pass through has an effect between active component, or activated centre is provided in catalysis reaction, transmitting electronics etc.
Play the role of co-catalysis.Excellent catalyst carrier should have the following conditions: (1) good electronic transmission performance；(2) it closes
The pore structure and surface area of reason, meet gas transfer requirement；(3) excellent stability, can be in acid and alkaline solution, tool
There is good corrosion resistance.In nitrobenzene hydrogenation, common carrier has metal oxide, carbon material, mesoporous material
(molecular sieve, aluminum phosphate crystals) etc..In these carriers, carbon material is since its stability is good, specific surface area is high, is convenient at chemistry
Reason and the good characteristics such as conductive, thermally conductive, acidproof, alkaline-resisting, are widely used in the carrier of all kinds of metal catalytics, are decades
Carry out flourishing long time one of catalyst carrier material.However in these composite materials, metal nanoparticle and carbon material are answered
It closes and the pattern of metallic, size Control and dispersibility is always a research hotspot.Publication number US3736266 is disclosed
It is a kind of that the value of the PH of solution being transferred to 12 and with reducing agents such as formaldehyde by hydroxide containing palladium with alkaline earth metal hydroxide
It is deposited on absorbent charcoal carrier.This technical process only could sink the hydroxide of palladium by means of alkaline earth metal hydroxide
It forms sediment on the activated carbon, and required pH value is then not achieved in other bases, preparation process is cumbersome, and noble metal active component grain
Diameter and distribution are poor, and granularity is excessive, therefore the activity of catalyst is not high.Therefore, how simply and efficiently to research and develop one kind can
There is certain pattern, certain size distribution in a mild condition while there is high activity, highly selective catalysis hydrogenation of chloronitrobenzene
The catalyst system of aniline processed seems particularly significant.The present invention first modifies carbon material with high molecular polymer, then closes
Noble metal is carried on a shoulder pole finally by the proportion of regulation noble metal and carbon material carrier at the noble metal nano particles of certain size
It being loaded on the carbon material carrier of functionalization, the catalyst preparation process is easy to operate, pollution is few, and noble metal granule is uniformly dispersed,
And to the selectivity of catalysis manufacturing process of aniline through nitrobenzene hydrogenation up to 95% or more.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods for nitro benzene and its derivative hydrogenation catalyst.The system
Preparation Method have it is easy to operate, it is easily controllable, be easy to the features such as amplifying synthesis, and noble metal granule is equal with certain size distribution
It is even to be dispersed in prepared catalyst.The selectivity of manufacturing process of aniline through nitrobenzene hydrogenation is catalyzed up to 95% or more.
A kind of preparation method for nitro benzene and its derivative hydrogenation catalyst of the invention, specific steps are as follows:
1) carbon material is mixed in certain density salting liquid with high molecular polymer, under certain temperature at ultrasound
0.5~6h is managed, the carbon material of functionalization is obtained；
2) salting liquid of noble metal is prepared to the noble metal of certain size distribution under the action of protective agent and reducing agent
Particle；
3) carbon material containing modified with functional group obtained by step 1) is dispersed in aqueous solution or organic solvent, at ultrasound
2~12h of mixing is carried out with the aqueous solution or organic solution of the resulting noble metal granule of step 2) after 0.5~2h of reason to be carried on a shoulder pole
Supported noble metal catalyst；
The carbon material be Nano carbon balls, carbon nanotube, carbon fiber, graphene, in BP2000, EC600, VXC-72
One or more kinds of mixing carbon；Specific surface area is 200~2000m2g-1；
The high molecular polymer is kayexalate, diallyl dimethyl ammoniumchloride, polyaniline, poly- pyrrole
The mixture one or more of coughed up；The mass ratio of high molecular polymer and functional carbon material is 2/5~5/2；
The salting liquid is sodium chloride, sodium sulphate, sodium nitrate；The concentration of salting liquid is 1~10wt%；The temperature
For
The precious metal salt be gold trichloride, gold chloride, potassium platinic chloride, chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, palladium nitrate,
The mixture of one or more of palladium chloride, tetrachloro-palladium acid amine, palladium acetylacetonate；
The organic solvent of the dispersion carbon material and noble metal nano particles includes: methanol, ethyl alcohol, acetone, dichloromethane
The mixture of one or more of alkane, chloroform；
The protective agent is polyvinylpyrrolidone (molecular weight ranges are 8000~50000), cetyl trimethyl
Ammonium bromide, KBr, NaBr etc.；The mass ratio of protective agent and precious metal salt is 1/6~6/1；
The reducing agent is ascorbic acid, sodium borohydride, formaldehyde, hydrazine hydrate, oleyl amine etc.；Reducing agent and precious metal salt
Mass ratio is 1/1~10/1；Recovery time is 2~12h；
The loading of the noble metal is 1~10wt%；
Catalyst and nitro benzene and its derivative are added in reaction dissolvent, carries out being catalyzed under hydrogen existence condition anti-
It answers, the reaction dissolvent is one or more of toluene, dodecane, fatty alcohol, hexamethylene mixed liquor；The nitrobenzene
Derivative be o-chloronitrobenzene, m-chloro-nitrobenzene, parachloronitrobenzene, ortho-methylnitrobenzene, meta-nitrotoluene, para-nitrotoluene,
One or more of o-nitrobenzaldehyde, paranitrobenzaldehyde, p-nitroacetophenone；The catalytic temperature are as follows: 20~100
℃；Reaction time be 2~for 24 hours；Reaction pressure is 0.5~5MPa；
With it is reported for the preparation method of nitro benzene and its derivative hydrogenation catalyst compared with, advantages of the present invention is such as
Under:
1) present invention modifies carbon material by high molecular polymer, forms the carbon material of functionalization, is conducive to
Stablize noble metal granule, improves carbon material to the load capacity of noble metal；
2) catalyst that the present invention synthesizes, prepared noble metal has certain particle size, the characteristics of being evenly distributed；
3) synthetic method of the invention is environmental-friendly, is easy to control, while not high to equipment requirement, is suitable for large-scale
It commercially produces；
4) prepared by the present invention to be used for nitro benzene and its derivative hydrogenation catalyst, it can by selection and regulation preparation condition
The catalyst of different noble metal loadings is obtained, prepared catalyst is shown in nitrobenzene and its derivatives catalysis field of hydrogenation
Excellent performance, post catalyst reaction are easily recycled.
Detailed description of the invention:
Fig. 1 is transmission electron microscope (TEM) figure that embodiment 1 prepares products therefrom.
Fig. 2 is the structural schematic diagram of kayexalate used in the catalyst of the preparation of embodiment 1.
Fig. 3 is transmission electron microscope (TEM) figure that embodiment 2 prepares products therefrom.
Fig. 4 is the structural schematic diagram of diallyl dimethyl ammoniumchloride used in the catalyst of the preparation of embodiment 2.
Specific embodiment
Specific description is done to the present invention below in conjunction with example:
Embodiment 1:
1) preparation of functional carbon material
100mg kayexalate is dispersed in volume is 500ml, mass fraction is in the sodium chloride solution of 1wt%,
Ultrasonic 10min；In the above solution by the dispersion of 100mg carbon nanotube, 2h is ultrasonically treated at 30 DEG C；Suction filtration is dried to obtain function
The carbon material of change；
2) preparation of noble metal nano particles
The polyvinylpyrrolidone 41.2mg that molecular weight is 8000 is added in the 10ml aqueous solution for containing 20.60mg gold chloride
In, 103.0mg sodium borohydride reduction 2h is added after 1h is mixed under the mixing speed of 1000rpm, obtains a nanometer Au particle
Catalyst；
3) noble metal nano particles are supported
The carbon material of 49mg functionalization is dispersed in 10ml ethanol solution, after ultrasonic 0.5h, then 5ml is instilled and contains 1mg
The ethanol solution of nanometer Au particle, is mixed 6h, and functional carbon material supports noble metal catalyst；
Such as Fig. 1, functional carbon material prepared by embodiment 1 supports the transmission electron microscope picture of noble metal catalyst, and Electronic Speculum is aobvious
Show that Au particle is distributed than more uniform on functional carbon material, particle size distribution range are as follows: 1.9~2.4nm.
Embodiment 2:
1) preparation of functional carbon material
50mg diallyl dimethyl ammoniumchloride is dispersed in the chlorination that volume is 500ml, mass fraction is 5wt%
In sodium solution, ultrasonic 10min；In the above solution by the dispersion of 100mg carbon nanotube, 2h is ultrasonically treated at 30 DEG C；Filter drying
Obtain the carbon material of functionalization；
2) preparation of noble metal nano particles
The polyvinylpyrrolidone that molecular weight is 10000 is added in the 10ml aqueous solution for containing 20.60mg gold chloride
20.6mg is added 164.8mg sodium borohydride reduction 4h after 1h is mixed under the mixing speed of 1000rpm, obtains a nanometer Au
Beaded catalyst；
3) noble metal nano particles are supported
The carbon material of 95mg functionalization is dispersed in 20ml ethanol solution, after ultrasonic 0.5h, 10ml is instilled and contains 5mg
Nanometer Au particle ethanol solution, is mixed 2h, and functional carbon material supports noble metal catalyst；
Such as Fig. 1, functional carbon material prepared by embodiment 1 supports the transmission electron microscope picture of noble metal catalyst, and Electronic Speculum is aobvious
Show that Au particle is distributed than more uniform on functional carbon material, particle size distribution range are as follows: 9.3~10.2nm.
Embodiment 3:
1) preparation of functional carbon material
100mg kayexalate is dispersed in volume is 500ml, mass fraction is in the sodium chloride solution of 2wt%,
Ultrasonic 10min；In the above solution by the dispersion of 50mg carbon nanotube, 2h is ultrasonically treated at 50 DEG C；Suction filtration is dried to obtain functionalization
Carbon material；
2) preparation of noble metal nano particles
The polyvinylpyrrolidone 41.2mg that molecular weight is 8000 is added in the 10ml aqueous solution for containing 20.60mg gold chloride
Addition 103.0mg ascorbic acid reductase 12 h obtains a nanometer Au particulate catalytic after 1h is mixed under the mixing speed of 1000rpm
Agent；
3) noble metal nano particles are supported
The carbon material of 92mg functionalization is dispersed in 10ml ethanol solution, after ultrasonic 0.5h, 10ml is instilled and contains 8mg
Nanometer Au particle ethanol solution, is mixed 10h, and functional carbon material supports noble metal catalyst；
Functional carbon material prepared by embodiment 4 supports the distribution of particles and size and embodiment of noble metal catalyst
1 is similar；Embodiment 4:
1) preparation of functional carbon material
100mg kayexalate is dispersed in volume is 500ml, mass fraction is in the sodium chloride solution of 1wt%,
Ultrasonic 10min；In the above solution by the dispersion of 100mg Nano carbon balls, 2h is ultrasonically treated at 30 DEG C；Suction filtration is dried to obtain functionalization
Carbon material；
2) preparation of noble metal nano particles
309mg cetyl trimethylammonium bromide is added in 1000rpm in the 20ml aqueous solution for containing 61.80mg palladium nitrate
Mixing speed under be mixed 1h after be added 103.0mg sodium borohydride reduction 2h obtain nano Pd particle beaded catalyst；
3) noble metal nano particles are supported
The carbon material of 49mg functionalization is dispersed in 10ml dichloromethane solution, after ultrasonic 0.5h, 10ml is instilled and contains
1mg nano Pd particle particle dichloromethane solution, is mixed 6h, and functional carbon material supports noble metal catalyst；
Functional carbon material prepared by embodiment 4 supports the distribution of particles and size and embodiment of noble metal catalyst
2 is similar；
Embodiment 5:
1) preparation of functional carbon material
100mg kayexalate is dispersed in volume is 500ml, mass fraction is in the sodium nitrate solution of 1wt%,
Ultrasonic 10min；In the above solution by 100mg BP2000 dispersion, 1h is ultrasonically treated at 60 DEG C；Suction filtration is dried to obtain functionalization
Carbon material；
2) preparation of noble metal nano particles
The polyvinylpyrrolidone 41.2mg that molecular weight is 8000 is added in the 20ml aqueous solution for containing 20.60mg palladium nitrate
Addition 103.0mg sodium borohydride reduction 2h obtains nano Pd particle particulate catalytic after 1h is mixed under the mixing speed of 1000rpm
Agent；
3) noble metal nano particles are supported
The carbon material of 90mg functionalization is dispersed in 10ml ethanol solution, after ultrasonic 0.5h, 10ml is instilled and contains 10mg
Nano Pd particle particle ethanol solution, is mixed 6h, and functional carbon material supports noble metal catalyst；
Functional carbon material prepared by embodiment 5 supports the distribution of particles and size and embodiment of noble metal catalyst
2 is similar；
Application example
The catalyst prepared according to the method for embodiment 1 selective catalysis nitrobenzene in toluene solvant, catalyst recycling
Rate 97.0%.
Claims (11)
1. one kind is used for nitro benzene and its derivative hydrogenation catalyst preparation method, include the following steps:
1) carbon material is mixed in salting liquid with high molecular polymer, is ultrasonically treated 0.5~6h, obtains the carbon of functionalization
Material；
2) salting liquid of noble metal is prepared to the noble metal granule of certain size distribution under the action of protective agent and reducing agent；
3) carbon material containing modified with functional group obtained by step 1) is dispersed in ultrapure water or organic solvent, ultrasonic treatment 0.5
Carry out after~2h with the aqueous solution of the resulting noble metal granule of step 2) or organic solvent 2~12h of mixing obtain supporting it is expensive
Metallic catalyst.
2. nitro benzene and its derivative hydrogenation catalyst preparation method according to claim 1, which is characterized in that step 1)
In, the carbon material is one of Nano carbon balls, carbon nanotube, carbon fiber, graphene, BP2000, EC600, VXC-72
Or two or more mixing carbon；Specific surface area is 200~2000m2g-1；
In step 1), the high molecular polymer is kayexalate, diallyl dimethyl ammoniumchloride, polyphenyl
The mixture of one or more of amine, polypyrrole；The mass ratio of high molecular polymer and carbon material is 2/5~5/2；
In step 1), the salting liquid is one or more of sodium chloride, sodium sulphate, sodium nitrate；Salting liquid it is dense
Degree is 1~10wt%；The temperature of the ultrasonic treatment is 20~60 DEG C.
3. nitro benzene and its derivative hydrogenation catalyst preparation method according to claim 1, which is characterized in that
In step 2), the precious metal salt is gold trichloride, gold chloride, potassium platinic chloride, chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, nitre
The mixture of one or more of sour palladium, palladium chloride, tetrachloro-palladium acid amine, palladium acetylacetonate；
It is rapid 2) in, the protective agent is polyvinylpyrrolidone (molecular weight ranges be 8000~50000), cetyl front three
One or more of base ammonium bromide, KBr, NaBr；The mass ratio of protective agent and precious metal salt is 1/6~6/1；
In step 2), the reducing agent be one or both of ascorbic acid, sodium borohydride, formaldehyde, hydrazine hydrate, oleyl amine with
On；The mass ratio of reducing agent and precious metal salt is 1/1~10/1；Recovery time is 2~12h.
4. nitro benzene and its derivative hydrogenation catalyst preparation method according to claim 1, which is characterized in that step 3)
In, the organic solvent of the dispersion carbon material and noble metal nano particles include: methanol, ethyl alcohol, acetone, methylene chloride,
The mixture of one or more of chloroform.
5. nitro benzene and its derivative hydrogenation catalyst preparation method according to claim 1, which is characterized in that step 3)
In, the loading of the noble metal in the catalyst is 1~10wt%.
6. a kind of nitro benzene and its derivative hydrogenation catalyst that any preparation method of claim 1-5 obtains.
7. a kind of application of the hydrogenation catalyst described in claim 6 in the reaction of nitro benzene and its derivative hydrogenation catalyst.
8. application according to claim 7, it is characterised in that: catalyst and nitrobenzene are added in reaction dissolvent and its spreads out
Biology carries out catalysis reaction in the presence of hydrogen.
9. application according to claim 7, it is characterised in that: the reaction dissolvent be toluene, dodecane, fatty alcohol,
One or more of hexamethylene mixed liquor.
10. application according to claim 7, it is characterised in that: the nitro benzene derivate be o-chloronitrobenzene,
Chloronitrobenzene, parachloronitrobenzene, ortho-methylnitrobenzene, meta-nitrotoluene, para-nitrotoluene, o-nitrobenzaldehyde, p-nitrophenyl first
One or more of aldehyde, p-nitroacetophenone；The catalytic temperature are as follows: 20~100 DEG C；Reaction time be 2~
24h；Reaction Hydrogen Vapor Pressure is 0.5~5MPa.
11. application according to claim 10, it is characterised in that: after 3~10h of reaction, the conversion ratio of nitrobenzene is 95%
~97.2%；The selectivity of aniline is 96.8%~98.0%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013561A (en) * | 2019-12-31 | 2020-04-17 | 贵研工业催化剂（云南）有限公司 | Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline |
| CN113398922A (en) * | 2021-06-02 | 2021-09-17 | 山西大学 | Noble metal-loaded carbon material catalyst and preparation method and application thereof |
| CN113492277A (en) * | 2020-03-19 | 2021-10-12 | 江苏奥匠新材料科技有限公司 | Low-temperature tin paste material with metal coating and carbon nanotube reinforcement and preparation method thereof |
| CN113578316A (en) * | 2021-08-27 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene |
| CN115911424A (en) * | 2022-12-01 | 2023-04-04 | 烯湾科城(广州)新材料有限公司 | Noble metal/carbon catalyst, preparation method thereof and fuel cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
| CN101569859A (en) * | 2009-05-21 | 2009-11-04 | 江苏康恒化工有限公司 | Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
-
2017
- 2017-10-11 CN CN201710940720.XA patent/CN109647517A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966144A (en) * | 2006-09-06 | 2007-05-23 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
| CN101569859A (en) * | 2009-05-21 | 2009-11-04 | 江苏康恒化工有限公司 | Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
Non-Patent Citations (2)
| Title |
|---|
| JAE YOUNG PARK, SEOK KIM: "Preparation and electroactivity of polymer-functionalized graphene oxide-supported platinumnano particles catalysts", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| YUFAN ZHANG, LIJUN ZENG, XIANGJIE BO, HUAN WANG, LIPING GUO: "Electrochemical study of nitrobenzene reduction using novel Pt nanoparticles/macroporous carbon hybrid nanocomposites", 《ANALYTICA CHIMICA ACTA》 * |
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| CN111013561A (en) * | 2019-12-31 | 2020-04-17 | 贵研工业催化剂（云南）有限公司 | Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline |
| CN113492277A (en) * | 2020-03-19 | 2021-10-12 | 江苏奥匠新材料科技有限公司 | Low-temperature tin paste material with metal coating and carbon nanotube reinforcement and preparation method thereof |
| CN113398922A (en) * | 2021-06-02 | 2021-09-17 | 山西大学 | Noble metal-loaded carbon material catalyst and preparation method and application thereof |
| CN113398922B (en) * | 2021-06-02 | 2023-09-22 | 山西大学 | Noble metal-loaded carbon material catalyst and preparation method and application thereof |
| CN113578316A (en) * | 2021-08-27 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene |
| CN115911424A (en) * | 2022-12-01 | 2023-04-04 | 烯湾科城(广州)新材料有限公司 | Noble metal/carbon catalyst, preparation method thereof and fuel cell |
| CN115911424B (en) * | 2022-12-01 | 2023-08-15 | 广州烯湾氢能科技有限公司 | Noble metal/carbon catalyst, preparation method thereof and fuel cell |
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