CN102513100A - Active carbon loaded catalyst and preparation method and application thereof - Google Patents

Active carbon loaded catalyst and preparation method and application thereof Download PDF

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CN102513100A
CN102513100A CN2011103946083A CN201110394608A CN102513100A CN 102513100 A CN102513100 A CN 102513100A CN 2011103946083 A CN2011103946083 A CN 2011103946083A CN 201110394608 A CN201110394608 A CN 201110394608A CN 102513100 A CN102513100 A CN 102513100A
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active carbon
aqueous solution
activated carbon
filter cake
catalyst
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陈素琴
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Wenzhou University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses an active carbon loaded catalyst and a preparation method and application thereof. The catalyst uses active carbon as a carrier and uses platinum and palladium as active ingredients. The preparation method comprises the following steps that: (1) active carbon is soaked by nitric acid water solution for 4 hours, then, the filtering is carried out, filter cake is washed to the neutral state, and the treated active carbon is obtained; (2) the active carbon treated in the first step is impregnated in H2PdCl4 water solution and H2PtCl6 water solution for 4 to 8 hours, the pH value of the reaction solution is regulated to the alkaline state after the impregnation completion, the filtering is carried out, the filter cake is washed to the neutral state and is filtered, and the filter cake is obtained; and (3) the filter cake obtained in the second step is added into reducing agents to take reaction at 10 to 50 DEG C for 1 to 5 hours, the reaction is completed, the reaction liquid is filtered, the filter cake is filtered again after being washed, the obtained filter cake is dried, and the active carbon loaded catalyst is prepared. The catalyst has the advantages that the activity, the selectivity and the stability are extremely high, the preparation method is simple, the environmental-friendly effect is realized, and the catalyst is applicable to industrial application.

Description

A kind of activated carbon supported Catalysts and its preparation method and application
(1) technical field
The present invention relates to a kind of catalyst and preparation thereof and use particularly a kind of activated carbon supported Catalysts and its preparation method and application.
(2) background technology
Para-aminophenol (being called for short PAP) is important industrial chemicals and organic intermediate, is widely used in fields such as medicine, rubber, dye well photosensitive material.As medicine intermediate; PAP can be used for medicines such as synthetic paracetamol (acamol), benoral, clofibrate, vitamin B1, practolol, complexing agent niacinamide, sal phenol, 6-oxyquinoline, and is wherein maximum with the consumption figure of synthetic paracetamol again.Paracetamol is assert it is kind preferably by various countries the world of medicine in the antipyretic analgesic medicine.After it is found that taking common antipyretic analgesic medicine (like antifebrin and phenetidine etc.) can resolve into poisonous aniline in human body the seventies in 20th century; People's attention extremely; American and Britain, day etc., developed country forbade producing these medicines of use, thereby the demand of paracetamol heightens.Another important application of PAP is a synthetic p phenylenediamine type antioxidant 4020,4030 etc.; These products are supporting age resistor of rising radial-ply tyre product; Also be at present universally acknowledged low toxicity, efficient, oligosaprobic rubber industry good age resistor commonly used, it will progressively replace the naphthylamines class and the thiazoles age resistor becomes main rubber antioxidant kind.
Baeyer in 1874 and Caro are at first with the synthetic PAP of method of glass putty reduction p-nitrophenol; Extensive use along with PAP; Its preparation method develops into multiple; The preparation method of PAP can be divided into p-nitrophenol method, phenol method, para-nitrochloro-benzene method, nitrobenzene method etc. by raw material, wherein is that raw material employing catalytic hydrogenating reduction method production PAP is the most advanced at present production technology with nitrobenzene, has plurality of advantages such as raw material is easy to get, technology is simple, production cost is low.The nitrobenzene catalytic hydrogenation prepares the heterogeneous reaction system that PAP is a complicacy, comprises gas phase (H 2), solid phase (catalyst), organic facies (nitrobenzene) and water are totally four mutually.The reaction mechanism of this reaction is as follows; The surface reduction that nitrobenzene and hydrogen at first are adsorbed in catalyst generates the hydroxyanilines intermediate; Be that a competitive reaction takes place raw material with the hydroxyanilines intermediate then; Be that hydroxyanilines the Bamberger rearrangement reaction takes place in acid medium obtains PAP, hydroxyanilines is if further hydrogenation then is reduced to accessory substance aniline, and reaction equation is as follows:
Figure BDA0000115366770000021
The ratio of para-aminophenol/aniline is mainly determined by the adsorption capacity of catalyst para hydroxybenzene amine intermediate; If a little less than the adsorption capacity of the adsorption capacity of catalyst para hydroxybenzene amine intermediate comparison hydrogen; Then the Bamberger rearrangement reaction takes place and generates PAP in the easy desorption of hydroxyanilines intermediate, otherwise before desorption not further hydrogenating reduction generate accessory substance aniline.Be under the situation of target product with PAP, except the acid condition that the Bamberger rearrangement reaction needs, hydrogenation catalyst is crucial to the contrast of hydrogen, hydroxyanilines intermediate adsorption capacity and the complexity of hydroxyanilines intermediate desorption.
The basic research in the present invention early stage shows, palladium, platinum reactive metal are different to suction, the desorption ability of hydrogen, hydroxyanilines intermediate.Compare with the platinum reactive metal; Thereby the palladium reactive metal can be realized the absorption of dissociating of hydrogen more quickly the nitrobenzene reduction that adsorbs is become the hydroxyanilines intermediate; But the adsorption capacity of palladium reactive metal para hydroxybenzene amine intermediate also is better than the platinum reactive metal, is unfavorable for behind the para hydroxybenzene amine intermediate desorption Bamberger rearrangement reaction generation PAP taking place.Therefore, activated carbon supported one pack system palladium catalyst hydrogenation reaction speed is faster than activated carbon supported one pack system platinum catalyst, but the PAP selectivity will be lower than activated carbon supported one pack system platinum catalyst.
(3) summary of the invention
The object of the invention provides a kind of activated carbon supported Catalysts and its preparation method and application; Activated carbon supported catalyst of the present invention has successfully remedied the defective of activated carbon supported one pack system palladium catalyst and activated carbon supported one pack system platinum catalyst; This catalyst activity, selectivity and stability are higher; The preparation method is simple, and environmental friendliness is suitable for commercial Application.
The technical scheme that the present invention adopts is:
A kind of activated carbon supported catalyst, described catalyst are carrier with the active carbon, are active component with platinum and palladium; Said active component is in the carrier quality, and the loading of platinum is 0.2～2wt%, and the loading of palladium is 0.2～2wt%.
Described active component is in the carrier quality, and the loading of platinum is preferably 0.5～1.0wt%, and the loading of palladium is preferably 0.5～1.0wt%.
Described active carbon specific area is preferably 1600～1800m 2/ g.
A kind of method for preparing activated carbon supported catalyst of the present invention, described method is carried out according to following steps: (1) is soaked 4h with active carbon with aqueous solution of nitric acid, filters then, Cake Wash is to neutral, the active carbon after obtaining to handle; (2) active carbon after step (1) processing is added entry and adds H 2PdCl 4The aqueous solution and H 2PtCl 6Stir 4～8h in the mixed liquor that the aqueous solution is processed, reaction finishes conditioned reaction liquid pH value to alkalescence, filters, and the filter cake washing is filtered to neutral, obtains filter cake; H in the described mixed liquor 2PdCl 4The Theoretical Mass of middle Pd is counted 0.2～2wt% with the quality of the active carbon of input; Said H 2PtCl 6It is 0.2～2wt% that the Theoretical Mass of middle Pt is counted with the quality of the active carbon of input; (3) filter cake that step (2) is obtained adds reducing agent in 10～50 ℃ of reaction 1～5h, and reaction finishes, reacting liquid filtering, and filtration cakes torrefaction makes activated carbon supported catalyst; Described reducing agent is a hydrazine hydrate; The volumetric usage of said reducing agent is with H 2PdCl 4In Pd Theoretical Mass and H 2PtCl 6The gross mass of the Theoretical Mass of middle Pt is counted 10～30mL/g, and the metering method of the volumetric usage of said reducing agent is this area universal method, and said reducing agent consumption does not influence the present invention in premier's opinion quality of Pd and Pt.
Further, the mass concentration of aqueous solution of nitric acid is 1～10% in the described step (1), and the volumetric usage of said aqueous solution of nitric acid is counted 10mL/g with quality of activated carbon.
H in the described step (2) 2PdCl 4The aqueous solution and H 2PtCl 6The mass concentration of the aqueous solution is 0.05g/mL.
Reducing agent hydrazine hydrate described in the described step (3) adds with the form of mass concentration 55% hydrazine hydrate aqueous solution.
Further, earlier step (1) active carbon processed is added in the entry in the described step (2), be heated to 60～90 ℃, be made into the active carbon slurries, add H again 2PdCl 4The aqueous solution and H 2PtCl 6In the mixed liquor that the aqueous solution is processed, the consumption of said water makes active carbon become slurries and gets final product, said H 2PdCl 4The aqueous solution and H 2PtCl 6The mixed liquor consumption of the aqueous solution is according to H 2PdCl 4And H 2PtCl 6The loading of middle platinum and palladium is fixed.
Further, dipping finishes conditioned reaction liquid pH value to 7～9 in the described step (2).
Further, described activated carbon supported Preparation of catalysts method recommends to carry out according to following steps: (1) is with specific area 1600～1800m 2The active carbon of/g impregnated in the aqueous solution of nitric acid of mass concentration 1～10%, and reflux temperature is dipping 4h down, and filtration then, Cake Wash are extremely neutral, the active carbon after obtaining to handle; The volumetric usage of said aqueous solution of nitric acid is counted 10mL/g with quality of activated carbon; (2) active carbon after step (1) processing is added in the entry, be heated to 60～90 ℃, be mixed with the active carbon slurries, slowly be added dropwise to the H of mass concentration 0.05g/mL again 2PdCl 4The H of the aqueous solution and mass concentration 0.05g/mL 2PtCl 6The mixed liquor that the aqueous solution is processed, 60～90 ℃ are stirred 4～8h, and reaction finishes conditioned reaction liquid pH value to 7～9, filters, and the filter cake washing is filtered to neutral, obtains filter cake; H in the described mixed liquor 2PdCl 4The Theoretical Mass of Pd is counted 0.2～2wt% with the quality of the active carbon of input in the aqueous solution; Said H 2PtCl 6The Theoretical Mass of Pt is counted 0.2～2wt% with the quality of the active carbon of input in the aqueous solution; (3) filter cake that step (2) is obtained adds in the entry, is heated to 10～50 ℃ and processes slurries, adds the reducing agent hydrazine hydrate again in 10～50 ℃ of reaction 1～5h; Reaction finishes, reacting liquid filtering, Cake Wash; Filter after the washing, the filtration cakes torrefaction of acquisition makes activated carbon supported catalyst again; Described reducing agent adds with the form of mass concentration 55% aqueous solution, and the volumetric usage of said reducing agent is with H 2PdCl 4In Pd Theoretical Mass and H 2PtCl 6The gross mass of the Theoretical Mass of middle Pt is counted 10～30mL/g;
In the activated carbon supported Preparation of catalysts method of the present invention, preferred 25～35 ℃ of the reduction reaction temperature described in the described step (3), preferred 2～3h of reaction time.
Filter cake is dry down in room temperature (25 ℃), gets wet appearance and is described activated carbon supported catalyst.
Activated carbon supported catalyst of the present invention prepares the application in the para-aminophenol at the nitrobenzene catalytic hydrogenation, described being applied as: nitrobenzene, softex kw are mixed in reactor with 15% aqueous sulfuric acid, under the effect of said activated carbon supported catalyst; Earlier with the air in the nitrogen replacement reactor; Use nitrogen in the hydrogen exchange reactor again, stirring reaction under 50～110 ℃, 0.1～0.3MPa condition needs 4h usually; Reaction finishes; Reacting liquid filtering, filter cake reclaims catalyst, and filtrating is product para-aminophenol bullion; The mass ratio that feeds intake of described nitrobenzene and softex kw, catalyst is 1: 0.0005～0.01: 0.001～0.1, and the volumetric usage of described aqueous sulfuric acid is counted 1～20mL/g with the nitrobenzene quality.
Further; Described activated carbon supported catalyst prepares the application in the para-aminophenol at the nitrobenzene catalytic hydrogenation; The mass ratio that feeds intake of described nitrobenzene and softex kw, catalyst is preferably 1: 0.002～and 0.005: 0.02～0.05, the volumetric usage of described sulfuric acid solution is preferably 2～10mL/g in the nitrobenzene quality.
Further, described activated carbon supported catalyst prepares the application in the para-aminophenol at the nitrobenzene catalytic hydrogenation, preferred 60～90 ℃ of described reaction temperature, the preferred 0.1～0.2MPa of reaction pressure.
Further, described activated carbon supported catalyst prepares the application in the para-aminophenol (PAP) at the nitrobenzene catalytic hydrogenation, and described para-aminophenol bullion adopts high performance liquid chromatograph that PAP is carried out quantitative analysis (chromatographic column C184.6*150, flowing phase V Methyl alcohol/ V Water=60/40, flow velocity: 1.0mL/min, column temperature: 25 ℃; Wavelength: 254nm), adopt gas chromatograph p-nitrophenyl and accessory substance aniline to carry out quantitative analysis (chromatographic column SE-30 capillary column, fid detector; Hydrogen 50mL/min; Air 60mL/min, injector temperature 533K, 10K/min rises to 523K by 373K).
The prepared active carbon-supported palladium of the present invention-platinum bicomponent catalyst has obtained the PAP product yield up to 77% in the nitrobenzene catalytic hydrogenation prepares para-aminophenol reaction.
Compared with prior art; Beneficial effect of the present invention is mainly reflected in: activated carbon supported catalyst of the present invention has successfully remedied the defective of activated carbon supported one pack system palladium catalyst and activated carbon supported one pack system platinum catalyst; Palladium-platinum dual-active property component had both guaranteed hydrogenation reaction speed faster, can obtain higher PAP selectivity again, and active carbon-supported palladium-platinum bicomponent catalyst shows the catalytic performance that is superior to other catalyst of the same type in the nitrobenzene catalytic hydrogenation prepares para-aminophenol reaction; This catalyst activity, selectivity and stability are higher; The preparation method is simple, and environmental friendliness is suitable for commercial Application.
(4) specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Adopt high performance liquid chromatograph that PAP is carried out quantitative analysis (chromatographic column C184.6*150, flowing phase V Methyl alcohol/ V Water=60/40, flow velocity: 1.0mL/min, column temperature: 25 ℃; Wavelength: 254nm), adopt gas chromatograph p-nitrophenyl and accessory substance aniline to carry out quantitative analysis (chromatographic column SE-30 capillary column, fid detector; Hydrogen 50mL/min; Air 60mL/min, injector temperature 533K, 10K/min rises to 523K by 373K).
Embodiment 1
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m 2It is in 1% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed 4 hours; Reacting liquid filtering, the cakes with deionized water washing adds the active carbon of handling in the entry to neutral then; Be heated to 60 ℃ and be mixed with the 100mL slurries, drip the H of 0.4 milliliter of 0.05g/mL successively 2PdCl 4The H of the 0.05g/mL of the aqueous solution (Pd content is 0.02g) and 4 milliliters 2PtCl 4The aqueous solution (Pt content is 0.2g), 60 ℃ are stirred 4h, again with 10% NaOH solution regulator solution pH value neutrality (pH=7) extremely, and cool the temperature to room temperature (25 ℃); Filter, the washing of filter cake deionized water is filtered to neutral, and filter cake adds entry; Under 30 ℃, be configured to the slurries of 150mL, slowly drip 2.2 milliliters 55% hydrazine hydrate aqueous solution then, 30 ℃ are continued to stir reacting liquid filtering 2 hours; The washing of filter cake deionized water is neutrality (pH=7) extremely, secondary filter, and the secondary filter cake is preliminarily dried under room temperature (25 ℃), gets wet appearance and seals preservation; Be described activated carbon supported catalyst 15.65g, the loading of Pd is 0.2wt%, and the loading of Pt is 2.0wt%.
Embodiment 2
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m 2It is in 2.5% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed 4 hours; Reacting liquid filtering, the cakes with deionized water washing adds the active carbon of handling in the entry to neutral then; Be heated to 70 ℃ and be mixed with the 100mL slurries, drip the H of 1 milliliter of 0.05g/mL successively 2PdCl 4The H of the aqueous solution (Pd content is 0.05g) and 3 milliliters of 0.05g/mL 2PtCl 4The aqueous solution (Pt content is 0.15g), 70 ℃ are stirred 4h, again with 10% NaOH solution regulator solution pH value to alkalescent (pH=8), and cool the temperature to room temperature (25 ℃); Reacting liquid filtering, the washing of filter cake deionized water is filtered to neutral, and filter cake adds in the entry; Be heated to 30 ℃ and be mixed with the 150mL slurries, slowly drip 4 milliliters 55% hydrazine hydrate solution then, 30 ℃ are continued to stir 2 hours, filter; The cakes with deionized water washing is filtered to neutral (pH=7), and filter cake is got wet appearance sealing and preserved in room temperature (25 ℃) preliminarily dried; Be described activated carbon supported catalyst 15.52g, the loading of Pd is 0.5wt%, and the loading of Pt is 1.5wt%.
Embodiment 3
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m 2It is in 5% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed reacting liquid filtering 4 hours; The cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 80 ℃, be mixed with the 100mL slurries, drip the H of 2 milliliters of 0.05g/mL successively 2PdCl 4The H of the aqueous solution (Pd content is 0.1g) and 2 milliliters of 0.05g/mL 2PtCl 4The aqueous solution (Pt content is 0.1g), 80 ℃ are stirred 6h, again with 10% NaOH solution regulator solution pH value extremely alkaline (pH=8.5), and cool the temperature to 25 ℃ of room temperatures; Filter, the cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 35 ℃, be mixed with the 150mL slurries, slowly drip 4 milliliters 55% hydrazine hydrate solution then, 35 ℃ are continued to stir 3 hours; Filter, the cakes with deionized water washing is filtered to neutral, and filter cake is in room temperature (25 ℃) preliminarily dried; Get wet appearance sealing and preserve, be described activated carbon supported catalyst 15.66g, the loading of Pd is 1.0wt%, and the loading of Pt is 1.0wt%.
Embodiment 4
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m 2It is in 10% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed 4 hours, filtered; The cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 90 ℃, be mixed with the 100mL slurries, drip the H of 4 milliliters of 0.05g/mL successively 2PdCl 4The H of the aqueous solution (Pd content is 0.2g) and 0.4 milliliter of 0.05g/mL 2PtCl 4The aqueous solution (Pt content is 0.02g), 90 ℃ are stirred 8h, again with 10% NaOH solution regulator solution pH value extremely alkaline (pH=9), and cool the temperature to room temperature (25 ℃); Filter, the cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 25 ℃ and be mixed with the 150mL slurries, slowly drip 6.6 milliliters 55% hydrazine hydrate solution then, 25 ℃ are continued to stir 2 hours, filter; The cakes with deionized water washing is filtered to neutral, and filter cake is got wet appearance sealing and preserved in room temperature (25 ℃) preliminarily dried; Be described activated carbon supported catalyst 15.50g, the loading of Pd is 2.0wt%, and the loading of Pt is 0.2wt%.
Embodiment 5
Take by weighing the 10g active carbon, the specific area of active carbon is 1700m 2It is in 5% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed 4 hours, filters, and the cakes with deionized water washing is to neutral, and filter cake adds in the entry, is heated to 85 ℃ and is mixed with the 100mL slurries, drips the H of 2 milliliters of 0.05g/mL successively 2PdCl 4The H of the aqueous solution (Pd content is 0.1g) and 2 milliliters of 0.05g/mL 2PtCl 4The aqueous solution (Pt content is 0.1g), 85 ℃ are stirred 6h, again with 10% NaOH solution regulator solution pH value extremely alkaline (pH=8), and cool the temperature to room temperature (25 ℃); Filter, the cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 30 ℃ and be mixed with the 150mL slurries, slowly drip 3 milliliters 55% hydrazine hydrate solution then, 30 ℃ are continued to stir 3 hours, filter; Cakes with deionized water washing is filtered to neutral, filter cake in room temperature in drying; Get wet appearance sealing preservation and be described activated carbon supported catalyst 15.70g, the loading of Pd is 1.0wt%, and the loading of Pt is 1.0wt%.
Embodiment 6
Take by weighing the 10g active carbon, the specific area of active carbon is 1800m 2It is in 5% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed 4 hours; Filter, the cakes with deionized water washing is filtered to neutral; Filter cake adds in the entry, is heated to 85 ℃ and is mixed with the 100mL slurries, drips the H of 1 milliliter of 0.05g/mL successively 2PdCl 4The H of the aqueous solution (Pd content is 0.05g) and 3 milliliters of 0.05g/mL 2PtCl 4The aqueous solution (Pt content is 0.15g), 85 ℃ are stirred 6h, again with 10% NaOH solution regulator solution pH value extremely alkaline (pH=8.5), and cool the temperature to room temperature (25 ℃); Filter, the cakes with deionized water washing is filtered to neutral, and filter cake adds entry; Under 30 ℃, be mixed with the 150mL slurries, slowly drip 4 milliliters 55% hydrazine hydrate solution then, 30 ℃ are continued to stir 3 hours, filter; The cakes with deionized water washing is filtered to neutral, and filter cake is got wet appearance sealing and preserved in drying at room temperature; Be described activated carbon supported catalyst 15.85g, the loading of Pd is 0.5wt%, and the loading of Pt is 1.5wt%.
Embodiment 7
In 250mL glass closed reactor, add the activated carbon supported catalyst 0.24g of embodiment 1 preparation, nitrobenzene 12g; Mass concentration is 15% sulfuric acid solution 60mL, softex kw 0.024g, off-response device; Use the air in the nitrogen replacement reactor to use the nitrogen three times in the hydrogen exchange reactor for three times then and keep the pressure in the reactor to be 0.1MPa, be warming up to 60 ℃, begin to stir; 1000 rev/mins of stir speed (S.S.)s, isothermal reaction 4 hours stops reaction; Take out reactant liquor, remove by filter catalyst, filtrating is used high performance liquid chromatography and gas chromatographic analysis respectively; The nitrobenzene conversion ratio is 82.1%, and para-aminophenol (PAP) yield is 67.3% (in the nitrobenzene quality).
Embodiment 8
In 250mL glass closed reactor, add the activated carbon supported catalyst 0.48g of embodiment 2 preparations, nitrobenzene 12g, mass concentration is 15% sulfuric acid solution 96mL; Softex kw 0.048g, the off-response device uses the air in the nitrogen replacement reactor to use the nitrogen three times in the hydrogen exchange reactor for three times then and keep the pressure in the reactor to be 0.15MPa, is warming up to 70 ℃; Begin to stir 1000 rev/mins of stir speed (S.S.)s, isothermal reaction 4 hours; Stop reaction, take out reactant liquor, remove by filter catalyst; It is 88.3% that filtrating is used high performance liquid chromatography and gas chromatographic analysis, nitrobenzene conversion ratio respectively, and the PAP yield is 72.7%.
Embodiment 9
In 250mL glass closed reactor, add the activated carbon supported catalyst 0.6g of embodiment 3 preparations, nitrobenzene 12g, mass concentration is 15% sulfuric acid solution 120mL; Softex kw 0.06g, the off-response device uses the air in the nitrogen replacement reactor to use the nitrogen three times in the hydrogen exchange reactor for three times then and keep the pressure in the reactor to be 0.2MPa, is warming up to 80 ℃; Begin to stir 1000 rev/mins of stir speed (S.S.)s, isothermal reaction 4 hours; Stop reaction, take out reactant liquor, remove by filter catalyst; It is 94.5% that filtrating is used high performance liquid chromatography and gas chromatographic analysis, nitrobenzene conversion ratio respectively, and the PAP yield is 76.3%.
Embodiment 10
Add the activated carbon supported catalyst 0.6g of embodiment 4 preparations, be warming up to 90 ℃, the logical embodiment 9 of other operations, the nitrobenzene conversion ratio is 98.1%, the PAP yield is 65.9%.
Embodiment 11
The activated carbon supported catalyst 0.6g that adds embodiment 5 preparations, keeping the pressure in the reactor is 0.15MPa, is warming up to 80 ℃, and other are operated with embodiment 9, and the nitrobenzene conversion ratio is 96.2%, and the PAP yield is 77.0%.
Embodiment 12
Active carbon-supported palladium-platinum bicomponent catalyst the 0.6g that adds embodiment 6 preparations, keeping the pressure in the reactor is 0.15MPa, is warming up to 80 ℃, and other are operated with embodiment 9, and the nitrobenzene conversion ratio is 91.5%, and the PAP yield is 75.4%.
Comparative Examples 1
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m 2It is in 5% the aqueous solution of nitric acid that/g, active carbon are immersed in 100 milliliters of mass concentrations, and 92 ℃ were refluxed reacting liquid filtering 4 hours; The cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 80 ℃, be mixed with the 100mL slurries, drip the H of 4 milliliters of 0.05g/mL 2PtCl 4The aqueous solution (Pt content is 0.2g), 80 ℃ are stirred 6h, again with 10% NaOH solution regulator solution pH value extremely alkaline (pH=8.5), and cool the temperature to 25 ℃ of room temperatures; Filter, the cakes with deionized water washing is filtered to neutral, and filter cake adds in the entry; Be heated to 35 ℃, be mixed with the 150mL slurries, slowly drip 4 milliliters 55% hydrazine hydrate solution then, 35 ℃ are continued to stir 3 hours; Filter, the cakes with deionized water washing is filtered to neutral, and filter cake is in room temperature (25 ℃) preliminarily dried; Get wet appearance sealing and preserve, be described activated carbon supported catalyst 15.32g, the loading of Pt is 2.0wt%.
In 250mL glass closed reactor, add the Pt/C catalyst 0.50g that Comparative Examples 1 makes, 12g nitrobenzene, mass concentration is 15% sulfuric acid solution 60mL, the 0.05g softex kw.The off-response device uses the air in the nitrogen replacement reactor to use the nitrogen three times in the hydrogen exchange reactor for three times then and keep the pressure in the reactor to be 0.2MPa, is warming up to 85 ℃; Begin to stir 1000 rev/mins of stir speed (S.S.)s, isothermal reaction 4 hours; Stop reaction, take out reactant liquor, remove by filter catalyst; It is 89.2% that filtrating is used high performance liquid chromatography and gas chromatographic analysis, nitrobenzene conversion ratio respectively, and the PAP yield is 53.4%.

Claims (9)

1. an activated carbon supported catalyst is characterized in that described catalyst is carrier with the active carbon, is active component with platinum and palladium; Said active component is in the carrier quality, and the loading of platinum is 0.2～2wt%, and the loading of palladium is 0.2～2wt%.
2. activated carbon supported catalyst as claimed in claim 1 is characterized in that described active component in the carrier quality, and the loading of platinum is 0.5～1wt%, and the loading of palladium is 0.5～1wt%.
3. activated carbon supported catalyst as claimed in claim 1 is characterized in that described active carbon specific area is 1600～1800m 2/ g.
4. method for preparing activated carbon supported catalyst as claimed in claim 1; It is characterized in that described method carries out according to following steps: (1) is soaked 4h with active carbon with aqueous solution of nitric acid; Filtration then, Cake Wash are extremely neutral, the active carbon after obtaining to handle; (2) active carbon after step (1) processing is added entry and adds H 2PdCl 4The aqueous solution and H 2PtCl 6Stir 4～8h in the mixed liquor that the aqueous solution is processed, reaction finishes conditioned reaction liquid pH value to alkalescence, filters, and the filter cake washing is filtered to neutral, obtains filter cake; H in the described mixed liquor 2PdCl 4The Theoretical Mass of middle Pd is counted 0.2～2wt% with the quality of the active carbon of input; Said H 2PtCl 6The Theoretical Mass of middle Pt is counted 0.2～2wt% with the quality of the active carbon of input; (3) filter cake that step (2) is obtained adds reducing agent in 10～50 ℃ of reaction 1～5h, and reaction finishes, reacting liquid filtering, and filtration cakes torrefaction makes activated carbon supported catalyst; Described reducing agent is a hydrazine hydrate; The volumetric usage of said reducing agent is with described mixed liquor H 2PdCl 4In Pd Theoretical Mass and H 2PtCl 6The gross mass of the Theoretical Mass of middle Pt is counted 10～30mL/g.
5. activated carbon supported Preparation of catalysts method as claimed in claim 4 is characterized in that the mass concentration of aqueous solution of nitric acid in the described step (1) is 1～10%, and the volumetric usage of said aqueous solution of nitric acid is counted 10mL/g with quality of activated carbon.
6. activated carbon supported Preparation of catalysts method as claimed in claim 4 is characterized in that H in the described step (2) 2PdCl 4The aqueous solution and H 2PtCl 6The mass concentration of the aqueous solution is 0.05g/mL.
7. activated carbon supported Preparation of catalysts method as claimed in claim 4 is characterized in that the reducing agent hydrazine hydrate described in the described step (3) adds with the form of mass concentration 55% hydrazine hydrate aqueous solution.
8. activated carbon supported Preparation of catalysts method as claimed in claim 4, it is characterized in that described method is: (1) is with specific area 1600～1800m 2The active carbon of/g impregnated in the aqueous solution of nitric acid of mass concentration 1～10%, and reflux temperature is dipping 4h down, and filtration then, Cake Wash are extremely neutral, the active carbon after obtaining to handle; The volumetric usage of said aqueous solution of nitric acid is counted 10mL/g with quality of activated carbon; (2) active carbon after step (1) processing is added in the entry, be heated to 60～90 ℃, be mixed with the active carbon slurries, slowly drip the H of mass concentration 0.05g/mL again 2PdCl 4The H of the aqueous solution and mass concentration 0.05g/mL 2PtCl 6The mixed solution of the aqueous solution, 60～90 ℃ are stirred 4～8h, and reaction finishes conditioned reaction liquid pH value to 7～9, filters, and the filter cake washing is filtered to neutral, obtains filter cake; H in the described mixed liquor 2PdCl 4The Theoretical Mass of Pd is counted 0.2～2wt% with the quality of the active carbon of input in the aqueous solution; Said H 2PtCl 6The Theoretical Mass of Pt is counted 0.2～2wt% with the quality of the active carbon of input in the aqueous solution; (3) filter cake that step (2) is obtained adds in the entry, is heated to 10～50 ℃ and processes slurries, adds the reducing agent hydrazine hydrate again in 10～50 ℃ of reaction 1～5h; Reaction finishes, reacting liquid filtering, Cake Wash; Filter, the filtration cakes torrefaction of acquisition makes activated carbon supported catalyst again; Described reducing agent adds with the form of mass concentration 55% aqueous solution, and the volumetric usage of said reducing agent is with H 2PdCl 4In Pd Theoretical Mass and H 2PtCl 6The gross mass of the Theoretical Mass of middle Pt is counted 10～30mL/g.
9. activated carbon supported catalyst as claimed in claim 1 prepares the application in the para-aminophenol at the nitrobenzene catalytic hydrogenation; It is characterized in that described being applied as: nitrobenzene, softex kw are mixed in reactor with 15% aqueous sulfuric acid, under the effect of said activated carbon supported catalyst, earlier with the air in the nitrogen replacement reactor; Use nitrogen in the hydrogen exchange reactor again; Stirring reaction 4h under 50～110 ℃, 0.1～0.3MPa condition, reaction finishes, reacting liquid filtering; Filter cake reclaims catalyst, and filtrating is product para-aminophenol bullion; The mass ratio that feeds intake of described nitrobenzene and softex kw, catalyst is 1: 0.0005～0.01: 0.001～0.1, and the volumetric usage of described aqueous sulfuric acid is counted 1～20mL/g with the nitrobenzene quality.
CN2011103946083A 2011-12-02 2011-12-02 Active carbon loaded catalyst and preparation method and application thereof Pending CN102513100A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103071486A (en) * 2012-12-21 2013-05-01 江苏扬农化工集团有限公司 Preparation method of palladium-platinum bimetallic catalyst
CN104667909A (en) * 2015-03-07 2015-06-03 刘平 Preparation method of high-activity long-acting platinum-carbon catalyst
CN108927146A (en) * 2017-05-23 2018-12-04 中国石油天然气股份有限公司 Inferior heavy oil hydrogenation catalyst and preparation method thereof
CN108097243A (en) * 2017-12-26 2018-06-01 江西省汉氏贵金属有限公司 Activated carbon supported palladium catalyst of alkali modification and preparation method thereof
CN110841636A (en) * 2019-12-02 2020-02-28 西安凯立新材料股份有限公司 Catalyst for preparing 5-amino isophthalic acid and preparation method and application thereof
CN110841636B (en) * 2019-12-02 2023-10-17 西安凯立新材料股份有限公司 Catalyst for preparing 5-amino isophthalic acid and preparation method and application thereof
CN115532254A (en) * 2022-11-29 2022-12-30 山东国邦药业有限公司 Preparation method of novel palladium-carbon catalyst for doxycycline production
CN115532254B (en) * 2022-11-29 2023-03-03 山东国邦药业有限公司 Preparation method of palladium-carbon catalyst for doxycycline production

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