CN104028283B - The method of magnetic carbon material load metallic catalyst and the dechlorination of catalysis chlorophenol thereof - Google Patents
The method of magnetic carbon material load metallic catalyst and the dechlorination of catalysis chlorophenol thereof Download PDFInfo
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Abstract
The present invention relates to the method for magnetic carbon material load metallic catalyst and the dechlorination of catalysis chlorophenol thereof, belong to organic synthesis and field of catalytic reactions.Technical problem to be solved by this invention is to provide a class magnetic carbon material load metallic catalyst and adopts the method for this catalyst chlorophenol dechlorination.Magnetic carbon material load metallic catalyst of the present invention, it is load Fe on the carbon material
3o
4with the compound that active metallic element obtains; Wherein, described material with carbon element is active carbon, CNT or Graphene, described active metallic element be in platinum, palladium and rhodium one or both.Catalyst preparation step of the present invention is simple, and this catalyst is reduced in preparation process simultaneously, saves reduction step; Such catalyst p-Chlorophenic acid has extraordinary hydrogenation-dechlorination performance, and for chlorophenol dechlorination, reaction condition is more gentle, and do not add any inorganic or organic additive in reaction system, catalyst can reuse.
Description
Technical field
The present invention relates to the method for magnetic carbon material load metallic catalyst and the dechlorination of catalysis chlorophenol thereof, belong to water treatment and water pollutions processing technology field.
Background technology
Chlorobenzene phenol organic compound is the very important industrial chemicals of a class, is widely used in the production of dyestuff, anticorrisive agent, herbicide and agrochemical.This kind of compound chemistry stability is strong, and be difficult to biodegradation in the environment, a large amount of uses in industrial and agricultural production cause severe contamination to environment.Therefore, develop new organic polluting water processing method, research degradation mechanism, to preserving the ecological environment, maintaining the sound development of national economy and society, having important practical significance.
Catalytic hydrogenation and dechlorination technology is considered to be the most effective way addressed this problem.Catalytic hydrogenation and dechlorination comes into one's own in the environmental pollution eliminating Substituted Chloro-phenols And Their gradually as a kind of simple, effective dechlorination method and technology.This method does not generally need higher pressure and temperature, usually just complete dechlorination can be realized at ambient pressure, having the feature of low waste discharge, is the green catalysis process that Atom economy is high, meets the requirement that current environmental pollution wastewater treatment process also wants " green ".The most frequently used metal active constituent of catalyst is Ni, Pd, Rh, Pt etc.
But, the HCl of the high concentration produced in existing catalysis chlorophenol hydrogenation-dechlorination process can on the activated centre of catalyst strong adsorption, suppress absorption and the activation of reaction substrate and hydrogen, thus cause catalyst poisoning inactivation.Current most research system all needs to add a large amount of alkali simultaneously and suppresses catalyst poisoning as NaOH, triethylamine etc. as additive, thus there is following problem: one is add a large amount of inorganic and organic bases can increase secondary pollution; Two is can react with the HCl that produces in degradation process add the alkali such as NaOH in reaction system after to generate salt NaCl, and NaCl can be adsorbed in the duct of carrier equally or cover catalyst surface, thus hinders organochlorine for thing and H
2absorption and activation, can catalysqt deactivation be caused.Modify and modification the carrying out of catalyst carrier, making catalyst activity metal and carrier have stronger interaction is conventional can effectively suppress one of approach of HCl adverse effect.Such as, after the people such as Takehira find the MCM-41 supported active metals after Al modifies, catalytic activity is significantly improved, and is conducive to aromatic hydrocarbons activation (AppliedCatalysisB:Environmental, 66 (2006) 151).Chinese patent (CN101565356A) adopts prepares mesoporous carbon-silica composite load P d catalytic hydrogenation and dechlorination chloro organic cpd, can realize efficient dechlorination at low temperatures, but this system needs to add a large amount of auxiliary agent triethylamines.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of magnetic carbon material load metallic catalyst.
Magnetic carbon material load metallic catalyst of the present invention, it is load Fe on the carbon material
3o
4with the compound that active metallic element obtains; Wherein, described material with carbon element is active carbon, CNT or Graphene, described active metallic element be in platinum, palladium and rhodium one or both
In order to obtain the magnetic carbon material load metallic catalyst of better effects if, preferably material with carbon element: Fe in mass ratio
3o
4middle Fe element: active metallic element=1 ~ 5:2 ~ 4:0.05 ~ 0.18; More preferably material with carbon element: Fe in mass ratio
3o
4middle Fe element: active metallic element=1:3 ~ 3.6:0.1 ~ 0.18.
Second technical problem to be solved by this invention is to provide the preparation method of magnetic carbon material load metallic catalyst of the present invention, comprises the steps:
A, get ferrous salt and add in deionized water, add material with carbon element after dissolving, ultrasonic wave is uniformly dispersed, and obtains solution A;
Wherein, described material with carbon element active carbon, CNT or Graphene; In material with carbon element and ferrous salt, the mass ratio of iron is 1 ~ 5:2 ~ 4;
B, add in deionized water by carried metal class material, then add NaOH, ultrasonic wave is uniformly dispersed, and obtains mixture B;
Wherein, in carried metal class material, in metallic element and step a, the mass ratio of material with carbon element is 0.05 ~ 0.18:1 ~ 5; The mass ratio of carried metal class material and NaOH is 1 ~ 5:40; Described carried metal class material is one or both in the nitrate of chloroplatinic acid, chloropalladite, the chloride of palladium, the chloride of platinum, the chloride of rhodium, the nitrate of palladium, the nitrate of platinum and rhodium;
C, to be mixed with solution A by mixture B, stir and obtain black precipitate, adopt magnet black precipitate to be adsorbed, respectively with water and ethanol washing black precipitate, vacuum drying, obtains magnetic carbon material load metallic catalyst.
In order to obtain the better catalyst of performance, ferrous salt described in preferred steps a is ferrous sulfate, frerrous chloride, green vitriol, six nitric hydrates ferrous irons, four hydration ferrous acetate or Iron dichloride tetrahydrates.
In order to make water and ferrous salt reach a rational ratio, the solid-liquid ratio of ferrous salt described in preferred steps a and deionized water is 0.6 ~ 1:12 ~ 18g/mL, and more preferably the solid-liquid ratio of ferrous salt and deionized water is 0.8:15g/mL.
In order to obtain the better magnetic carbon material load metallic catalyst of the present invention of performance, in material with carbon element described in preferred steps a and ferrous salt, the mass ratio of iron is 1:3 ~ 3.6.
In order to make water and carried metal class material reach a rational proportioning, in preferred steps b, the solid-liquid ratio of carried metal class material and deionized water is 3:500 ~ 1500g/mL; More preferably the solid-liquid ratio of carried metal class material and deionized water is 3:700g/mL;
In order to obtain the better magnetic carbon material load metallic catalyst of the present invention of performance, in preferred steps b, in carried metal class material, in metallic element and step a, the mass ratio of material with carbon element is 0.1 ~ 0.18:1;
Further, the mass ratio of the class material of carried metal described in preferred steps b and NaOH is 3:40.
3rd technical problem to be solved by this invention is to provide the method for the magnetic carbon material load metallic catalyst catalysis chlorophenol dechlorination adopting the present invention to obtain.
The method of chlorophenol dechlorination, carry out as follows: get the magnetic carbon material load metallic catalyst that the present invention obtains and add in the chlorophenol aqueous solution, the mass ratio of magnetic carbon material load metallic catalyst and chlorophenol is 5:7 ~ 21, pass into hydrogen, stirring reaction at temperature is 25 ~ 40 DEG C, react complete, after cooling, take out reactant liquor.
Further, preferred described chlorophenol is monochloro substituting phenol, dichloro-phenol or trichlorophenol, 2,4,6,-T; The mass ratio of preferred described magnetic carbon material load catalyst and chlorophenol is 5:12.5.
Further, the concentration of the aqueous solution of preferred described chlorophenol is 1 ~ 3g/L.
Further, pass into hydrogen preferably, Hydrogen Vapor Pressure is 1atm; The speed of preferred described stirring is 800 ~ 1200rpm; The reaction time of described chlorophenol dechlorination reaction is 1 ~ 4h.
The beneficial effect that the present invention has:
1, one-step method is adopted to prepare one or both active metals in the carrier loaded palladium of magnetic carbon Material cladding, platinum and rhodium, this catalyst is in preparation process, by solution A and mixture B are mixed, utilize ferrous ion and redox reaction between palladium, platinum or rhodium ion, while formation magnetic particle, make palladium, platinum or rhodium ion be reduced to metal, eliminate extra reduction step; Simplify the preparation flow of catalyst.Such catalyst p-Chlorophenic acid thing has extraordinary catalysis dechlorination performance, enables chlorophenol catalytic degradation completely.
2, reaction condition is more gentle, at normal temperatures and pressures can the complete dechlorination of p-Chlorophenic acid.Catalyst stability is good, and reactant concentration is high.The reactant concentration of such as bibliographical information is generally at 0.1g/L, and with catalyst prepared by the inventive method, reactant concentration can reach 3.0g/L.
3, do not add any inorganic or organic additive in dechlorination reaction system of the present invention, this makes the isolated or purified process of product greatly simplify, and production cost reduces.
4, Fe is had in magnetic carbon material load metallic catalyst of the present invention
3o
4there is magnetic, after having reacted, can easily catalyst be separated with reactant liquor by magnet, easy and simple to handle, avoid high speed centrifugation and complicated post-processing step.
Detailed description of the invention
First technical problem to be solved by this invention is to provide a kind of magnetic carbon material load metallic catalyst.
Magnetic carbon material load metallic catalyst is load Fe on the carbon material
3o
4with the compound that active metallic element obtains; Wherein, described material with carbon element is active carbon, CNT or Graphene, and described active metallic element is at least one in platinum, palladium and rhodium.
Further, in order to obtain performance better magnetic carbon material load metallic catalyst, preferably material with carbon element: Fe in mass ratio
3o
4middle Fe element: active metallic element=1 ~ 5:2 ~ 4:0.05 ~ 0.18; More preferably material with carbon element: Fe in mass ratio
3o
4middle Fe element: active metallic element=1:3 ~ 3.6:0.1 ~ 0.18.
Second technical problem to be solved by this invention is to provide the preparation method of magnetic carbon material load metallic catalyst of the present invention.
The preparation method of magnetic carbon material load metallic catalyst of the present invention, comprises the steps:
A, get ferrous salt and add in deionized water, add material with carbon element after dissolving, ultrasonic wave is uniformly dispersed, and obtains solution A;
Wherein, described material with carbon element active carbon, CNT or Graphene; In material with carbon element and ferrous salt, the mass ratio of iron is 1 ~ 5:2 ~ 4;
B, add in deionized water by carried metal class material, then add NaOH, ultrasonic wave is uniformly dispersed, and obtains mixture B;
Wherein, in carried metal class material, in metallic element and step a, the mass ratio of material with carbon element is 0.05 ~ 0.18:1 ~ 5, and the mass ratio of carried metal class material and NaOH is 1 ~ 5:40;
Described carried metal class material is one or both in the nitrate of chloroplatinic acid, chloropalladite, the chloride of palladium, the chloride of platinum, the chloride of rhodium, the nitrate of palladium, the nitrate of platinum and rhodium;
C, to be mixed with solution A by mixture B, stir and obtain black precipitate, adopt magnet black precipitate to be adsorbed, respectively with water and ethanol washing black precipitate, vacuum drying, obtains magnetic carbon material load metallic catalyst.
In order to make the magnetic of magnetic carbon material load metallic catalyst of the present invention better, preferred described ferrous salt is ferrous sulfate, frerrous chloride, green vitriol, six nitric hydrates ferrous irons, four hydration ferrous acetate or Iron dichloride tetrahydrates.
In order to fully be uniformly dispersed, do not waste deionized water again, the solid-liquid ratio of ferrous salt described in preferred steps a and deionized water is 0.6 ~ 1:12 ~ 18g/mL, and more preferably the solid-liquid ratio of ferrous salt and deionized water is 0.8:15g/mL.
In order to reach a good dispersion effect, in preferred steps a, ultrasonic wave dispersion adopts 300W ultrasonic wave dispersion 30min.
In order to obtain catalyst of good performance, in material with carbon element described in preferred steps a and ferrous salt, the mass ratio of iron is 1:3 ~ 3.6.
In order to fully be uniformly dispersed, do not waste deionized water again, in preferred steps b, the solid-liquid ratio of carried metal class material and deionized water is 3:500 ~ 1500g/mL; More preferably the solid-liquid ratio of carried metal class material and deionized water is 3:700g/mL.
In order to obtain catalyst of good performance, in preferred steps b, in carried metal class material, in metallic element and step a, the mass ratio of material with carbon element is 0.1 ~ 0.18:1.
Further, the mass ratio of the class material of carried metal described in preferred steps b and NaOH is 3:40.
In order to reach a good dispersion effect, in step b, ultrasonic wave dispersion adopts 300W ultrasonic wave dispersion 30min.
Stirring the time obtaining black precipitate in step c is generally 4 ~ 12h.
Further, adopt water and ethanol washing in preferred steps c respectively, washing times is respectively 3 times; The temperature of described drying is 50 ~ 70 DEG C, and the temperature of preferred described drying is 60 DEG C.
3rd technical problem to be solved by this invention is to provide the method for chlorophenol dechlorination.
The method of chlorophenol dechlorination, operating procedure is as follows: get the magnetic carbon material load metallic catalyst that the present invention obtains and add in the chlorophenol aqueous solution, the mass ratio of magnetic carbon material load metallic catalyst and chlorophenol is 5:7 ~ 21, pass into hydrogen, stirring reaction at temperature is 25 ~ 40 DEG C, react complete, after cooling, take out reactant liquor.
Wherein said chlorophenol comprises monochloro substituting phenol, dichloro-phenol and trichlorophenol, 2,4,6,-T.The concentration of the aqueous solution of chlorophenol is 1 ~ 3g/L.
Further, the mass ratio of preferred described magnetic carbon material load catalyst and chlorophenol is 5:12.5.
The present invention can react under Hydrogen Vapor Pressure is 1atm.
Further, the speed of preferred described stirring is 800 ~ 1200rpm.
Further, the reaction time of chlorophenol dechlorination reaction is 1 ~ 4h.
Whether chlorophenol dechlorination reaction is complete can pass through line sampling mode, detects with gas chromatographic analysis.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
The preparation of embodiment 1 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
The ferrous sulfate of 0.8g is added in the deionized water of 15mL, makes it fully dissolve, then add 0.1g Graphene (A).25 DEG C of ultrasonic wave process 30min, obtain solution A;
Added by 30mg sodium chloropalladite in 7mL deionized water, after fully dissolving, add the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Add in solution A by mixture B, stirring at room temperature 8 hours, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic graphene loaded palladium catalyst;
5.0mg catalyst being added 5mL4-chlorophenol concentration is in the aqueous solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 1h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 100%.
The preparation of embodiment 2 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the ferrous sulfate of 0.8g, make it fully dissolve, then add 0.1g CNT, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
30mg sodium chloropalladite is added in 7mL deionized water, after fully dissolving, adds the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Mixture B is added in solution A, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic carbon nano-tube carried metal palladium catalyst;
5.0mg catalyst being added 5mL4-chlorophenol concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 1.5h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 100%.
The preparation of embodiment 3 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the ferrous sulfate of 0.8g, make it fully dissolve, then add 0.1g active carbon, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
Added by 30mg sodium chloropalladite in 7mL deionized water, after fully dissolving, add the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Mixture B is added in solution A, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic active carbon carried metal palladium catalyst;
It is in the solution of 2.5g/L that 5.0mg magnetic active carbon carried metal palladium catalyst is added 5mL4-chlorophenol concentration, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 2h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 100%.
The preparation of embodiment 4 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the ferrous nitrate of 0.8g, make it fully dissolve, then add 0.4g Graphene, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
30mg sodium chloropalladite is added in 7mL deionized water, after fully dissolving, adds the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Add in solution A by mixture B, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic graphene loaded palladium catalyst;
5.0mg catalyst being added 5mL4-chlorophenol concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 4h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 82%.
The preparation of embodiment 5 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the frerrous chloride of 0.8g, make it fully dissolve, then add 0.1g Graphene, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
15mg sodium chloropalladite is added in 7mL deionized water, after fully dissolving, adds the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Add in solution A by mixture B, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic graphene loaded palladium catalyst;
5.0mg catalyst being added 5mL4-chlorophenol concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 2h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 62%.
The preparation of embodiment 6 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the ferrous sulfate of 0.8g, make it fully dissolve, then add 0.1g Graphene, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
Added in 7mL deionized water by 30mg palladium bichloride, add the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Add in solution A by mixture B, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic graphene loaded palladium catalyst;
5.0mg catalyst being added 5mL4-chlorophenol concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 2h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 98%.
The preparation of embodiment 7 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the ferrous sulfate of 0.8g, make it fully dissolve, then add 0.1g Graphene, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
Added in 7mL deionized water by 30mg chloroplatinic acid, add the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Add in solution A by mixture B, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, catalyst ethanol is washed 3 times, 60 DEG C of vacuum drying 12h, obtain magnetic graphene load platinum catalyst;
5.0mg catalyst being added 5mL4-chlorophenol concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 3h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 99%.
The method of the magnetic graphene loaded palladium catalyst catalysis 4-chlorophenol dechlorination that embodiment 8 adopts embodiment 1 obtained
It is in the solution of 1.0g/L that obtained magnetic graphene loaded palladium catalyst 5.0mg in embodiment 1 is added 5mL4-chlorophenol concentration, and pass into hydrogen, Hydrogen Vapor Pressure is 1atm, reacts 0.5h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 100%.
The method of the magnetic graphene loaded palladium catalyst catalysis 4-chlorophenol dechlorination that embodiment 9 adopts embodiment 1 obtained
It is in the solution of 2.5g/L that obtained magnetic graphene loaded palladium catalyst 10.0mg in embodiment 1 is added 5mL4-chlorophenol concentration, and pass into hydrogen, Hydrogen Vapor Pressure is 1atm, reacts 0.5h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 99%.
The method of the magnetic graphene loaded palladium catalyst catalysis 2-chlorophenol dechlorination that embodiment 10 adopts embodiment 1 obtained
It is in the solution of 2.5g/L that obtained magnetic graphene loaded palladium catalyst 5.0mg in embodiment 1 is added 5mL2-chlorophenol concentration, and pass into hydrogen, Hydrogen Vapor Pressure is 1atm, reacts 1h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 2-chlorophenol is 100%.
The method of magnetic graphene loaded palladium catalyst catalysis 2, the 4-chlorophenesic acid dechlorination that embodiment 11 adopts embodiment 1 obtained
Obtained magnetic graphene loaded palladium catalyst 5.0mg in embodiment 1 is added 5mL2, and 4-chlorophenesic acid concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 2h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 2,4-chlorophenesic acid is 96%.
The method of magnetic graphene loaded palladium catalyst catalysis 2, the 6-chlorophenesic acid dechlorination that embodiment 12 adopts embodiment 1 obtained
Obtained magnetic graphene loaded palladium catalyst 5.0mg in embodiment 1 is added 5mL2, and 6-chlorophenesic acid concentration is in the solution of 2.5g/L, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 2h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 2,6-chlorophenesic acid is 98%.
The preparation of embodiment 13 magnetic carbon material load metallic catalyst and adopt the method for this catalyst 4-chlorophenol dechlorination
Add in the deionized water of 15mL by the ferrous sulfate of 0.8g, make it fully dissolve, then add 0.1g Graphene, 25 DEG C of ultrasonic wave process 30min, obtain solution A;
Add in 7mL deionized water by 15mg sodium chloropalladite and 15mg chloroplatinic acid, after fully dissolving, add the NaOH of 0.4g, 25 DEG C of ultrasonic wave process 30min, obtain mixture B;
Mixture B is added in solution A, stirring at room temperature 8h, adopt magnet by catalyst sucking-off, after catalyzer with water being washed 3 times, then wash 3 times with ethanol, 60 DEG C of vacuum drying 12h, obtain magnetic graphene supported palladium platinum catalyst;
It is in the solution of 2.5g/L that 5.0mg magnetic graphene supported palladium platinum catalyst is added 5mL4-chlorophenol concentration, passes into hydrogen, and Hydrogen Vapor Pressure is 1atm, reacts 0.5h, take out reactant liquor after cooling under room temperature;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 100%.
The method of the magnetic graphene supported palladium platinum catalyst catalysis 4-chlorophenol dechlorination that embodiment 14 adopts embodiment 13 obtained
Take out by solution reacted in embodiment 13 and analyze, solid catalyst is still retained in reactor, adds new 4-chlorophenol 5mL, 4-chlorophenol concentration is 2.5g/L, passes into hydrogen, reaction temperature 25 DEG C, Hydrogen Vapor Pressure is react 1h under 1atm, takes out reactant liquor after cooling;
Reactant liquor is through gas chromatographic analysis, and the dechlorination conversion ratio of 4-chlorophenol is 99%.
Claims (6)
1. the preparation method of magnetic carbon material load metallic catalyst, is characterized in that: comprise the steps:
A, get ferrous salt and add in deionized water, add material with carbon element after dissolving, ultrasonic wave is uniformly dispersed, and obtains solution A;
Wherein, described material with carbon element is active carbon, CNT or Graphene; In material with carbon element and ferrous salt, the mass ratio of iron is 1 ~ 5:2 ~ 4;
B, add in deionized water by carried metal class material, then add NaOH, ultrasonic wave is uniformly dispersed, and obtains mixture B;
Wherein, in carried metal class material, in metallic element and step a, the mass ratio of material with carbon element is 0.05 ~ 0.18:1 ~ 5; The mass ratio of carried metal class material and NaOH is 1 ~ 5:40; Described carried metal class material is one or both in the nitrate of chloroplatinic acid, chloropalladite, the chloride of palladium, the chloride of platinum, the chloride of rhodium, the nitrate of palladium, the nitrate of platinum and rhodium;
C, to be mixed with solution A by mixture B, stir and obtain black precipitate, adopt magnet black precipitate to be adsorbed, respectively with water and ethanol washing black precipitate, vacuum drying, obtains magnetic carbon material load metallic catalyst.
2. the preparation method of magnetic carbon material load metallic catalyst according to claim 1, is characterized in that: ferrous salt described in step a is ferrous sulfate, frerrous chloride, green vitriol, six nitric hydrates ferrous irons, four hydration ferrous acetate or Iron dichloride tetrahydrates.
3. the preparation method of magnetic carbon material load metallic catalyst according to claim 1, is characterized in that: the solid-liquid ratio of ferrous salt described in step a and deionized water is 0.6 ~ 1:12 ~ 18g/mL; In material with carbon element described in step a and ferrous salt, the mass ratio of iron is 1:3 ~ 3.6.
4. the preparation method of magnetic carbon material load metallic catalyst according to claim 3, is characterized in that: the solid-liquid ratio of ferrous salt described in step a and deionized water is 0.8:15g/mL.
5. the preparation method of the magnetic carbon material load metallic catalyst according to any one of Claims 1 to 4, is characterized in that: in step b, the solid-liquid ratio of carried metal class material and deionized water is 3:500 ~ 1500g/mL; In step b, in carried metal class material, in metallic element and step a, the mass ratio of material with carbon element is 0.1 ~ 0.18:1; The mass ratio of the class material of carried metal described in step b and NaOH is 3:40.
6. the preparation method of magnetic carbon material load metallic catalyst according to claim 5, is characterized in that: in step b, the solid-liquid ratio of carried metal class material and deionized water is 3:700g/mL.
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| CN104841455A (en) * | 2015-04-24 | 2015-08-19 | 华东理工大学 | Preparation method and application of platinum-loaded ferriferrous oxide catalyst |
| CN104891635B (en) * | 2015-05-12 | 2017-01-18 | 浙江清华长三角研究院 | Wastewater treatment method realized via reductive dehalogenation of iron powder under Pd catalysis |
| CN105148937A (en) * | 2015-08-07 | 2015-12-16 | 江苏大学 | Magnetic graphene-loaded palladium nano-composite catalyst and preparation method thereof |
| CN105461575B (en) * | 2015-12-31 | 2018-07-03 | 江苏尚莱特医药化工材料有限公司 | The preparation method of 4,6- diamino resorcins or its salt |
| CN106053581B (en) * | 2016-05-18 | 2018-07-27 | 南京师范大学 | One kind being based on PEDOT/g-C3N4The method of electrode detection o-chlorphenol |
| CN107051552B (en) * | 2017-05-22 | 2019-09-27 | 安徽大学 | Preparation of magnetic carbon nanotube-loaded rhodium catalyst and application of catalyst in selective hydrogenation of nitrile rubber |
| CN107486219A (en) * | 2017-08-22 | 2017-12-19 | 兰州大学 | A kind of preparation method and applications of palladium carried magnetic carbon fiber catalyst |
| CN107774293B (en) * | 2017-10-20 | 2020-06-09 | 四川理工学院 | N-doped graphene-loaded Pd catalyst, and preparation method and application thereof |
| CN109848435A (en) * | 2019-01-25 | 2019-06-07 | 浙江工业大学 | Nano-scale Pd/Fe/MWCNTs/Fe3O4Method for preparing composite material |
| CN112080280B (en) * | 2019-06-13 | 2022-01-11 | 天津大学 | Application of modified charcoal material in degrading dichloro-diphenyl-trichloroethane |
| CN110385138B (en) * | 2019-08-14 | 2022-02-01 | 重庆工商大学 | Preparation method of rhodium-loaded porous tubular carbon nitride photocatalyst applied to chlorophenol hydrodechlorination catalytic reaction |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
| CN113813958B (en) * | 2020-06-19 | 2023-07-25 | 台州学院 | Palladium-platinum supported metal oxide catalyst, preparation method and application thereof, working electrode and battery system |
| CN115282959B (en) * | 2022-07-26 | 2024-02-27 | 万华化学集团股份有限公司 | Ru-Nb-Ce trimetallic catalyst loaded by carbon nano tube, method and application thereof in preparing coconut aldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921143A (en) * | 2012-10-30 | 2013-02-13 | 中国科学院烟台海岸带研究所 | Method for efficiently degrading chlorinated phenolic compound |
| CN103111306A (en) * | 2013-02-07 | 2013-05-22 | 浙江工业大学 | Magnetic load type nanometer palladium/iron grain catalyst and preparation method and application thereof |
-
2014
- 2014-07-01 CN CN201410308813.7A patent/CN104028283B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921143A (en) * | 2012-10-30 | 2013-02-13 | 中国科学院烟台海岸带研究所 | Method for efficiently degrading chlorinated phenolic compound |
| CN103111306A (en) * | 2013-02-07 | 2013-05-22 | 浙江工业大学 | Magnetic load type nanometer palladium/iron grain catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Effective hydrodechlorination of 4-chlorophenol catalysed by magnetic palladium/reduced graphene oxide under mild conditions;Yanlin，et al;《RSC Advances》;20140416;第4卷(第48期);第25441页2.2、2.4节 * |
| Pd负载磁性多壁碳纳米管催化对氯苯酚脱氯的研究;邓红英等;《应用化工》;20131130;第42卷(第11期);文章摘要，第1957页1、2.2节 * |
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