CN104307578B - Ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts - Google Patents
Ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts Download PDFInfo
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Abstract
Ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts, carries out NaBH under existing at ceramic caltalyst4Reduction paranitrophenol after completion of the reaction, reclaims ceramic caltalyst；Then in reaction system, add reducing agent make the α Fe in ceramic monolith2O3It is reduced to ferromagnetic material；Under additional the action of a magnetic field, by the ceramic caltalyst sucking-off in solution, finally it is oxidized to initial ceramic caltalyst, recycled for multiple times by having magnetic ceramic catalyst.The inventive method is simple, the response rate is high, cost is low and environment friendly and pollution-free produce raw.This ceramic caltalyst can make filter membrane catalyst simultaneously, is contained between suitable filter by this filter membrane, makes reactant liquor pass through slowly the filter membrane of caltalyst, and reactant liquor is also slowly by catalysis.This filter membrane catalytic effect is obvious, and simple to operate, cost is low, it is possible to this filter membrane is applied to the process etc. of sewage, waste water.
Description
Technical field
The present invention relates to noble metal catalyst reclaim, especially with respect to ceramic catalyst sodium borohydride reduction paranitrophenol react in rejuvenation method.
Background technology
Noble metal is widely used in the manufacture of catalyst in recent years, in a lot of purposes, noble metal catalyst can provide the catalysis activity of necessity, selectivity and stability for reaction, but wherein platinum group metal picture (Pt, Pd, Rh) can be widely used in the reactions such as hydrogenation, oxidation, dehydrogenation, hydrogenolysis, ammonia synthesis, methanol-fueled CLC, is wherein most widely used with Pt and Rh；Their d electron orbit is all unfilled, the easy adsorption reaction thing in surface, is beneficial in the middle of formation " reactive compound ", has higher catalysis activity, also there is high temperature resistant, antioxidation, the comprehensive good characteristic such as corrosion-resistant simultaneously, become most important catalyst material [1].But owing to noble metal reserves are limited, yield poorly, price high, and catalyst needs the initial investment of great number, therefore effectively reclaims noble metal catalyst extremely important [2].Metal nano catalyst granules is little, and surface can be high, it is easy to reunites；Although catalyst being loaded to carrier surface can play physical barrier effect, the process that can prevent granule catalysis in reactant liquor to a certain extent is reunited, but how effectively to reclaim noble metal catalyst and to increase its stability recycled be problem demanding prompt solution.([1] Peng Hongjian, Xie Youqing, Tao Huijin. the electronic structure of metal R and physical property [J]. material Leader, 2005,19 (9): 121 one 123. [2] yellow successions. reclaim from useless carried catalyst and refine high-purity platinum [J]. regenerated resources research, 2000 (3): 24-25.).
At present, the method reclaiming the noble metal catalysts such as platinum has much, totally can be summarized as following 5 kinds [3]: 1. carrier dissolution method, 2. Selective dissolution method, 3. complete molten method, 4. pyrometallurgical smelting, 5. combustion method.The most long flow path of these methods, cost are high, the response rate is low and can produce a large amount of waste liquid in removal process.([3] Yang Zhiping, Li Yonghua, Tang Baobin. from dead catalyst, reclaim the technical study [J] that platinum comes. hydrometallurgy, 1999 (2): 9-13.).
In view of the above problems, instant invention overcomes the defect existed in above-mentioned all technology, it is provided that a kind of do not have the recovery method that waste liquid produces and environmental protection is very low cost.
Summary of the invention
Solve the technical problem that:It is an object of the invention to provide a kind of ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts, effectively reclaim the caltalyst in reaction.
Technical scheme:Ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts, carries out NaBH under existing at ceramic caltalyst4Reduction paranitrophenol after completion of the reaction, reclaims ceramic caltalyst；Then in reaction system, add reducing agent make the α Fe in ceramic monolith2O3It is reduced to ferromagnetic material；Under additional the action of a magnetic field, by the ceramic caltalyst sucking-off in solution, finally it is oxidized to initial ceramic caltalyst, recycled for multiple times by having magnetic ceramic catalyst.
Described ceramic caltalyst includes the catalyst of ceramic monolith and carrier surface.
A kind of material in described ceramic monolith includes α Fe2O3Nanofiber.
Described ceramic monolith includes redox graphene.
α Fe in described ceramic monolith2O3It is 20-1 with the mass ratio of redox graphene.
The catalyst of described carrier surface is noble metal nano particles Pt, Pd, Rh or Ag.
In described ceramic monolith, carrier is 100-1 with the mass ratio of noble metal.
In described reaction mixture, paranitrophenol and NaBH4Its mass ratio is 200-1.
In described reaction mixture, the mass ratio of paranitrophenol and ceramic caltalyst is 1-10.
Described method for oxidation is 200-300 DEG C of heating and logical oxygen.
By the metal-oxide α Fe in ceramic monolith in this experiment2O3It is reduced to magnetisable material Fe3O4Process in without influence on the size of Pt nano-particle and catalytic effect；The reducing agent used is NaBH4, because the catalyst that model reaction uses is NaBH4, reuse NaBH4Do not have impurity to introduce as reducing agent.
Beneficial effect:The inventive method is simple, the response rate is high, cost is low and environment friendly and pollution-free produce raw.This ceramic caltalyst can make filter membrane catalyst simultaneously, is contained between suitable filter by this filter membrane, makes reactant liquor pass through slowly the filter membrane of caltalyst, and reactant liquor is also slowly by catalysis.This filter membrane catalytic effect is obvious, and simple to operate, cost is low, it is possible to this filter membrane is applied to the process etc. of sewage, waste water.
Accompanying drawing explanation
Fig. 1 is that catalyst reclaims schematic diagram；
Fig. 2 is Fe3O4Hysteresis curve figure；
Fig. 3 is the TEM collection of illustrative plates of ceramic caltalyst；
Fig. 4 is the catalytic rate collection of illustrative plates of ceramic caltalyst circulation catalysis paranitrophenol, and slope of a curve represents reaction rate constant.
Detailed description of the invention
The present invention can be widely applied to the NaBH of ceramic caltalyst4Reduction paranitrophenol model reaction, the preferred Pt of noble metal catalyst therein, Pd, Ru, Au and Ag etc., particularly Pt catalytic reaction.
Ceramic monolith includes α Fe2O3, it is because α Fe on the one hand2O3Ferromagnetic Fe can be reduced under the effect of reducing agent3O4, and then ceramic caltalyst is recycled；It is because α Fe on the other hand2O3Ceramic nanofibers has bigger specific surface area and certain pore structure, is conducive to flowing and the catalyst load on its surface of fluid, it is often more important that α Fe2O3Ceramic nano quasiconductor is also good photocatalyst, visible ray and ultraviolet light are all demonstrated by good photoelectric respone, the utilization rate of sunlight is high, because light can electronics in vitalizing semiconductor, electronics is generated from valence to conduction band light induced electron, and valence band produces corresponding photohole, electronics and hole are diffused into semiconductor surface respectively, react from different reaction objects on surface.Light induced electron has reproducibility, and hole has oxidisability, and they all can carry out the reaction of oneself；But the electronics in conduction band is unstable in the process be diffused into semiconductor surface, it is easy to the hole-recombination in valence band, cause that the efficiency of light induced electron is very low.But Graphene has the physical property of many excellences, such as electrical properties, optical property, at room temperature electron mobility is high for it, heat conductivity is good, specific surface area is big, and Graphene also has certain catalytic performance, bi-material is combined and can form very excellent catalyst carrier and composite photo-catalyst.
Metal-oxide (as: Fe2O3) and noble metal (as: Pt) having strong synergism, metallic particles loads to metal oxide surface, catalytic performance (includes light-catalyzed reaction performance) and is significantly improved.Therefore, after metallic particles loads to metal-oxide and graphene composite carrier surface, the catalysis activity of three is substantially better than the catalytic effect of single metallic particles.
The present invention does not limit following example in without departing from situation described above.Following instance is using precious metals pt as catalysts.By infusion process, Pt being loaded to carrier surface, wherein in ceramic monolith, the mass ratio of carrier and noble metal is 100-1, with 10-50 for optimum.Hereinafter reaction is applicable not only to NaBH4The model reaction of reduction paranitrophenol, the reaction of other precious metal catalysts is all applicable.
Embodiment 1
In the reaction with Pt for catalysts, adopt NaBH4Reduction paranitrophenol carrys out qualitative assessment carrier (α Fe as model reaction2O3/ RGO) above the catalysis of Pt recycling is active.Paranitrophenol and NaBH before using every time4Aqueous solution needs fresh preparation, simultaneously NaBH4Solution need to be prepared in ice bath.By paranitrophenol and NaBH4Mixing, then ceramic caltalyst adds in reaction solution.In reaction mixture, NaBH4Being 1:1 with its mass ratio of paranitrophenol, the mass ratio of paranitrophenol and ceramic caltalyst is 10:1.Then under the effect of externally-applied magnetic field, ceramic caltalyst is removed, washes with water clean, finally by have magnetic ceramic caltalyst be oxidized to initial ceramic caltalyst again with.Described method for oxidation is 200-300 DEG C of heating and logical oxygen.
NaBH4The stopping of the mould reaction of reduction paranitrophenol-start again, adds same NaBH again by the ceramic caltalyst after oxidation4In the model reaction of reduction paranitrophenol, again carry out NaBH4Reduction paranitrophenol reaction；Reaction terminates to add in backward reactor reducing agent, makes the α Fe in ceramic monolith2O3It is reduced to ferromagnetic material；Under additional the action of a magnetic field, by the ceramic caltalyst sucking-off solution outside reactor, finally the magnetic ceramic caltalyst of tool is oxidized to initial ceramic caltalyst and again recycles.
As above circulation catalysis 5 times, detects the catalytic effect (such as Fig. 4) repeatedly circulated by uv-vis spectra.
Embodiment 2
In the reaction with Pt for catalysts, adopt NaBH4Reduction paranitrophenol carrys out qualitative assessment carrier (α Fe as model reaction2O3/ RGO) above the catalysis of Pt recycling is active.Paranitrophenol and NaBH before using every time4Aqueous solution needs fresh preparation, simultaneously NaBH4Solution need to be prepared in ice bath.By paranitrophenol and NaBH4Mixing, then ceramic caltalyst adds in reaction solution.In reaction mixture, NaBH4Being 50:1 with its mass ratio of paranitrophenol, the mass ratio of paranitrophenol and ceramic caltalyst is 1:1.Then under the effect of externally-applied magnetic field, ceramic caltalyst is removed, washes with water clean, finally by have magnetic ceramic caltalyst be oxidized to initial ceramic caltalyst again with.Described method for oxidation is 200-300 DEG C of heating and logical oxygen.
NaBH4The stopping of the mould reaction of reduction paranitrophenol-start again, adds same NaBH again by the ceramic caltalyst after oxidation4In the model reaction of reduction paranitrophenol, again carry out NaBH4Reduction paranitrophenol reaction；Reaction terminates to add in backward reactor reducing agent, makes the α Fe in ceramic monolith2O3It is reduced to ferromagnetic material；Under additional the action of a magnetic field, by the ceramic caltalyst sucking-off solution outside reactor, finally the magnetic ceramic caltalyst of tool is oxidized to initial ceramic caltalyst and again recycles.
As above circulation catalysis 5 times, detects the catalytic effect repeatedly circulated by uv-vis spectra.
Embodiment 3
In the reaction with Pt for catalysts, adopt NaBH4Reduction paranitrophenol carrys out qualitative assessment carrier (α Fe as model reaction2O3/ RGO) above the catalysis of Pt recycling is active.Paranitrophenol and NaBH before using every time4Aqueous solution needs fresh preparation, simultaneously NaBH4Solution need to be prepared in ice bath.By paranitrophenol and NaBH4Mixing, then ceramic caltalyst adds in reaction solution.In reaction mixture, NaBH4Being 25:1 with its mass ratio of paranitrophenol, the mass ratio of paranitrophenol and ceramic caltalyst is 5:1.Then under the effect of externally-applied magnetic field, ceramic caltalyst is removed, washes with water clean, finally by have magnetic ceramic caltalyst be oxidized to initial ceramic caltalyst again with.Described method for oxidation is 200-300 DEG C of heating and logical oxygen.
NaBH4The stopping of the mould reaction of reduction paranitrophenol-start again, adds same NaBH again by the ceramic caltalyst after oxidation4In the model reaction of reduction paranitrophenol, again carry out NaBH4Reduction paranitrophenol reaction；Reaction terminates to add in backward reactor reducing agent, makes the α Fe in ceramic monolith2O3It is reduced to ferromagnetic material；Under additional the action of a magnetic field, by the ceramic caltalyst sucking-off solution outside reactor, the most backward ceramic caltalyst with magnetic is oxidized to initial ceramic caltalyst and again recycles.
As above circulation catalysis 5 times, detects the catalytic effect repeatedly circulated by uv-vis spectra.
Embodiment 4
In the reaction with Pt for catalysts, adopt NaBH4Reduction paranitrophenol carrys out qualitative assessment carrier (α Fe as model reaction2O3/ RGO) above the catalysis of Pt recycling is active.Paranitrophenol and NaBH before using every time4Aqueous solution needs fresh preparation, simultaneously NaBH4Solution need to be prepared in ice bath.By paranitrophenol and NaBH4Mixing, then ceramic caltalyst adds in reaction solution.In reaction mixture, NaBH4Being 200:1 with its mass ratio of paranitrophenol, the mass ratio of paranitrophenol and ceramic caltalyst is 3:1.Then under the effect of externally-applied magnetic field, ceramic caltalyst is removed, washes with water clean, finally by have magnetic ceramic caltalyst be oxidized to initial ceramic caltalyst again with.Described method for oxidation is 200-300 DEG C of heating and logical oxygen.
NaBH4The stopping of the mould reaction of reduction paranitrophenol-start again, adds same NaBH again by the ceramic caltalyst after oxidation4In the model reaction of reduction paranitrophenol, again carry out NaBH4Reduction paranitrophenol reaction；Reaction terminates to add in backward reactor reducing agent, makes the α Fe in ceramic monolith2O3It is reduced to ferromagnetic material；Under additional the action of a magnetic field, by the ceramic caltalyst sucking-off solution outside reactor, the most backward ceramic caltalyst with magnetic is oxidized to initial ceramic caltalyst and again recycles.
As above circulation catalysis 5 times, detects the catalytic effect repeatedly circulated by uv-vis spectra.
Method used according to the invention easily again with, and the activity of catalyst is basically unchanged.The catalytic effect that ceramic caltalyst repeatedly recycles is shown in Fig. 4.
Claims (1)
1. ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts, it is characterised in that in the reaction with Pt for catalysts, adopts NaBH4Reduction paranitrophenol carrys out, as model reaction, the catalysis activity that on qualitative assessment ceramic caltalyst, Pt recycles, and described ceramic caltalyst is the α Fe being loaded with Pt2O3/ RGO ceramic monolith, α Fe in described ceramic monolith2O3Being 20-1 with the mass ratio of RGO, the mass ratio of ceramic monolith and noble metal is 100-1；Paranitrophenol and NaBH before using every time4Aqueous solution needs fresh preparation, simultaneously NaBH4Solution need to be prepared in ice bath；By paranitrophenol and NaBH4Mixing, then ceramic caltalyst adds in reaction solution, in reaction mixture, NaBH4Being 200:1 with its mass ratio of paranitrophenol, the mass ratio of paranitrophenol and ceramic caltalyst is 3:1；Then under the effect of externally-applied magnetic field, ceramic caltalyst is removed, washes with water clean, finally by have magnetic ceramic caltalyst be oxidized to initial ceramic caltalyst again with, described method for oxidation is 200-300 DEG C of heating and logical oxygen.
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| CN101703936A (en) * | 2009-11-30 | 2010-05-12 | 上海交通大学 | Magnetic nano catalyst and preparation method thereof |
| CN102527437A (en) * | 2010-12-16 | 2012-07-04 | 中国科学院福建物质结构研究所 | Magnetically-separable noble metal catalyst and preparation method thereof |
| CN102847533A (en) * | 2012-10-12 | 2013-01-02 | 南京师范大学 | Microwave method for synthesizing attapulgite and palladium nanocomposite catalyst |
| CN102921422A (en) * | 2012-11-06 | 2013-02-13 | 常州大学 | Preparation of magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of composite catalyst in reduction of nitro-compounds |
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