CN105056965A - Biological carbon sphere supported FeMoO4 Fenton catalyst, preparation method and application - Google Patents
Biological carbon sphere supported FeMoO4 Fenton catalyst, preparation method and application Download PDFInfo
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- CN105056965A CN105056965A CN201510426858.9A CN201510426858A CN105056965A CN 105056965 A CN105056965 A CN 105056965A CN 201510426858 A CN201510426858 A CN 201510426858A CN 105056965 A CN105056965 A CN 105056965A
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Abstract
The invention discloses a biological carbon sphere supported FeMoO4 Fenton catalyst, a preparation method and an application. The catalyst adopts micro-spheres with a core-shell structure, the core of each micro-sphere is a biological carbon sphere obtained through yeast cell transformation, and the shell of each micro-sphere adopts a FeMoO4 layer. The cheap yeast cells are taken as sources of the biological carbon spheres, tetrahydrate ferrous chloride and dehydrate sodium molybdate are taken as main raw materials, and a biological carbon sphere supported FeMoO4 Fenton catalyst powder material with a core-shell structure is prepared through an environment-friendly reaction and generation environment; the biological carbon sphere supported FeMoO4 Fenton catalyst prepared with the method has excellent catalytic degradation performance in degradation of methylene blue simulative dyeing wastewater.
Description
Technical field
The present invention relates to molybdate field, especially relate to the ferrous Fenton catalyst of biological carbon ball load molybdic acid, preparation method and application.
Background technology
Molybdic acid ferrous iron (FeMoO
4) as a kind of important bimetallic oxide, there is excellent catalytic activity and thermoelectricity capability, be widely used in the fields such as rechargeable battery cathode material, magnetic material, catalyst.At present, it is ferrous that industry has adopted various preparation method to obtain the molybdic acid of different dimensions and size, and the representational Hu Chenguo of being exactly of most teaches project team, and successively by water heat transfer, diameter is the FeMoO of 1 micron
4hollow ball and diameter are 50 ~ 150nm, length about 2 ~ 3 microns of one dimension monocline molybdic acid ferrous iron nanometer bar materials.
Fenton (Fenton) method is a kind of advanced oxidation processes, namely utilizes iron ion and H
2o
2between chain reaction catalysis generate and there is the OH free radical of strong oxidizing property, to reach the object of oxidative degradation pollutant.The method is specially adapted to difficult for biological degradation or is difficult to the organic wastewater of chemical oxidation, is a kind of wastewater processing technology with broad prospect of application.But there is following defect in traditional F enton method: H during process high density pollution thing
2o
2consumption is large, and applicable pH range little (generally must carry out when pH<3), causes cost for wastewater treatment higher; Conventional Fenton reagent belongs to homogeneous catalysis system, and its cost recovery is higher, easily causes secondary pollution etc.In recent years, the research report much Fenton catalyst cupport being obtained support type heterogeneous Fenton catalyst at various carrier surface is emerged.Large quantity research confirms, by the suitable carrier loaded synergy realizing absorption-advanced oxidation, effectively improves the efficiency of Fenton advanced oxidation.There is at present report using materials such as resin, active carbon, CNTs as at carrier, be applied to the preparation of heterogeneous Fenton catalysis material.But these carriers generally all need the surface modification of carrier before special carrier preparation technology and load, operating procedure is complicated, has certain limitation.
In the last few years, micro Nano material based on biological cell causes the extensive concern of people in the industry, the biological carbon material wherein obtained by living beings, the role of excellent carrier can be born at numerous areas, wherein, by the representative that the carbon micron-spheres obtained after yeast cells carbonization is exactly this kind of bio-based material with carbon element, there are wide material sources, cheap, good stability and strong etc. the advantage of absorption property.But at present, there is not yet the biological carbon ball obtained by transformation into yeast cell is applied to heterogeneous Fenton catalyst cupport report as carrier.
Summary of the invention
For defect of the prior art and deficiency, the invention provides the ferrous Fenton catalyst of a kind of biological carbon ball load molybdic acid, preparation method and application, biological carbon ball load molybdic acid of the present invention ferrous Fenton catalyst powder material is made up of the ellipsoid shape micron bead with nucleocapsid structure, in nucleocapsid structure, being positioned at inner core is the biological carbon ball obtained by transformation into yeast cell, being positioned at outside shell is the ferrous layer of molybdic acid, the ferrous Fenton catalyst of biological carbon ball load molybdic acid shows excellent catalytic degradation performance in the degraded of methylene blue dye wastewater.
For achieving the above object, the technical scheme that the present invention takes is:
The ferrous Fenton catalyst of a kind of biological carbon ball load molybdic acid, this catalyst is the micron ball of nucleocapsid structure, and the core of micron ball is the biological carbon ball that transformation into yeast cell obtains, and the shell of micron ball is the ferrous layer of molybdic acid.
Concrete, described micron ball is spheroid, and the minor axis * major diameter of micron ball is 2.2 ~ 3.0 μm * 3.5 ~ 5.0 μm, and described biological carbon ball is spheroid, the minor axis * major diameter of biological carbon ball is 1.0 ~ 1.6 μm * 1.5 ~ 4.2 μm, and the thickness of the ferrous layer of described molybdic acid is 400 ~ 600nm.
Prepare a preparation method for the ferrous Fenton catalyst of described biological carbon ball load molybdic acid, the method comprises:
Step one: the yeast cells solution of activation is mixed with Iron dichloride tetrahydrate solution and stirs, in mixed liquor, the concentration of Iron dichloride tetrahydrate is 0.02 ~ 0.2mol/L, in mixed liquor, the concentration of yeast cells is 0.556 ~ 1.5mol/L, and whipping temp is 30 ~ 80 DEG C;
Step 2: add two molybdic acid hydrate sodium solutions in the mixed liquor in step one, the concentration of two molybdic acid hydrate sodium in mixed liquor is made to be 0.02 ~ 0.2mol/L, liquid is uniformly mixed to there is yellow mercury oxide at 20 ~ 60 DEG C, then that solution is still aging at 20 ~ 50 DEG C;
Step 3: calcine in protective gas environment after the precipitation drying that step 2 is obtained; sample after calcining is cooled to room temperature and namely obtains the ferrous Fenton catalyst of biological carbon ball load molybdic acid; calcining heat is 300 ~ 600 DEG C; calcination time is 2 ~ 5h, and protective gas is the mist of nitrogen, argon gas or 5% hydrogen and 95% nitrogen.
Concrete, the preparation method of described activated yeast cell solution comprises:
The consumption that dusty yeast and dispersant add 30 ~ 900L dispersant by every 500 ~ 1500g yeast is carried out the cleaning of dispersant to dusty yeast, and then the dusty yeast activator after cleaning is carried out surface active, the consumption of activator is identical with the consumption of dispersant;
Described dispersant is deionized water, and described activator is absolute ethyl alcohol.
More specifically, the drying described in step 3 be by step 2 gained be deposited in the temperature of 40 ~ 80 DEG C under carry out drying.
The ferrous Fenton catalyst of described biological carbon ball load molybdic acid is for the treatment of the application of methylene blue dye wastewater.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention is primary raw material by employing two molybdic acid hydrate sodium, Iron dichloride tetrahydrate, utilize friendly reaction and build environment, and adopt cheap yeast cells to obtain the ferrous Fenton catalysis material of biological carbon ball load molybdic acid, selection yeast cells is the carrier source of heterogeneous Fenton catalyst, utilize the functional group that its surface is abundant, realize the efficient adsorption to ferrous ion, for the ferrous hybrid material of the molybdic acid obtaining yeast cells load provides important material base;
(2) in the ferrous hybrid material preparation technology of the molybdic acid of yeast cells load, focus on the strict control to the solution concentration in course of reaction and reaction temperature, effectively reduce absorption and Coprecipitation to the impact of ferrous ion valence state and material concentration, facilitate molybdic acid ferrous iron in effective precipitation of yeast cell surface, growth and load;
(3) by by the calcination of the ferrous hybrid particulates of yeast cells load molybdic acid under suitable protective atmosphere condition, the ferrous Fenton catalyst of molybdic acid of biological carbon ball load is directly obtained.Calcination atmosphere protection suitable in this step; not only effectively realize the conversion of yeast cells to carbon micron-spheres; and to avoid in calcination process from oxygen molecule in yeast cells and reaction environment the oxidation of ferrous ion, ensure that the purity of biological carbon ball load molybdic acid ferrous Fenton catalysis material product.To sum up, had the technical guarantee of above many innovations in the present invention, prepared molybdic acid ferrous Fenton catalysis material purity is high, and impurity particle is few, and physical and chemical performance is excellent; Utilize X-ray diffraction (XRD), ESEM (SEM), the means such as elementary analysis (EDX) and Raman spectrum are studied the biological carbon ball load molybdic acid ferrous Fenton catalyst powder material that the present invention obtains, result shows, the composition of the ferrous microballoon of the molybdic acid made under these conditions is molybdic acid ferrous materia, microballoon average-size is 2.2 ~ 3.0*3.5 ~ 5.0 μm, the size of Internal biological carbon ball is about 1.0 ~ 1.6*1.5 ~ 4.2 μm, and the ferrous layer wall thickness of outer molybdic acid is about 400 ~ 600nm.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the ferrous Fenton catalyst of biological carbon ball load molybdic acid prepared by embodiment 3;
Fig. 2 is the scanning electron microscope (SEM) photograph of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3;
Fig. 3 is the scanning electron microscope (SEM) photograph of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3;
Fig. 5 is the scanning electron microscope (SEM) photograph of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3;
Fig. 6 is the energy spectrogram of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3;
Fig. 7 is the Raman spectrogram of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3;
Fig. 8 is that the ferrous Fenton catalyst of molybdic acid of biological carbon ball load prepared by embodiment 3 is to the Fenton catalytic degradation figure of methylene blue stimulated dye wastewater;
Below in conjunction with Figure of description and embodiment, the invention will be further described.
Detailed description of the invention
Technical scheme involved in the present invention and method, be not only applicable to the preparation of the ferrous Fenton catalyst of described biological carbon ball load molybdic acid, also can as basic syntheti c route, use for reference and be applied to the preparation of the carbon material supported multiple heterogeneous Fenton catalyst of other biological matter.In the preparation of the carbon material supported multiple heterogeneous Fenton catalyst of other biological matter: on the one hand, biological carbon material category is chosen as string, plant pollen, microorganism mycelia, microbial cell and cell mass etc.; The multiple Fenton catalyst that can realize load on the other hand can select ferrous sulfate, the Fenton material that frerrous chloride etc. are common, the preparation of the multiple heterogeneous Fenton catalyst that other biological matter possible is above carbon material supported, only need according to the basic characteristics of biological carbon material source and biological adsorption performance difference in preparation, and the concrete preparation condition of other Fenton catalysis materials preparation synthesis, do to adjust and can obtain based on the carbon material supported multiple heterogeneous Fenton catalyst of the basic syntheti c route multiple other biological matter in the present invention.
Reaction mechanism of the present invention is: in the preparation technology of the ferrous Fenton catalyst of biological carbon ball load molybdic acid, yeast through repeatedly washing and activation process after, first mix in system with Iron dichloride tetrahydrate, and with magnetic stirring apparatus, solution is mixed, in the process, the functional group of yeast cell surface can interact with the ferrous ion dissociated in solution, and ferrous ion is progressively adsorbed in cell surface by cell, thus defines hydration ferrous ion layer at cell surface.After with the addition of two molybdic acid hydrate sodium in system, in solution and the ferrous ion the being adsorbed in yeast cell surface molybdenum acid ion that all can dissociate with two molybdic acid hydrate sodium react, start to form molybdic acid ferrous molecules nanometer bundle in the yeast cell surface and the aqueous solution of absorption ferrous ion simultaneously.According to slaking and gathering theory, the molybdic acid ferrous iron nanometer bundle formed in system can realize the growth of particle by mutual Fast Collision.Under the condition ensureing certain reactant concentration and system temperature, the molybdic acid ferrous iron nanometer harness being incorporated into yeast cell surface has very large surface area, thus ensure that the molybdic acid ferrous molecules nanometer bundle in the efficiency that molybdic acid ferrous iron nanometer Shu Yougeng on yeast vector is high and solution carries out Collision coagulation and combines, this greatly reduces the generation of impurity in system.So in ageing process, the molybdic acid ferrous iron nanometer particle growth progressively that cell membrane is formed, the ferrous wall thickness of molybdic acid constantly increases, and finally defines the hybrid particulates of the nucleocapsid structure of yeast-molybdic acid ferrous iron.Through centrifugal; cleaning; vacuum drying obtains the molybdic acid ferrous materia of yeast cells load; this material is calcined under suitable protective atmosphere condition; the transformation into yeast cell being positioned at nucleocapsid structure inside is not only made to be biological carbon ball; and promote the ferrous particle of the outer molybdic acid of nucleocapsid structure not by with oxidation while realize crystallization, thus define the ferrous Fenton catalyst of biological carbon ball load molybdic acid.Above preparation technology can obtain the ferrous Fenton catalyst of biological carbon ball load molybdic acid through simple step, compared with traditional load technology, no longer need the surface optimization before special carrier preparation technology and load and modification, greatly reduce the preparation process of support type Fenton catalyst, preparation technology's environmental protection, has outstanding advantage.
When the ferrous Fenton catalyst application of biological carbon ball load molybdic acid is in Fenton catalytic reaction time, outer molybdic acid ferrous ion in this material nucleocapsid structure can play catalytic activity effectively, and the biological carbon ball of nucleocapsid structure inside can assist the effect playing absorption mass transfer simultaneously.Therefore, the Unique physical design of the ferrous Fenton catalyst of biological carbon ball load molybdic acid and suitable preparation condition, achieve layer materials coupling cleverly and performance superposition on functional plane in nucleocapsid structure, the synergy of absorption-advanced oxidation can be realized, effectively improve the Fenton advanced oxidation degradation efficiency of the ferrous Fenton catalyst of biological carbon ball load molybdic acid at methylene blue stimulated dye wastewater.
The ferrous Fenton catalyst of biological carbon ball load molybdic acid prepared by the present invention, reaches more than 95% when reaching more than 85%, 150min to the degradation rate of methylene blue dye wastewater when 120min.
The method that the present invention prepares the ferrous Fenton catalyst of biological carbon ball load molybdic acid comprises:
1, the washing of yeast cells and activation
Take dusty yeast to mix in container with the ratio that dispersant adds 30 ~ 900L dispersant in every 500 ~ 1500g yeast, after stirring at room temperature dissolves 30min, the centrifugal 5min of 3000r/min in centrifuges, after centrifugal end, abandoning supernatant, again centrifugal with dispersant, repeat this operation three times, realize the abundant cleaning of dispersant to yeast cell surface.After third time centrifugal end, abandoning supernatant, yeast sedimentation absolute ethyl alcohol and stirring after cleaning is dissolved, the centrifugal 5min of 3000r/min in centrifuges, after centrifugal end, abandoning supernatant, repeats this operation twice, yeast cell pellet proceeds in container, namely obtains the bio-carrier yeast cells of surface active.
Above-mentioned dispersant is deionized water, and the usage ratio of dusty yeast and dispersant and activator is: every 500g yeast uses 30L dispersant or activator.
2, yeast cells is to the absorption of ferrous ion
The Iron dichloride tetrahydrate taking 0.5 ~ 5mol, in container, adds a small amount of deionized water and makes it dissolve completely and join in the yeast cells solution of step 1 preparation, add deionized water and be settled to certain volume.Utilize magnetic stirring apparatus to stir at 30-80 DEG C of temperature solution, thus promote that yeast cells is to the absorption of ferrous ion.
Adding deionized water in above-mentioned system makes the concentration of Iron dichloride tetrahydrate solution be 0.02 ~ 0.2mol/L.Magnetic agitation temperature is 30 ~ 80 DEG C and stirs 2 ~ 5h.
3, molybdic acid ferrous iron generates and grows in the ageing of yeast cell surface
Take the two molybdic acid hydrate sodium of 0.5 ~ 5mol, be added in system with after a small amount of deionized water dissolving, and in system, add appropriate amount of deionized water to 30 ~ 900L, stir at a certain temperature with magnetic stirring apparatus until obtain a large amount of brown color precipitation, then solution left standstill ageing.
Above-mentioned interpolation appropriate amount of deionized water volume when liquor capacity being returned to ferrous ion adsorption step, the concentration of two molybdic acid hydrate sodium is 0.02 ~ 0.2mol/L, after the mixing of question response liquid, be stirred at 20 ~ 60 DEG C and occur a large amount of yellow mercury oxide, then solution still aging 8 ~ 14h at 20 ~ 50 DEG C.
4, the acquisition of hybrid material and vacuum drying
By once centrifugal at 3000r/min for the system of step 3 gained; centrifugal 5min; after centrifugal end; abandoning supernatant; then with absolute ethyl alcohol, sediment is washed 3 times; each washing is afterwards all at 3000r/min centrifuge, and centrifugal 5min, namely obtains the ferrous hybrid particulates yellow powder of yeast ~ molybdic acid after precipitating a few hours of vacuum drying in an oven.
Above-mentioned baking oven vacuum drying temperature is 40 ~ 80 DEG C, time 4 ~ 12h.
5, high-temperature calcination is to the ferrous Fenton catalyst of biological carbon ball load molybdic acid
Vacuum drying powder key step 4 obtained moves to crucible; and high-temperature calcination under certain atmosphere protection condition; after calcining terminates, after taking out sample, naturally cool to room temperature, obtain micron-sized biological carbon ball load molybdic acid ferrous Fenton catalyst shape powder body material.
Above-mentioned calcining heat is 300 ~ 600 DEG C, and calcination time is 2 ~ 5h, and protective gas may be selected to be the mist of nitrogen, argon gas or 5% hydrogen and 95% nitrogen.
Below in conjunction with specific embodiment, the present invention is illustrated:
Embodiment 1:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.03mol/L.Fully 4h is stirred at 40 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.03mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 25 DEG C of still aging 8h at 25 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 3min under 2500r/m condition, and sediment is put into 40 DEG C of baking oven vacuum drying 4h; Powder after vacuum drying is moved to crucible, and 300 DEG C of calcining 2h, naturally cool to room temperature after taking out sample under nitrogen protection.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
Embodiment 2:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.04mol/L.Fully 4h is stirred at 40 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.03mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 25 DEG C of still aging 10h at 35 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 4min under 2500r/m condition, and sediment is put into 50 DEG C of baking oven vacuum drying 6h; Powder after vacuum drying is moved to crucible, and under argon shield, 400 DEG C of calcining 2.5h, naturally cool to room temperature after taking out sample.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
Embodiment 3:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.05mol/L.Fully 3h is stirred at 55 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.03mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 25 DEG C of still aging 12h at 45 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 5min under 3000r/m condition, and sediment is put into 60 DEG C of baking oven vacuum drying 8h; Powder after vacuum drying is moved to crucible, calcines 3h 5% hydrogen and 95% nitrogen mixed gas protected lower 500 DEG C, after taking out sample, naturally cool to room temperature.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
The biological carbon ball load molybdic acid that the present embodiment prepares ferrous Fenton catalysis powder body material, the experiment through applicant proves, can be used in the Fenton catalytic degradation of methylene blue dye wastewater, specific experiment step is as follows:
Fenton catalytic performance test: carry out in 20P-250 type constant temperature oscillator (the upper grand experimental facilities Co., Ltd of Nereid), accurately measure and take the ferrous sample of 10mg biological carbon ball load molybdic acid, join in the 250ml conical flask of the 20mg/ml methylene blue solution that 50ml is housed, first lucifuge in oscillator also back and forth shakes 60min with the speed of 100r/min, after reaching adsorption equilibrium, in 250ml conical flask, 1.8ml hydrogenperoxide steam generator is added with pipette, lucifuge concussion is continued with the speed of 100r/min in earthquake case, 4ml supernatant is got every 5 ~ 15 minutes, centrifugal 5min is carried out at 3500r/min, get supernatant.By the maximum absorption wavelength λ max=664nm place of supernatant at methylene blue, utilize 752N type ultraviolet-uisible spectrophotometer (upper Nereid section) working sample absorbance, and logical formula D=[(A
0-A
i)/A
0] × 100% calculates Fenton catalysis degradation modulus, wherein A
0the absorbance of methylene blue solution during for reaching adsorption equilibrium, A
ifor the absorbance of the methylene blue solution that timing sampling measures.
Composition graphs 8, reaches more than 95% when the catalyst prepared of the present embodiment reaches more than 85%, 150min to the degradation rate of methylene blue dye wastewater when 120min; Illustrate that the ferrous Fenton catalyst of biological carbon ball load molybdic acid shows excellent Fenton catalytic degradation performance in the degraded of methylene blue dye wastewater;
In addition, the catalyst also prepared the present embodiment has carried out the mensuration of X-ray scanning, electron-microscope scanning, power spectrum and Raman spectrum, the results are shown in Figure 1-7:
Fig. 1 is the X-ray diffractogram of the ferrous Fenton catalyst of biological carbon ball load molybdic acid, and the product prepared by illustrating from the angle of crystalline structure is the composite of molybdic acid ferrous iron and agraphitic carbon; Accompanying drawing 2 to accompanying drawing 5 is scanning electron microscope (SEM) photographs of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load, illustrate that the ferrous Fenton catalyst material of the molybdic acid of prepared biological carbon ball load is made up of the oval micron ball of favorable dispersibility from profile angle, micron ball is of a size of 2.2 ~ 3.0 μm * 3.5 ~ 5.0 μm, be positioned at inner biological carbon ball in nucleocapsid structure and be of a size of 1.0 ~ 1.6 μm * 1.5 ~ 4.2 μm, the thickness being positioned at the ferrous layer of outside molybdic acid is 400 ~ 600nm; Accompanying drawing 6 be the ferrous Fenton catalyst of molybdic acid of biological carbon ball load can spectrogram, illustrates and prepare products therefrom by carbon, iron, oxygen, the chemical element compositions such as molybdenum, the basic element of these elements ferrous composite of molybdic acid of biological carbon ball load just forms; Accompanying drawing 7 is Raman spectrograms of the ferrous Fenton catalyst of molybdic acid of biological carbon ball load, by means of molecular vibration and rotation aspect information, and the molecular structure of the ferrous composite of molybdic acid of the biological carbon ball load prepared by explanation.
Embodiment 4:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.06mol/L.Fully 3h is stirred at 55 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.06mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 35 DEG C of still aging 8h at 45 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 5min under 3000r/m condition, and sediment is put into 60 DEG C of baking oven vacuum drying 4h; Powder after vacuum drying is moved to crucible, and 600 DEG C of calcining 3.5h, naturally cool to room temperature after taking out sample under nitrogen protection.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
Embodiment 5:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.07mol/L.Fully 2h is stirred at 70 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.07mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 35 DEG C of still aging 10h at 35 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 7min under 3500r/m condition, and sediment is put into 50 DEG C of baking oven vacuum drying 6h; Powder after vacuum drying is moved to crucible, and under argon shield, 500 DEG C of calcining 5h, naturally cool to room temperature after taking out sample.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
Embodiment 6:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.08mol/L.Fully 2h is stirred at 70 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.08mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 25 DEG C of still aging 12h at 25 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 8min under 3500r/m condition, and sediment is put into 40 DEG C of baking oven vacuum drying 8h; Powder after vacuum drying is moved to crucible, calcines 4.5h 5% hydrogen and 95% nitrogen mixed gas protected lower 400 DEG C, after taking out sample, naturally cool to room temperature.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
Embodiment 7:
Take dusty yeast and add in appropriate amount of deionized water, fully 30min is stirred with magnetic stirring apparatus under room temperature, then centrifugal 5min under 3000r/m condition, abandoning supernatant, centrifugal after again using deionized water dispensing laundry, repeatedly carry out three times, again the yeast absolute ethyl alcohol and stirring after cleaning is dissolved, under 3000r/m condition after centrifugal 5min, abandoning supernatant, again with absolute ethyl alcohol dispersion activation, repeat this operation twice; The precipitation obtained is added appropriate amount of deionized water, and add Iron dichloride tetrahydrate in above-mentioned solution, make Iron dichloride tetrahydrate concentration be 0.2mol/L.Fully 2h is stirred at 30 DEG C with magnetic stirring apparatus; Also slowly be added in above-mentioned system with deionized water dissolving two molybdic acid hydrate sodium again, and again add appropriate amount of deionized water, solution ferrous ions and molybdenum acid ion concentration is made to be 0.2mol/L, above-mentioned solution is stirred until obtain a large amount of tan precipitate, by solution at 25 DEG C of still aging 12h at 25 DEG C with magnetic stirring apparatus; Then to gained solution centrifugal 8min under 3500r/m condition, and sediment is put into 40 DEG C of baking oven vacuum drying 8h; Powder after vacuum drying is moved to crucible, and 400 DEG C of calcining 4.5h, naturally cool to room temperature after taking out sample under nitrogen protection.Biological carbon ball load molybdic acid ferrous nucleocapsid structure Fenton catalyst material can be obtained.
Claims (6)
1. the ferrous Fenton catalyst of biological carbon ball load molybdic acid, it is characterized in that, this catalyst is the micron ball of nucleocapsid structure, and the core of micron ball is the biological carbon ball that transformation into yeast cell obtains, and the shell of micron ball is the ferrous layer of molybdic acid.
2. the ferrous Fenton catalyst of biological carbon ball load molybdic acid as claimed in claim 1, it is characterized in that, described micron ball is spheroid, the minor axis * major diameter of micron ball is 2.2 ~ 3.0 μm * 3.5 ~ 5.0 μm, described biological carbon ball is spheroid, the minor axis * major diameter of biological carbon ball is 1.0 ~ 1.6 μm * 1.5 ~ 4.2 μm, and the thickness of the ferrous layer of described molybdic acid is 400 ~ 600nm.
3. prepare a method for the ferrous Fenton catalyst of biological carbon ball load molybdic acid described in claim 1 or 2, it is characterized in that, the method comprises:
Step one: mixed with Iron dichloride tetrahydrate solution by the yeast cells solution of activation, in mixed liquor, the concentration of frerrous chloride is 0.02 ~ 0.2mol/L, and in mixed liquor, the concentration of yeast cells is 0.556 ~ 1.5g/L, and temperature is 30 ~ 80 DEG C;
Step 2: add sodium molybdate solution in the mixed liquor in step one, make the concentration of sodium molybdate in mixed liquor be 0.02 ~ 0.2mol/L, at 20 ~ 60 DEG C, be uniformly mixed liquid to there is yellow mercury oxide, then solution is still aging at 20 ~ 50 DEG C;
Step 3: calcine in protective gas environment after the precipitation drying that step 2 is obtained; sample after calcining is cooled to room temperature and namely obtains the ferrous Fenton catalyst of biological carbon ball load molybdic acid; calcining heat is 300 ~ 600 DEG C; calcination time is 2 ~ 5h, and protective gas is the mist of nitrogen, argon gas or 5% hydrogen and 95% nitrogen.
4. prepare the method for the ferrous Fenton catalyst of biological carbon ball load molybdic acid as claimed in claim 3, it is characterized in that, the preparation method of the yeast cells of described activation comprises:
The consumption that dusty yeast and dispersant add 30 ~ 900L dispersant by every 500 ~ 1500g yeast is carried out the cleaning of dispersant to dusty yeast, then the dusty yeast activator after cleaning is carried out surface active and obtain yeast cells, the consumption of activator is identical with the consumption of dispersant;
Described dispersant is deionized water, and described activator is absolute ethyl alcohol.
5. the preparation method of the ferrous Fenton catalyst of biological carbon ball load molybdic acid as claimed in claim 3, is characterized in that, the drying described in step 3 be by step 2 gained be deposited in the temperature of 40 ~ 80 DEG C under carry out drying.
6. the ferrous Fenton catalyst of the biological carbon ball load molybdic acid described in claim 1,2,3,4 or 5 is for the treatment of the application of methylene blue dye wastewater.
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