CN106809921A - A kind of preparation method of kaolinite soil matrix three dimensional particles electrode - Google Patents
A kind of preparation method of kaolinite soil matrix three dimensional particles electrode Download PDFInfo
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- CN106809921A CN106809921A CN201710035738.5A CN201710035738A CN106809921A CN 106809921 A CN106809921 A CN 106809921A CN 201710035738 A CN201710035738 A CN 201710035738A CN 106809921 A CN106809921 A CN 106809921A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention discloses a kind of preparation method of kaolinite soil matrix three dimensional particles electrode, comprise the following steps：(1) grind：Kaolin and black algae are milled to powdered, drying to constant weight；(2) mixed-forming：Green vitriol and Salzburg vitriol are dissolved in the water, mixed liquor is obtained, kaolin powder and black algae powder are put into mixed liquor, carried out incipient impregnation and adsorb 1 3h, the bead that particle diameter is 3 5mm is made after being well mixed；(3) dry：Bead is dried treatment；(4) calcine：Bead is calcined and can obtain kaolin basal granule sub-electrode.The kaolin basal granule sub-electrode that the inventive method is prepared, and the kaolin with loose structure is carrier, black algae is loaded on kaolin granule electrode Fe and Cu bimetallic catalysts as pore former, and the support type granule electrode can provide homogeneous Fe for reaction2+And Cu2+Catalyst and heterogeneous Fenton catalyst, good degrading effect to waste water from dyestuff, can reuse.
Description
Technical field
The present invention relates to environmental protection and treatment field, more particularly to a kind of preparation side of kaolinite soil matrix three dimensional particles electrode
Method.
Background technology
Dyestuff is widely applied in daily life, especially in industries such as printing and dyeing, printing, weaving and cosmetics.Waste water from dyestuff
The features such as because of contaminant component complexity, deep colourity, difficult degradation and toxicity high, if directly discharged without treatment, can be to human body
Serious harm is caused with aquatile.Water treatment technology traditional at present is difficult to obtain ideal effect to waste water from dyestuff.Therefore,
It is necessary to study the treatment technology of such material.
Electrochemistry is widely used as a kind of Green Technologies For Waste Water Treatment in persistent organic pollutants control aspect.Wherein,
Three-diemsnional electrode is that granular or other clastic electrode materials are loaded between two electrodes of conventional two-dimensional electrode, forms many micro- electricity
, there is electrochemical reaction on working electrode material surface in Xie Chi.Compared with two-dimensional electrode, the face body ratio of three-diemsnional electrode significantly increases
Plus, interparticle distance reduces, and mass transfer effect is improved.But used as electrochemical techniques, the more general high-level oxidation technology of its energy consumption is still
It is higher, in terms of practical application, current efficiency is improved, processing cost is reduced, wastewater treatment can be widely used in.
Fenton technology is that H is produced in reaction system using electrochemistry2O2, so as to Fenton reactions occur to organic
The method that thing is aoxidized, but traditional Electro-Fenton process because the dosage and pH ranges of application that there is difficult control ferrous salt it is narrow etc.
It is not enough.Introducing other transition metal such as Cu salt is currently based on, the carrying out of Fenton's reaction and the scope of application of raising pH can be promoted.
But, the shortcomings of the reaction of traditional Fenton technology can produce a large amount of iron cements and the catalyst can not to recycle after terminating, make it
Using being restricted.
Fenton catalyst is loaded three-dimensional electrode/electro Fenton technologies Based on Three-dimensional Electrode Method and Fenton method organic couplings
In on granule electrode, can not only be used for heterogeneous Fenton catalyst while also serving as granule electrode, in same reactor simultaneously
Three-diemsnional electrode electro-catalysis and Fenton reactions are carried out, both reaction advantages are had concurrently, cooperative effect is formed, traditional electricity is overcome fragrant
The electrode surface area of method is small, difficult recovery, mass transfer effect difference and the shortcomings of the narrower pH scope of applications, drastically increase electric current effect
Rate and unit space-time yield.
The information for being disclosed in the background section is merely intended to increase the understanding to general background of the invention, without answering
In being considered as recognizing or imply in any form that the information structure has been the prior art well known to persons skilled in the art.
The content of the invention
It is an object of the invention to provide a kind of preparation method of kaolinite soil matrix three dimensional particles electrode, the particle for preparing
Electrode as heterogeneous Fenton catalyst and can be also capable as three-diemsnional electrode, make it have that catalysis activity is high, pH is applicable model
The advantages of enclosing wide and reusable.
To achieve the above object, the invention provides a kind of preparation method of kaolinite soil matrix three dimensional particles electrode, including with
Lower step：
(1) grind：Kaolin and black algae are milled to powdered, then dried to constant weight；
(2) mixed-forming：Green vitriol and Salzburg vitriol are dissolved in the water, mixed liquor is obtained, by institute
State kaolin powder obtained in step (1) and black algae powder is put into mixed liquor, carry out incipient impregnation absorption 1-3h, can
The bead that particle diameter is 3-5mm is made after well mixed；
(3) dry：The bead prepared through the step (2) is dried treatment；
(4) calcine：The bead dried through the step (3) is calcined and can obtain kaolin basal granule sub-electrode.
Preferably, in above-mentioned technical proposal, dry temperature is 80-120 DEG C in the step (1).
Preferably, in above-mentioned technical proposal, green vitriol its active component Fe contents described in the step (2)
It is the 0.5-3wt% of kaolin basal granule sub-electrode quality.
Preferably, in above-mentioned technical proposal, Salzburg vitriol its active component Cu contents described in the step (2)
It is the 0.5-3wt% of kaolin basal granule sub-electrode quality.
Preferably, in above-mentioned technical proposal, the mass ratio of kaolin powder and black algae powder addition in the step (2)
It is 1.5-4:1.
Preferably, in above-mentioned technical proposal, the drying in the step (3) is to be done under conditions of temperature is for 80-120 DEG C
Dry 12-24h.
Preferably, in above-mentioned technical proposal, calcining is to be calcined under conditions of 450-750 DEG C in the step (4).
Preferably, in above-mentioned technical proposal, calcining is to be warming up to the heating rate of 5 DEG C/min in the step (4)
450-750 DEG C, then calcining at constant temperature 120-300min.
A kind of method for processing waste water from dyestuff, the kaolin basal granule sub-electrode prepared using the above method processes dyestuff
Waste water.
Compared with prior art, the present invention has the advantages that：
(1) the kaolin basal granule sub-electrode that the preparation method of kaolinite soil matrix three dimensional particles electrode of the present invention is prepared, leads to
Cross using nontoxic, pollution-free, cheap and easy to get, and the kaolin with loose structure is carrier, black algae as pore former, by Fe and
Cu bimetallic catalysts are loaded on kaolin granule electrode, and the support type granule electrode can provide homogeneous Fe for reaction2+And Cu2 +Catalyst and heterogeneous Fenton catalyst, solving traditional Fenton needs additional class fenton catalyst dosage occur
Whard to control and troublesome poeration, catalyst be difficult to be reclaimed, the low problem of current efficiency, good degrading effect to waste water from dyestuff, can
Recycling.
(2) one kind is prepared as heterogeneous Fenton catalyst with grinding, mixed-forming, drying and calcination method and make simultaneously
It is the three dimensional particles electrode of support type, the granule electrode specific surface area of preparation is big, electric conductivity and catalytic performance are good, is a kind of
New kaolin basal granule sub-electrode, considerably increases the response area of electrode, improves the reaction speed of electrode, can be efficiently
Degradation of dye waste water.
(3) kaolin basal granule sub-electrode can provide homogeneous and heterogeneous Fenton catalyst, solve traditional electricity
Fenton needs additional fenton catalyst dosage whard to control and troublesome poeration, the small pH scope of applications, high cost occur and urge
The problems such as agent hardly possible is reclaimed.
(4) Fe the and Cu active components with catalysis are carried on kaolin granule electrode by kaolin basal granule sub-electrode
On, the specific surface of catalyst is substantially increased, while it also avoid the loss of Fe, Cu active component, extend granule electrode
Service life, repeats and utilizes.
(5) preparation method of the invention is simple and easy to apply, it is easy to promote on a large scale.
Brief description of the drawings
The kaolinite soil matrix three dimensional particles that Fig. 1 is prepared for the preparation method of the kaolinite soil matrix three dimensional particles electrode of embodiment 1
The SEM figures of electrode.
The kaolinite soil matrix three dimensional particles that Fig. 2 is prepared for the preparation method of the kaolinite soil matrix three dimensional particles electrode of embodiment 1
The EDS energy spectrum diagrams of electrode.
Specific embodiment
Below in conjunction with the accompanying drawings, specific embodiment of the invention is described in detail, it is to be understood that guarantor of the invention
Shield scope is not limited by specific embodiment.
Explicitly indicated that unless otherwise other, otherwise in entire disclosure and claims, term " including " or its change
Change such as "comprising" or " including " etc. and will be understood to comprise stated element or part, and do not exclude other units
Part or other parts.
The principle of the preparation method of kaolinite soil matrix three dimensional particles electrode of the present invention is, using new three-dimensional electrode/electro
Fenton methods, Based on Three-dimensional Electrode Method and Electro-Fenton process are coupled, and can simultaneously carry out anode and granule electrode direct oxidation, anode
OH indirect oxidations, the Fe that granule electrode is produced are produced with granule electrode2+And Cu2+And in the heterogeneous sweet smell on granule electrode surface
The avtive spot of catalyst, the H produced with negative electrode2O2Generation Fenton reacts, and is a kind of various electricity for acting on one of synthesis
Chemical oxidation techniques.Compared with traditional Fenton technology, it has face body than increase, and interparticle distance is small, and pH is applicable
Scope increases, and catalyst is the advantages of easily reclaim.
Embodiment 1
A kind of preparation method of kaolinite soil matrix three dimensional particles electrode, comprises the following steps：
(1) grind：First, kaolin is ground with ball mill, then kaolin is tried one's best with mortar grinds to form thinner powder
Last shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Then, black algae is ground with ball mill
It is broken, then kaolin is tried one's best with mortar grind to form thinner powdered, 80 mesh molecular sieves are crossed, it is placed on thermostatic drying chamber and exists
Constant weight is put in drying at 120 DEG C；
(2) mixed-forming：Take 0.7446g (0.5wt%Fe) green vitriols and 0.5859g (0.5wt%Cu) five
Hydrated copper sulfate is dissolved in 20mL deionized waters, and 18g kaolin powders after pretreatment and the black algae powder of 12g are put into seven water
The mixed liquor of ferrous sulfate and Salzburg vitriol is closed, incipient impregnation absorption 1h is carried out, makes to be made particle diameter after it is well mixed
It is the bead of 3-5mm；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 24h is dried at 120 DEG C.
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 450 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 300min, you can obtain kaolin basal granule sub-electrode.Obtained granule electrode pattern is as shown in Figure 1.
Anode and negative electrode are respectively with graphite cake, stainless steel plate, by 30g/L addition by above-described embodiment prepare
Kaolin basal granule sub-electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.Experiment is 3 in pH, and voltage is 10V, electricity
Solution matter Na2SO4Concentration is 5g/L, and aeration rate is that 20mg/L rhodamine Bs are molten for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
Liquid 60min.The result of degradation time and clearance is listed in table 1, after 60min reachable 92.26% removal is processed as shown in Table 1
Rate.
Clearance result of the kaolin basal granule sub-electrode of the gained of 1 embodiment of table 1 to rhodamine B
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 36.82 | 50.96 | 65.37 | 72.41 | 85.69 | 92.46 |
Embodiment 2
A kind of preparation method of kaolinite soil matrix three dimensional particles electrode, comprises the following steps：
(1) grind：First, kaolin is ground with ball mill, then kaolin is tried one's best with mortar grinds to form thinner powder
Last shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 100 DEG C and puts constant weight；Then, by black algae ball mill
Grind, then kaolin is tried one's best with mortar grind to form thinner powdered, cross 80 mesh molecular sieves, be placed on thermostatic drying chamber and exist
Constant weight is put in drying at 100 DEG C；
(2) mixed-forming：Take 1.4892g (1.0wt%Fe) green vitriols and 1.1718g (1.0wt%Cu) five
Hydrated copper sulfate is dissolved in 20mL deionized waters, and 21.0g kaolin powders after pretreatment and the black algae powder of 9.0g are put into
The mixed liquor of green vitriol and Salzburg vitriol, carries out incipient impregnation absorption 3h, makes to be made after it is well mixed
Particle diameter is the bead of 3-5mm；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 24h is dried at 120 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 550 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 120min, you can obtain kaolin basal granule sub-electrode.
Anode and negative electrode are respectively with graphite cake, stainless steel plate, by 30g/L addition by above-described embodiment prepare
Kaolin basal granule sub-electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.Experiment is 3 in pH, and voltage is 10V, electricity
Solution matter Na2SO4Concentration is 5g/L, and aeration rate is that 20mg/L rhodamine Bs are molten for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
Liquid 60min.The result of degradation time and clearance is listed in table 2, after 60min reachable 98.63% removal is processed as shown in Table 2
Rate.
Clearance result of the kaolin basal granule sub-electrode of the gained of 2 embodiment of table 2 to rhodamine B
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 48.5 | 66.3 | 86.9 | 91.54 | 95.52 | 98.63 |
Embodiment 3
A kind of preparation method of kaolinite soil matrix three dimensional particles electrode, comprises the following steps：
(1) grind：First, kaolin is ground with ball mill, then kaolin is tried one's best with mortar grinds to form thinner powder
Last shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Then, black algae is ground with ball mill
It is broken, then kaolin is tried one's best with mortar grind to form thinner powdered, 80 mesh molecular sieves are crossed, it is placed on thermostatic drying chamber and exists
Constant weight is put in drying at 120 DEG C；
(2) mixed-forming：Take 2.9784g (2.0wt%Fe) green vitriols and 2.3436g (2.0wt%Cu) five
Hydrated copper sulfate is dissolved in 20mL deionized waters, and 24.0g kaolin powders after pretreatment and the black algae powder of 6.0g are put into
The mixed liquor of green vitriol and Salzburg vitriol, carries out incipient impregnation absorption 2h, makes to be made after it is well mixed
Particle diameter is the bead of 3-5mm；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 18h is dried at 100 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 650 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 180min, you can obtain kaolin basal granule sub-electrode.
Anode and negative electrode are respectively with graphite cake, stainless steel plate, by 30g/L addition by above-described embodiment prepare
Kaolin basal granule sub-electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.Experiment is 3 in pH, and voltage is 10V, electricity
Solution matter Na2SO4Concentration is 5g/L, and aeration rate is that 20mg/L rhodamine Bs are molten for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
Liquid 60min.The result of degradation time and clearance is listed in table 3, after 60min reachable 97.52% removal is processed as shown in Table 3
Rate.
Clearance result of the kaolin basal granule sub-electrode of the gained of 3 embodiment of table 3 to rhodamine B
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 46.81 | 68.25 | 79.15 | 85.24 | 92.37 | 97.52 |
Embodiment 4
A kind of preparation method of kaolinite soil matrix three dimensional particles electrode, comprises the following steps：
(1) grind：First, kaolin is ground with ball mill, then kaolin is tried one's best with mortar grinds to form thinner powder
Last shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Then, black algae is ground with ball mill
It is broken, then kaolin is tried one's best with mortar grind to form thinner powdered, 80 mesh molecular sieves are crossed, it is placed on thermostatic drying chamber and exists
Constant weight is put in drying at 120 DEG C；
(2) mixed-forming：Take 4.4676g (3.0wt%Fe) green vitriols and 3.5154g (3.0wt%Cu) five
Hydrated copper sulfate is dissolved in 20mL deionized waters, and 21.0g kaolin powders after pretreatment and the black algae powder of 9.0g are put into
The mixed liquor of green vitriol and Salzburg vitriol, carries out incipient impregnation absorption 3h, makes to be made after it is well mixed
Particle diameter is the bead of 3-5mm；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 18h is dried at 100 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 750 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 240min, you can obtain kaolin basal granule sub-electrode.
Anode and negative electrode are respectively with graphite cake, stainless steel plate, by 30g/L addition by above-described embodiment prepare
Kaolin basal granule sub-electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.Experiment is 3 in pH, and voltage is 10V, electricity
Solution matter Na2SO4Concentration is 5g/L, and aeration rate is that 20mg/L rhodamine Bs are molten for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
Liquid 60min.The result of degradation time and clearance is listed in table 4, after 60min reachable 91.62% removal is processed as shown in Table 4
Rate.
Clearance result of the kaolin basal granule sub-electrode of the gained of 4 embodiment of table 4 to rhodamine B
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 46.80 | 58.21 | 68.29 | 71.36 | 85.71 | 91.62 |
Embodiment 5
A kind of preparation method of kaolinite soil matrix three dimensional particles electrode, comprises the following steps：
(1) grind：First, kaolin is ground with ball mill, then kaolin is tried one's best with mortar grinds to form thinner powder
Last shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Then, black algae is ground with ball mill
It is broken, then kaolin is tried one's best with mortar grind to form thinner powdered, 80 mesh molecular sieves are crossed, it is placed on thermostatic drying chamber and exists
Constant weight is put in drying at 120 DEG C；
(2) mixed-forming：Take 2.9784g (2.0wt%Fe) green vitriols and 1.1718g (1.0wt%Cu) five
Hydrated copper sulfate is dissolved in 20mL deionized waters, and 18.0g kaolin powders after pretreatment and the black algae powder of 12.0g are put into
The mixed liquor of green vitriol and Salzburg vitriol, carries out incipient impregnation absorption 2h, makes to be made after it is well mixed
Particle diameter is the bead of 3-5mm；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 24h is dried at 120 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 650 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 240min, you can obtain kaolin basal granule sub-electrode.
Anode and negative electrode are respectively with graphite cake, stainless steel plate, by 30g/L addition by above-described embodiment prepare
Kaolin basal granule sub-electrode is thrown and is filled in reactor, and 3 D electrode reactor is obtained.Experiment is 3 in pH, and voltage is 10V, electricity
Solution matter Na2SO4Concentration is 5g/L, and aeration rate is that 20mg/L rhodamine Bs are molten for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
Liquid 60min.The result of degradation time and clearance is listed in table 5, after 60min reachable 93.25% removal is processed as shown in Table 5
Rate.
Clearance result of the kaolin basal granule sub-electrode of the gained of 5 embodiment of table 5 to rhodamine B
| Time/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Clearance/% | 31.08 | 49.25 | 52.89 | 72.57 | 85.63 | 93.25 |
Embodiment 6
Blank kaolin, Fe/ kaolin and Cu/ kaolin granule electrode are prepared as control granule electrode, by what is prepared
Fe-Cu/ kaolin granule electrode and control granule electrode carry out electrolytic experiment, investigate the Fe-Cu/ kaolin granule electrodes for preparing
With electro catalytic activity higher.
1st, the preparation method of blank kaolin granule electrode is：
(1) grind：Kaolin is first ground with ball mill, then kaolin is tried one's best with mortar is ground to form thinner powder
Shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Black algae is first ground with ball mill, then
Kaolin is tried one's best with mortar it is thinner powdered to grind to form, and crosses 80 mesh molecular sieves, is placed on thermostatic drying chamber at 120 DEG C
Constant weight is put in drying；
(2) mixed-forming：Processed 21.0g kaolin powders and the black algae powder of 9.0g are added to 20mL
Ionized water, is made the bead that particle diameter is 3-5mm after being well mixed；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 24h is dried at 120 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 550 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 120min, you can obtain blank kaolin granule electrode.
2nd, the preparation method of Fe/ kaolin granule electrode is：
(1) grind：Kaolin is first ground with ball mill, then kaolin is tried one's best with mortar is ground to form thinner powder
Shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Black algae is first ground with ball mill, then
Kaolin is tried one's best with mortar it is thinner powdered to grind to form, and crosses 80 mesh molecular sieves, is placed on thermostatic drying chamber at 120 DEG C
Constant weight is put in drying；
(2) mixed-forming：Take 1.4892g (1.0wt%Fe) green vitriol and be dissolved in 20mL deionized waters, will be through
Pretreated 21.0g kaolin powders and the black algae powder of 9.0g are put into the mixing of green vitriol and Salzburg vitriol
Liquid, carries out incipient impregnation absorption 3h, makes to be made the bead that particle diameter is 3-5mm after it is well mixed；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 24h is dried at 120 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 550 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 120min, you can obtain Fe/ kaolin granule electrodes.
3rd, the preparation method of Cu/ kaolin granule electrode is：
(1) grind：Kaolin is first ground with ball mill, then kaolin is tried one's best with mortar is ground to form thinner powder
Shape, crosses 100 mesh molecular sieves, is placed on thermostatic drying chamber drying at 80 DEG C and puts constant weight；Black algae is first ground with ball mill, then
Kaolin is tried one's best with mortar it is thinner powdered to grind to form, and crosses 80 mesh molecular sieves, is placed on thermostatic drying chamber at 120 DEG C
Constant weight is put in drying；
(2) mixed-forming：Take 1.1718g (1.0wt%Cu) Salzburg vitriol and be dissolved in 20mL deionized waters, will be through pre-
The black algae powder of 21.0g kaolin powders and 9.0g after treatment is put into the mixing of green vitriol and Salzburg vitriol
Liquid, carries out incipient impregnation absorption 3h, makes to be made the bead that particle diameter is 3-5mm after it is well mixed；
(3) dry：By being placed in thermostatic drying chamber through the bead of above-mentioned preparation 24h is dried at 120 DEG C；
(4) calcine：The bead for taking above-mentioned drying is placed in Muffle furnace, and 550 DEG C are warming up to the heating rate of 5 DEG C/min,
Calcining at constant temperature 120min, you can obtain Cu/ kaolin granule electrodes.
4th, the preparation method of Fe-Cu/ kaolin granule electrode is with embodiment 2.
Anode and negative electrode are respectively with graphite cake, stainless steel plate, the addition by 30g/L will be prepared in above-described embodiment 6
Blank kaolin, Fe/ kaolin and Cu/ kaolin granule electrode and Fe-Cu/ kaolin granule electrodes be filled in reactor
In, 3 D electrode reactor is obtained.Experiment is 3 in pH, and voltage is 10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is
Under the conditions of 0.8L/min, the degraded 400mL concentration that is powered is 20mg/L rhodamine B solution 60min.Different granule electrodes are existed
Result during 60min to rhodamine B clearance is listed in table 6.
Clearance result of the granule electrode prepared in the embodiment 6 of table 6 to rhodamine B
| Granule electrode | Blank kaolin | Fe/ kaolin | Cu/ kaolin | Fe-Cu/ kaolin |
| Clearance % | 62.05 | 80.16 | 72.84 | 98.63 |
As can be seen from Table 6, the Fe-Cu/ kaolin granule electrode that prepared by the present invention is to the clearance of rhodamine B higher than sky
The electro-catalysis efficiency of white kaolinic, Fe/ kaolin and Cu/ kaolin granule electrodes.
Embodiment 7：
Experiment of the kaolin basal granule sub-electrode in condition of different pH：
Anode and negative electrode are respectively with graphite cake, stainless steel plate, the addition by 30g/L will be prepared in above-described embodiment 2
Kaolin basal granule sub-electrode throw be filled in reactor, be obtained 3 D electrode reactor.Experiment is 3-9 in pH, and voltage is
10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is sieve 20mg/L for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
Red bright B solution 60min.By kaolin basal granule sub-electrode under condition of different pH, the reaction time goes when being 60min to rhodamine B
Except the result of rate is listed in table 7.
Clearance result of the granule electrode prepared in the embodiment 7 of table 7 to rhodamine B
| pH | 3.0 | 5.0 | 6.65 | 9.0 |
| Clearance % | 98.63 | 93.51 | 95.72 | 91.48 |
As can be seen from Table 7, the present invention prepare kaolin basal granule sub-electrode pH be 3-9 under the conditions of, to rhodamine B
Clearance reaches 90%, illustrates that kaolin basal granule sub-electrode has the larger pH scope of applications.
Embodiment 8：
The stability test of kaolin basal granule sub-electrode：
Anode and negative electrode are respectively with graphite cake, stainless steel plate, the addition by 30g/L will be prepared in above-described embodiment 2
Kaolin basal granule sub-electrode throw be filled in reactor, be obtained 3 D electrode reactor.Experiment is 6.65 in pH, and voltage is
10V, electrolyte Na2SO4Concentration is 5g/L, and aeration rate is sieve 20mg/L for the degraded 400mL concentration that under the conditions of 0.8L/min, is powered
After red bright B solution 60min, solution is carried out into simple filtration, after the granule electrode after separation is washed with deionized, is dried,
Electrocatalysis Degradation experiment is carried out under the same conditions.Continuously repeat 3 times, measure kaolin basal granule sub-electrode degradation rate and be followed successively by：
97.15%th, 93.28%, 90.715%.It can thus be seen that 3 recyclings of kaolin basal granule sub-electrode prepared by the present invention
Afterwards, the clearance of rhodamine B all maintains more than 90%, illustrates that kaolin basal granule sub-electrode stability is higher, with preferable
Repeat performance.
The foregoing description to specific illustrative embodiment of the invention be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that certain principles of the invention and its reality should
With so that those skilled in the art can realize and using a variety of exemplaries of the invention and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (9)
1. a kind of preparation method of kaolinite soil matrix three dimensional particles electrode, it is characterised in that comprise the following steps：
(1) grind：Kaolin and black algae are milled to powdered, then dried to constant weight；
(2) mixed-forming：Green vitriol and Salzburg vitriol are dissolved in the water, mixed liquor is obtained, by the step
Suddenly kaolin powder obtained in (1) and black algae powder are put into mixed liquor, carry out incipient impregnation absorption 1-3h, can be mixed
The bead that particle diameter is 3-5mm is made after uniform；
(3) dry：The bead prepared through the step (2) is dried treatment；
(4) calcine：The bead dried through the step (3) is calcined and can obtain kaolin basal granule sub-electrode.
2. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(1) dry temperature is 80-120 DEG C in.
3. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(2) its active component Fe of green vitriol described in contents are the 0.5-3wt% of kaolin basal granule sub-electrode quality.
4. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(2) Salzburg vitriol its active component Cu contents described in are the 0.5-3wt% of kaolin basal granule sub-electrode quality.
5. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(2) mass ratio of the amount that kaolin powder and black algae powder are added is 1.5-4 in:1.
6. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(3) drying in is to dry 12-24h under conditions of temperature is for 80-120 DEG C.
7. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(4) calcining is to be calcined under conditions of 450-750 DEG C in.
8. the preparation method of kaolinite soil matrix three dimensional particles electrode according to claim 1, it is characterised in that the step
(4) calcining is to be warming up to 450-750 DEG C with the heating rate of 5 DEG C/min in, then calcining at constant temperature 120-300min.
9. it is a kind of process waste water from dyestuff method, it is characterised in that the kaolin basal granule prepared using the claim 1
Sub-electrode processes waste water from dyestuff.
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| CN114835201B (en) * | 2022-03-18 | 2023-08-22 | 青岛理工大学 | Three-dimensional electrocatalytic reaction equipment system based on multifunctional catalytic particle electrode |
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