CN109052575A - A kind of γ-Al2O3The preparation method and application of-Ti- (Ag/W) three dimensional particles electrode - Google Patents
A kind of γ-Al2O3The preparation method and application of-Ti- (Ag/W) three dimensional particles electrode Download PDFInfo
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Abstract
The present invention provides a kind of γ-Al2O3The preparation method and application of-Ti- (Ag/W) three dimensional particles electrode, the method select γ-Al2O3Ti, Ag and W element are supported on carrier using sol-gel method and infusion process for predecessor carrier, in the way of temperature programming, Payload element is bonded on carrier in the form of metal-oxide film, novel granule electrode γ-Al is made2O3- Ti- (Ag/W), in three-dimensional micropore gas explosion reactor, coal chemical industrial waste water of degrading.The preparation method of three dimensional particles electrode of the present invention is simple, easy to operate, and catalytic activity is high, and three-dimensional reactor handles coal chemical industrial waste water by the way of micropore gas explosion, achieves the effect of efficient degradation sewage.
Description
Technical field
The invention belongs to environmentally friendly water treatment fields, are related to a kind of γ-Al2O3The preparation of-Ti- (Ag/W) three dimensional particles electrode
A kind of methods and applications, and in particular to sol-gel method cooperation infusion process synthesis γ-Al2O3- Ti- (Ag/W) three dimensional particles electrode
And the method for coal chemical industrial waste water of degrading in three-dimensional reactor.
Background technique
Important composition of the Coal Energy Source as China's energy resource structure, for ensuring that it is heavy to closing that China's the energy safety of supply has
The effect wanted.It was reported that display, with domestic petroleum, the growing tension of natural gas supply, domestic chemical industry occurs to coal
The inclined trend of chemical industry.It during coal processing and utilization, needs using a large amount of water, while can also generate the useless of incredible amount
Water, a large amount of coal chemical industrial waste water are the waste water of high pollution again, can do great damage to environment and ecology, also threaten people's
Drinking water safety.Coal chemical industrial waste water high organic content, and many organic matters are difficult for biological degradation, many dirts even in
Dye object such as cyanide, heterocyclic compound etc. is unfavorable for microbial survival to pole, therefore coal chemical industrial waste water biodegradability is poor, toxicity
Greatly.In addition, coal chemical industrial waste water coloration is higher, raw water color is very deep, or even blacks, relatively high effluent color dilution, water outlet
Color is more shallower, and color is with light yellow.Therefore, coal chemical industrial waste water be a kind of biochemical it is poor, it is very difficult, to environmental hazard
Biggish industrial wastewater.Currently, the predominantly tertiary treatment mode of coal chemical industrial waste water processing both at home and abroad: level-one materialized pretreatment, two
Grade is biochemical treatment, and three-level uses materialization advanced treating.But the process flow of tertiary treatment mode and processing time are all partially long,
And processing cost is fairly expensive.Therefore, how quickly, stablize, the processing coal chemical industrial waste water of low energy consumption, become coal chemical industrial waste water
The hot and difficult issue of process field.
Electrochemical water treatment technology because its have multi-functional, height flexibility, be easy to automate, it is without secondary pollution etc. its
The incomparable advantage of its water treatment technology just becomes the hot subject of domestic and international Processing Technology Research, is especially difficult to those
The removal of biochemical degradation great to human health risk " three cause " carcinogenic, teratogenesis, mutagenesis organic pollutant has very high
Efficiency, and a large amount of energy can be saved again.Thus, electrochemical water treatment technology has become world's water treatment technology phase in recent years
When active research field, by extensive concern both domestic and external.
Three-diemsnional electrode (Three-dimensional electrode) is to be proposed by Backhurst J.R in the latter stage sixties
Come, also known as bed electrode (bed electrode) or granule electrode (particle electrode).With two-dimentional degradation system
It compares, three-dimensional degradation system is the particle filled composite particle between the cathode-anode plate of two-dimensional system, to form a new pole, i.e. third
The electrochemical reactor of pole.Due to being filled with particle granules, cause three-diemsnional electrode that there are bigger specific surface area, and particle granules
The distance between electrode plate has been shortened, to improve mass transport process, so that the utilization efficiency of electric current is improved, ensure that three
Electrolysis tech is tieed up to the treatment effect of organic pollutant.The core of three-dimensional electrolysis is granule electrode.Because three-diemsnional electrode not only may be used
To carry out direct electrochemistry using cathode and anode, the granule electrode of filling can also degrade to organic pollutant.So
Three-dimensional electrolysis can greatly promote electrolytic efficiency, and current efficiency reduces energy consumption of reaction.Currently, granule electrode material is a variety of more
Sample, different base materials can load again, adulterate multiple element.But current electrode material has the following problems: electrode
The disadvantages such as catalytic activity is low, granule electrode stability is poor, mechanical strength is low.
Summary of the invention
Current three dimensional particles electrode there are aiming at the problem that and defect, the present invention provides it is a kind of prepare highly active ion electricity
The preparation method of pole.
It is a further object of the present invention to provide the γ-Al prepared in the method2O3- Ti- (Ag/W) three dimensional particles electrode.
It is yet another object of the invention to provide the γ-Al2O3- Ti- (Ag/W) three dimensional particles electrode is in degradation coal chemical industrial waste water
In application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, the following steps are included:
The first step, first to carrier particle γ-Al2O3It is pre-processed, weighs quantitative carrier particle and be put into etching solution
Rinse；Then particle is handled using acetone soln, repeated flushing is carried out to granule electrode with distilled water after cleaning, until
For neutrality；Finally pretreated particle is put into baking oven and is dried for standby；
Dehydrated alcohol and deionized water are mixed, adjust its pH to 2~3 with HCl solution by second step, and A liquid is made；By titanium
Sour four butyl esters, dehydrated alcohol and glacial acetic acid mixing, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, side
Instill side stirring；It continuously stirs 5min at room temperature after mixing, is then allowed to stand and completes TiO2The preparation of gel；It will then carry
Body particle is immersed in TiO obtained2In gel, and 1~4h is sufficiently reacted on shaking table；By impregnated Ti metal salt solution
Carrier particle taking-up is placed on dries in an oven；Dried particle is respectively put into Muffle furnace, is roasted at 100~800 DEG C
Burn 1~4h of activation；It repeats the above steps 2~5 times, required load Ti metal oxide particle is made；
Third step configures certain density AgNO3+H2WO4Ethanol solution；By the load Ti metal oxidation of second step preparation
Object particle is put into maceration extract AgNO3+H2WO4In ethanol solution, a period of time is sufficiently reacted on shaking table；Ag/W will then be impregnated
The load Ti metal oxide particle taking-up of metal salt solution is placed in an oven, and is dried at being 80 DEG C in temperature more than 12h,
It is dried for standby；Then dried particle is respectively put into Muffle furnace, 1~4h of calcination activation at 100~800 DEG C；It repeats
Above-mentioned steps 2~5 times, obtain γ-Al2O3- Ti- (Ag/W) three dimensional particles electrode.
The NH of HF and 2g/L that etching solution in the first step is 40ml/L4F by volume 1:4~8 mix it is molten
Liquid.γ-Al in the first step2O3The mass volume ratio of particle and etching liquid is 1:2~5 (g:ml).
The volume ratio of the second step dehydrated alcohol and deionized water is 1~3:1, preferably 2:1.
The second step dehydrated alcohol and glacial acetic acid volume ratio are 1:1~2, preferably 1:1:1；Butyl titanate is in anhydrous second
Concentration in pure and mild glacial acetic acid solution is 0.5~10.5mol/L.
The second step carrier particle and TiO2The mass volume ratio of gel is 1:2~5, preferably 1:3.
The third step AgNO3+H2WO4AgNO in ethanol solution3Concentration be 0.5mol/L, H2WO4Concentration be
0.05mol/L。
Heating means in the second step and third step in Muffle furnace take the mode of temperature programming, with 10~25 DEG C/
The speed of min is warming up to 100~800 DEG C.
γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode further preferably comprises the steps of:
The first step first pre-processes carrier particle, weighs quantitative carrier particle and is put into etching solution (BOE),
Rinse is carried out in the shaking table of waters；Then particle is impregnated using acetone soln, rinse processing, with distilled water pair after cleaning
Granule electrode carries out repeated flushing, until for neutrality；Finally pretreated particle is put into after drying 12h in 105 DEG C of baking ovens
It is spare；
Dehydrated alcohol and deionized water are mixed (volume ratio 2:1), adjust its pH to 2~3 with HCl solution by second step,
A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (volume ratio 1:1:1) are mixed, obtained B liquid is stirred evenly；By A
Liquid is added dropwise in isometric B liquid, is stirred when instilling；Continuously stir a period of time at room temperature after mixing, so
1h is stood afterwards completes TiO2The preparation of gel；Quantitative carrier particle is then immersed in TiO obtained2In gel, wherein carrier
The mass ratio of particle and butyl titanate is 1:3, and 4h is then sufficiently reacted on shaking table；By impregnated Ti metal salt solution
Carrier particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature；Dried particle is respectively put into Muffle
In furnace, 100~800 DEG C of calcination activations for a period of time；Repeat the above steps n times, and required load Ti metal oxide is made
Granule electrode；
Third step, loaded Ag/W metal oxide particle electrode preparation method.Configure the AgNO of 0.5mol/L3+
0.05mol/LH2WO4Ethanol solution；Carrier-Ti prepared by second step is put into maceration extract (mass/volume 1:4), is being shaken
Sufficiently reaction 4h on bed；Then the particle taking-up of the load Ti of impregnated Ag/W metal salt solution is placed in an oven, and
Drying is dried for standby more than 12h at being 80 DEG C in temperature；Then dried particle is respectively put into Muffle furnace, in 100-
800 DEG C of 1~4h of calcination activation；Repeat the above steps n times, obtains required load carriers-Ti- (Ag/W) metal oxide grain
Sub-electrode.
That the particle carrier in the first step is selected is γ-Al2O3, currently, the carrier material of three dimensional particles electrode has
Porous artificial zeolite, active carbon and bead etc..γ-Al2O3With porosity height, large specific surface area, high mechanical strength, change surely
The qualitative advantages such as strong, therefore this patent selects γ-Al2O3Carrier as Payload element.
Further, the first step etching solution chooses HF and NH4The BOE (buffered oxide etch liquid) of F composition is mixed
Solution is closed, etching speed about 10nm is per second, and wherein HF is main etching solution.
The first Payload element selected in the second step is Ti, Ti and O under hot conditions2Reaction generates anatase, gold
The TiO of three kinds of crystal forms of red stone and brockite2, and TiO of the crystal form based on anatase is formed in subsequent roasting2, have very high
Catalytic activity.Commonly used Payload element specifically includes that noble metal, rare metal and transition metal.Wherein noble metal and dilute
There is metallic catalyst activity high, strong applicability, the service life is long, can have a wide range of application, but theirs is at high price, it is difficult to be advised greatly
The industrial applications of mould.Transition metal also possesses stronger catalytic activity, but there are active components to be easy to run off, service life is opposite
The problems such as shorter.
Sol-gel method is utilized in the load of Ti element in the second step, glue -- and gel method will exactly contain high chemistry
The compound of active component by solution, colloidal sol, gel and solidify, then it is thermally treated made of oxide or other compounds it is solid
The method of body.In recent years, colloidal sol -- gel technique is in glass, oxide coating and function ceramics powder, especially conventional method
The application for being difficult to the composite oxide material prepared, succeeding in the synthesis of high-critical temperature (P) oxide superconducting materials.
Further, the second minor element of the load in the second step is Ag and W, using infusion process, by AgNO3
It is mixed with H2WO3, is then immersed in γ-Al2O3The granule electrode surface of-Ti.Point that infusion process can make Ag and W relatively uniform
Cloth plays the role of mutually cooperateing on the surface of particle carrier.And rear granule electrode prepared by infusion process is utilized, the metal of load
Sull can be in γ-Al2O3Surface is in succession distribution from inside to outside, so that multiple element can not play catalysis jointly and make
With.
Meanwhile the loading particle in the second step takes the mode (heating of temperature programming in the baking modes of Muffle furnace
Speed is 10-25 DEG C/min) it is roasted.The preparation of granule electrode generally uses roasting direct to simplify its preparation flow
Mode loading particle is roasted, temperature programming is conducive to Payload element and is aoxidized in carrier surface with the highest crystal form of activity
Object exists.
γ-the Al prepared according to preparation method of the present invention2O3- Ti- (Ag/W) three dimensional particles electrode.
γ-Al of the present invention2O3Application of-Ti- (Ag/W) the three dimensional particles electrode in degradation coal chemical industrial waste water.
Medium between anodic-cathodic plate is preferably put into the card slot of three-dimensional reactor by the application first, and cathode-anode plate spacing is arranged
For 5cm, external power supply；A certain amount of γ-Al is placed between cathode-anode plate2O3- Ti- (Ag/W) three dimensional particles electrode, takes coal chemical industry
Waste water is in three-dimensional reactor；Aerator and power supply are opened, aeration quantity size is adjusted and current strength degrades to waste water.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor as the present invention, certain pole plate spacing is set
(5-8cm), external power supply；The granule electrode of 60g is placed between cathode-anode plate, waste water 500ml is in three-dimensional reactor；It opens and exposes
Device of air and power supply carry out micro-pore aeration, adjust aeration quantity size and current strength degrades to waste water.
The preferably homemade micro-pore aeration aeration reactor of the 3 D electrode reactor, structure are as shown in Figure 1.Water at present
Processing must the bubble techniques such as domain aeration, air bearing there are mass-transfer efficiencies it is low, energy consumption is high the problems such as, it is therefore desirable to microbubble technology into
Row deeper into research be applied to it preferably in practical water treatment technology.Microbubble technology has as one to be widely applied
The front line science technology of prospect causes quotient's degree of people to be paid close attention in recent years, and research is applied supports in medicine, environment, agricultural, aquatic products
It grows equal fields and obtains encouraging achievement.Due to can produce epidemic disease base free radical etc. when microbubble has underwater rupture, rupture
Good characteristic.
Compared with current technology, present invention has the advantage that
1, the present invention selects γ-Al2O3As load carriers, have the characteristics that absorption property is strong, high mechanical strength
2, γ-Al prepared by the present invention2O3- Ti- (Ag/W) novel three-dimensional ion electrode, with catalytic activity is high, low energy consumption
And the advantages that high recycling rate.
3, the preparation method provided by the invention it is easy to operate, convenient for control, and using temperature programming by the way of to bear
The crystal form of oxygen carrier compound shows more preferably electro-catalysis effect.
4, the granule electrode that the present invention is finally prepared can be widely applied to the neck such as sewage treatment, papermaking, coal mining, weaving
Domain.
Detailed description of the invention
Fig. 1 three-dimensional reactor schematic diagram
1 aerator, 2 be flowmeter, and 3 regulating valves, 4 micro porous aeration heads, 5 be micro-pore aeration plate, and 6 be direct current
Source, 7 be graphite plate, and 8 be titanium plate
Fig. 2 granule electrode production process
Specific embodiment
Invention is further described in detail With reference to embodiment.
It in following case study on implementation, carries out at room temperature, the temperature of indoor environment is generally 5-30 DEG C, various medicines used
Agent is that analysis is pure.
Embodiment 1:
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:4 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
It is impregnated, rinse processing, so that particle surface organic matter be made to be removed.Granule electrode is carried out instead with distilled water after cleaning
It is multiple to rinse, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid volume ratio 1:1) are mixed into
The butyl titanate mixed liquor of 0.5mol/L stirs evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, when instilling
Stirring；It continuously stirs at room temperature after mixing, is then allowed to stand 1h and completes TiO2The preparation of gel, after weighing 60g pretreatment
γ-Al2O3Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal
γ-the Al of salting liquid2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；It will dry
Good particle is put into temperature programming Muffle furnace, with the heating rate of 10 DEG C/min at 200 DEG C calcination activation 3h；It repeats above-mentioned
Required load Ti metal oxide particle electrode is made in step 2 time.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 10 DEG C/min's
Heating rate calcination activation 3h at 200 DEG C；It repeats the above steps 2 times, obtains required loaded Ag/W metal oxide
γ-Al2O3- Ti- (Ag/W) three dimensional particles electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 234MPa, compared with other grains
Sub-electrode (< 200MPa) shows very big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, setting pole plate spacing is 6cm, external power supply；?
The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator and electricity
Source adjusts aeration quantity size 15ml/min and current strength 0.1A, starts Study on degradation；It is sampled once every 30min, point
It Fen Xi not the indexs such as total phenol, COD and ammonia nitrogen concentration.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 680mg/L, 2700mg/L, 450mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is gone
Except rate has respectively reached 44.4%, 40% and 39.3%.
Embodiment 2:
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:5 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 10 DEG C/min at 300 DEG C calcination activation 3h；It repeats the above steps 2 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 10 DEG C/min's
Heating rate calcination activation 3h at 300 DEG C；It repeats the above steps 2 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 239MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 6cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator
And power supply, aeration quantity size 15ml/min and current strength 0.1A is adjusted, Study on degradation is started；One is sampled every 30min
It is secondary, the indexs such as total phenol, COD and ammonia nitrogen concentration are analyzed respectively.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 620mg/L, 2400mg/L, 330mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is gone
Except rate has respectively reached 56.0%, 50.6% and 44.6%.
Embodiment 3:
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode is main including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:5 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
It is impregnated, rinse processing, so that particle surface organic matter be made to be removed.Granule electrode is carried out instead with distilled water after cleaning
It is multiple to rinse, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid volume ratio 1:1) are mixed into 0.5mol/L
Four ester mixed liquor of metatitanic acid fourth, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；It is mixed
It is continuously stirred at room temperature after conjunction, is then allowed to stand 1h and completes TiO2The preparation of gel weighs the pretreated γ-of 60g
Al2O3Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried grain
Son is put into Muffle furnace, with the heating rate of 25 DEG C/min at 500 DEG C calcination activation 3h；It repeats the above steps 2 times, institute is made
The load Ti metal oxide particle electrode needed.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 25 DEG C/min's
Heating rate calcination activation 3h at 500 DEG C；It repeats the above steps 2 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 225MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 7cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator
And power supply, aeration quantity size 15ml/min and current strength 0.1A is adjusted, Study on degradation is started；One is sampled every 30min
It is secondary, the indexs such as total phenol, COD and ammonia nitrogen concentration are analyzed respectively.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 700mg/L, 2560mg/L, 420mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is gone
Except rate has respectively reached 37.5%, 47.3% and 44.0%.
Embodiment 4
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:6 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 20 DEG C/min at 300 DEG C calcination activation 3h；It repeats the above steps 4 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 25 DEG C/min's
Heating rate calcination activation 3h at 300 DEG C；It repeats the above steps 4 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.
It is detected through resistance to compression, the compression strength of the electrode is up to 237MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 7cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator
And power supply, aeration quantity size 15ml/min and current strength 0.1A is adjusted, Study on degradation is started；One is sampled every 30min
It is secondary, the indexs such as total phenol, COD and ammonia nitrogen concentration are analyzed respectively.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 600mg/L, 200mg/L, 320mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is removed
Rate has respectively reached 44.7%, 50.6% and 56.0%.
Embodiment 5
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:6 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 20 DEG C/min at 700 DEG C calcination activation 3h；It repeats the above steps 4 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 20 DEG C/min's
Heating rate calcination activation 3h at 700 DEG C；It repeats the above steps 4 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 225MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 8cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water waste water 500ml in three-dimensional reactor；Open aeration
Device and power supply adjust aeration quantity size 15ml/min and current strength 0.1A, start Study on degradation；It is taken every 30min
Sample is primary, analyzes the indexs such as total phenol, COD and ammonia nitrogen concentration respectively.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 750mg/L, 2740mg/L, 430mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is gone
Except rate has respectively reached 33.1%, 43.6% and 42.7%.
Embodiment 6
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:7 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 10 DEG C/min at 200 DEG C calcination activation 3h；It repeats the above steps 2 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.1mol/L AgNO3+0.1mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 10 DEG C/min's
Heating rate calcination activation 3h at 200 DEG C；It repeats the above steps 2 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 217MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 8cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator
And power supply, aeration quantity size 15ml/min and current strength 0.1A is adjusted, Study on degradation is started；One is sampled every 30min
It is secondary, the indexs such as total phenol, COD and ammonia nitrogen concentration are analyzed respectively.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 760mg/L, 2760mg/L, 435mg/L respectively from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen,
Its removal rate has respectively reached 32.1%, 43.2% and 42%.
Embodiment 7
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:7 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 10 DEG C/min at 200 DEG C calcination activation 3h；It repeats the above steps 2 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.5mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 10 DEG C/min's
Heating rate calcination activation 3h at 200 DEG C；It repeats the above steps 2 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 206MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 8cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator
And power supply, aeration quantity size 15ml/min and current strength 0.1A is adjusted, Study on degradation is started；One is sampled every 30min
It is secondary, the indexs such as total phenol, COD and ammonia nitrogen concentration are analyzed respectively.
After three-dimensional micropore aeration reactor continuous operation 1h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
780mg/L, 3000mg/L, ammonia nitrogen 610mg/ are down to from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen
L, removal rate have respectively reached 30.3%, 40% and 33.3%.
Embodiment 8
A kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, mainly including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:8 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 20 DEG C/min at 300 DEG C calcination activation 3h；It repeats the above steps 4 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 20 DEG C/min's
Heating rate calcination activation 3h at 300 DEG C；It repeats the above steps 4 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 238MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 8cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g is placed between cathode-anode plate, takes coal chemical industrial waste water 500ml in three-dimensional reactor；Open aerator
And power supply, aeration quantity size 15ml/min and current strength 0.1A is adjusted, Study on degradation is started；One is sampled every 30min
It is secondary, the indexs such as total phenol, COD and ammonia nitrogen concentration are analyzed respectively.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 550mg/L, 1500mg/L, 400mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is gone
Except rate has respectively reached 50.8%, 69.1% and 51%.
Embodiment 9
A kind of γ-Al2O3The novel method of the preparation of-Ti- (Ag/W) three dimensional particles electrode and coal chemical industrial waste water of degrading, it is main
It wants including the following steps:
Step 1: weighing the NH of the HF and 2g/L of 40ml/L respectively4F is the proportional arrangement of 1:8 into oxide by volume
Etching solution (BOE)；Weigh 60g γ-Al2O3Particle is poured into configured 200ml etching liquid, is set in shaking table temperature
100min is rocked under the conditions of being 30 DEG C, after rocking, particle is rinsed with distilled water；Using acetone soln to particle
Carrying out washing treatment is carried out, so that particle surface organic matter be made to be removed.Granule electrode is rushed repeatedly with distilled water after cleaning
It washes, until for neutrality；Pretreated particle is put into baking oven, is dried 12 hours at 105 DEG C, it is spare.
Step 2: the ratio that dehydrated alcohol and deionized water are 2:1 by volume is mixed, its pH is adjusted with HCl solution
To 2~3, A liquid is made；Butyl titanate, dehydrated alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid=1:1) are mixed into 0.5mol/L
Butyl titanate mixed liquor, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, is stirred when instilling；Mixing
After continuously stir at room temperature, be then allowed to stand 1h complete TiO2The preparation of gel weighs the pretreated γ-Al of 60g2O3
Particle is immersed in 200mlTiO obtained2In gel, and sufficiently reacted on shaking table；By impregnated Ti metal salt solution
γ-Al2O3Particle taking-up is placed in an oven, and dries 12h at being 105 DEG C in temperature, is dried for standby；By dried particle
Be put into Muffle furnace, with the heating rate of 20 DEG C/min at 300 DEG C calcination activation 3h；It repeats the above steps 4 times, needed for being made
Load Ti metal oxide particle electrode.
Step 3: loaded Ag/W metal oxide particle electrode preparation method.Configure 0.5mol/L AgNO3+0.05mol/
LH2WO3Ethanol solution (mixed volume ratio of the two is 1:1)；The pretreated particle of 60g is weighed, is put it into maceration extract,
4h is sufficiently reacted on shaking table；By the γ-Al of impregnated Ag/W metal salt solution2O3Particle taking-up is placed in an oven, and
Temperature is that drying is dried for standby more than 12h at 80 DEG C；Dried particle is respectively put into Muffle furnace, with 20 DEG C/min's
Heating rate calcination activation 3h at 300 DEG C；It repeats the above steps 4 times, obtains required loaded Ag/W metal oxide grain
Sub-electrode.It is detected through resistance to compression, the compression strength of the electrode is up to 236MPa, shows very compared with other granule electrodes (< 200MPa)
Big advantage.
Medium between anodic-cathodic plate is put into first in the card slot of three-dimensional reactor, it is 8cm, external electricity that certain pole plate spacing, which is arranged,
Source；The granule electrode that 60g has reused 20 times (same degradation 3h every time) is placed between cathode-anode plate.Granule electrode at this time
Mechanical strength be 233MPa.Take coal chemical industrial waste water 500ml in three-dimensional reactor；Aerator and power supply are opened, adjusts and exposes
Tolerance size 15ml/min and current strength 0.1A starts Study on degradation；It is sampled once every 30min, analysis is total respectively
The indexs such as phenol, COD and ammonia nitrogen concentration.
After three-dimensional micropore aeration reactor continuous operation 3h, preferable wastewater degradation effect is achieved, wherein total phenol, COD
It is down to 620mg/L, 2030mg/L, 430mg/L from 1223mg/L, 4500mg/L, 741mg/L respectively with the content of ammonia nitrogen, is gone
Except rate has respectively reached 49.3%, 54.9% and 42%,.It can be seen that ion electrode produced by the present invention have it is splendid steady
It is qualitative.
Finally illustrate: the above case study on implementation is only used to illustrate technical solution of the present invention, referring to best experiment of the invention
The detailed description that condition carries out case study on implementation, meanwhile, when those skilled in the art repair technical solution of the present invention
Change or approximation is replaced, and do not depart from the range of technical solution of the present invention, claim model of the invention should all be covered on
In enclosing.
Claims (10)
1. a kind of γ-Al2O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, it is characterised in that the following steps are included:
The first step, first to carrier particle γ-Al2O3It is pre-processed, weighs quantitative carrier particle and be put into etching solution profit
It washes；Then particle is handled using acetone soln, repeated flushing is carried out to granule electrode with distilled water after cleaning, until being
It is neutral；Finally pretreated particle is put into baking oven and is dried for standby；
Dehydrated alcohol and deionized water are mixed, adjust its pH to 2~3 with HCl solution by second step, and A liquid is made；By metatitanic acid four
Butyl ester, dehydrated alcohol and glacial acetic acid mixing, stir evenly obtained B liquid；A liquid is added dropwise in isometric B liquid, side instills
Side stirring；It continuously stirs 5min at room temperature after mixing, is then allowed to stand and completes TiO2The preparation of gel；Then by carrier grain
Son is immersed in TiO obtained2In gel, and 1~4h is sufficiently reacted on shaking table；By the carrier of impregnated Ti metal salt solution
Particle taking-up is placed on dries in an oven；Dried particle is respectively put into Muffle furnace, roasts and lives at 100~800 DEG C
Change 1~4h；It repeats the above steps 2~5 times, required load Ti metal oxide particle is made；
Third step configures certain density AgNO3+H2WO4Ethanol solution；Load Ti metal oxide grain prepared by second step
Son is put into maceration extract AgNO3+H2WO4In ethanol solution, a period of time is sufficiently reacted on shaking table；Ag/W metal will then be impregnated
The load Ti metal oxide particle taking-up of salting liquid is placed in an oven, and is dried at being 80 DEG C in temperature more than 12h, drying
It is spare；Then dried particle is respectively put into Muffle furnace, 1~4h of calcination activation at 100~800 DEG C；It repeats above-mentioned
Step 2~5 time obtain γ-Al2O3- Ti- (Ag/W) three dimensional particles electrode.
2. γ-Al according to claim 12O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, which is characterized in that
The NH of HF and 2g/L that etching solution in the first step is 40ml/L4The F mixed solution in 1:4~8 by volume.
3. γ-Al according to claim 12O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, which is characterized in that
The volume ratio of the second step dehydrated alcohol and deionized water is 1~3:1, preferably 2:1.
4. γ-Al according to claim 12O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, which is characterized in that
The second step dehydrated alcohol and glacial acetic acid volume ratio are 1:1~2, preferably 1:1:1；Butyl titanate is in dehydrated alcohol and ice vinegar
Concentration in acid solution is 0.5~10.5mol/L.
5. γ-Al according to claim 12O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, which is characterized in that
State second step carrier particle and TiO2The mass volume ratio of gel is 1:2~5, preferably 1:3.
6. γ-Al according to claim 12O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, which is characterized in that
The third step AgNO3The concentration of ethanol solution is 0.5mol/L, H2WO4The concentration of ethanol solution is 0.05mol/L；AgNO3Second
Alcoholic solution and H2WO4The volume ratio of ethanol solution is 1:1.
7. γ-Al according to claim 12O3The preparation method of-Ti- (Ag/W) three dimensional particles electrode, which is characterized in that
Heating means in the second step and third step in Muffle furnace take the mode of temperature programming, with the speed of 10~25 DEG C/min
It is warming up to 100~800 DEG C.
8. γ-the Al prepared according to preparation method according to any one of claims 1 to 72O3- Ti- (Ag/W) three dimensional particles electricity
Pole.
9. γ-Al according to any one of claims 82O3Application of-Ti- (Ag/W) the three dimensional particles electrode in degradation coal chemical industrial waste water.
10. application according to claim 9, it is characterised in that medium between anodic-cathodic plate is put into the card slot of three-dimensional reactor first
Interior, setting pole plate spacing is 5cm, external power supply；A certain amount of γ-Al according to any one of claims 8 is placed between cathode-anode plate2O3-
Ti- (Ag/W) three dimensional particles electrode, takes coal chemical industrial waste water in three-dimensional reactor；Aerator and power supply are opened, aeration is adjusted
Amount size and current strength degrade to waste water.
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| CN112723621A (en) * | 2020-12-28 | 2021-04-30 | 华南理工大学 | Co-Ce-Zr/gamma-Al for treating ciprofloxacin wastewater2O3Composite particle electrode and preparation method and application thereof |
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