CN110156119A - A kind of ferrite modification carbon fiber cloth electrode and the preparation method and application thereof - Google Patents
A kind of ferrite modification carbon fiber cloth electrode and the preparation method and application thereof Download PDFInfo
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- CN110156119A CN110156119A CN201910498749.6A CN201910498749A CN110156119A CN 110156119 A CN110156119 A CN 110156119A CN 201910498749 A CN201910498749 A CN 201910498749A CN 110156119 A CN110156119 A CN 110156119A
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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
- C02F1/467—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4619—Supplying gas to the electrolyte
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of ferrite modification carbon fiber cloth electrodes and its preparation method and application, comprising the following steps: 1) prepared by modified carbon fiber cloth；2) prepared by Ferrite Material modification carbon cloth electrochemical cathode.The invention also discloses the Ferrite Material modification carbon fiber cloth electrode and its applications.The Ferrite Material modification carbon cloth electrochemical cathode, can be used for electrochemistry/ozone coupling water treatment system.The preparation method raw material drawing is convenient, preparation process is simple, low in cost, catalytic activity is high, electrode performance is superior, is a kind of low energy consumption, high efficiency, the complete water treatment technology of pollutant mineralising.It is had broad application prospects using the modified carbon fiber cloth electrochemical cathode of the modification of ferrite prepared by the present invention in circulation electric filter system degradation persistence organic pollutant (POPs).
Description
Technical field
The invention belongs to advanced treatment of wastewater fields, and in particular to ferrite modification carbon fiber cloth electrode and its preparation
Methods and applications, in particular to using ferrite modification carbon cloth electrochemical cathode and carbon cloth anode in electrification
Application in terms of/ozone coupling system degradation POPs pollutant.
Background technique
The source of POPs is mainly to pass through following two approach in water environment: first is that the life containing higher concentration POPs is dirty
Water, industrial wastewater, hospital wastewater etc. are not exclusively removed into the natural waters such as rivers and lakes by sewage treatment plant；Second is that agriculture
Industry, animal husbandry, aquatic products industry direct discharging of waste water or underground diafiltration enter POPs in water environment.Due to POPs component extensively and
Concentration is low in sewage, and the ability that conventional processing technique removes this pollutant is extremely limited.Therefore need to study degradation effect more
Good technique, further increases the water quality of sewage treatment.
The development of high-level oxidation technology (Advanced oxidation processes, AOPs) in recent years is increasingly
Good, it is the advanced treatment of wastewater technology with the characteristics of the hydroxyl radical free radical of stronger oxidability (OH).Hydroxyl radical free radical
Oxidation-reduction potential is 2.8V, is higher than ozone (2.08V) and liquid chlorine (1.36V), when reacting with organic pollutant, is had higher
Reaction rate is (up to 106~109Mol/ (Ls)), and non-selectivity when being aoxidized, the organic matter in water can thoroughly be turned
Turn to CO2And H2O.Currently used high-level oxidation technology have Fenton oxidation method, electrochemical oxidation process, catalytic ozonation method with
And H2O2/O3、UV/O3Deng coupling ozonation process.
Summary of the invention
The technical problem to be solved by the present invention is to due to POPs component extensively in sewage concentration it is low, conventional process skill
The ability that art removes this pollutant is extremely limited.
Based on the above technical problem,
The present invention provides a kind of preparation method of ferrite modification carbon fiber cloth electrode, the preparation method raw material
Drawing materials, convenient, preparation process is simple, low in cost, catalytic activity is high, electrode performance is superior, is a kind of low energy consumption, high efficiency, dirt
Contaminate the complete water treatment technology of object mineralising.
Modified carbon fiber cloth in the preparation of the electrode carries out surface by strong oxidizing solution or alkaline solution and is modified, iron oxygen
Body is the oxide of single or polynary iron.
The present invention also provides the ferrite modification carbon fiber cloth electrodes that the preparation method obtains, for electrification
/ ozone coupling water treatment system, modified carbon fiber cloth and ferrite co-catalysis original position hydrogen peroxide and ozone efficiently generate hydroxyl
Base free radical improves water process efficiency.
The present invention also provides the applications of ferrite modification carbon cloth electrochemical cathode.Using prepared by the present invention
Ferrite modification carbon fiber cloth electrode efficient catalytic hydrogen peroxide and ozone generate hydroxyl radical free radical in terms of have it is very big before
Scape.
Specifically, the technical scheme adopted by the invention is as follows:
A kind of preparation method of ferrite modification carbon fiber cloth electrode, which comprises the following steps:
1) preparation of modified carbon fiber cloth: carrying out surface to carbon cloth with strong oxidizing solution or alkaline solution and be modified,
Drying is obtained by drying；
2) preparation of ferrite modification carbon cloth: step 1) is added when hydrothermal co-precipitation method prepares ferrite and obtains
Modified carbon fiber cloth, obtain ferrite modification carbon fiber cloth electrode.
Further,
Strong oxidizing solution described in step 1) are as follows: concentrated nitric acid, the concentrated sulfuric acid, chlorine, bromine, iodine oxyacid, Fenton reagent, mistake
Sulfate liquor, the one or more of potassium ferrate solution；In the present invention, the selection for strong oxidizing solution includes but unlimited
In above several.
Chlorine of the present invention, bromine, iodine oxyacid with no restriction, can choose chlorine in the prior art, bromine, iodine and contain
Oxygen acid, such as: hypochlorous acid, hypobromous acid, hypoiodous acid.
For example, can be concentrated nitric acid, the concentrated sulfuric acid, chlorine, bromine, iodine oxyacid, Fenton reagent, persulfate solution, high-speed rail
Any one of sour potassium solution；It can be commonly used in the prior art for being applied in combination of above-mentioned strong oxidizing solution
Combination is also possible to following combination: concentrated nitric acid, the mixed solution of the concentrated sulfuric acid；The mixing of persulfate and potassium ferrate is molten
Liquid etc..
Alkaline solution described in step 1) is strong alkali solution, be can choose as in the prior art, available strong basicity is molten
Liquid；
It is further preferred that the strong alkali solution is KOH solution and/or NaOH solution, for example, can be KOH solution
Or the mixture of NaOH solution or KOH solution and NaOH solution.
Further, the preparation of step 1) modified carbon fiber cloth: carbon cloth is fully immersed in molten equipped with strong oxidizing property
In liquid, ultrasound is subsequently placed in isothermal reaction kettle and reacts, after surface residual debris impurity is washed with water, until pH, to neutrality, rear vacuum is dried
Case modified carbon fiber cloth obtained by drying；In the step, ultrasonic time is with no restrictions.
Further；The mass volume ratio of the carbon cloth and strong oxidizing solution or alkaline solution is 1.0g:(100
~300mL)；That is, every addition 1.0g carbon cloth, needs the lye of 100-300mL.
Further, in step 1), isothermal reaction kettle reaction temperature is 35-80 DEG C；Such as 35 DEG C, 40 DEG C, 45 DEG C, 60
DEG C, 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79 DEG C, 80 DEG C etc..
Further, in step 1), isothermal reaction kettle reaction temperature is 40-60 DEG C；Such as 40 DEG C, 45 DEG C, 46 DEG C, 47
DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 55 DEG C, 56 DEG C, 57 DEG C, 58 DEG C, 59 DEG C, 60 DEG C etc..
Further, in step 1), isothermal reaction kettle reaction temperature is 50 DEG C；
Further, in step 1), the isothermal reaction kettle reaction time is 12h~72h；Such as can be non-limiting selection it is dry
The dry time be 12h, 13h, 15h, 18h, 20h, for 24 hours, 30h, 36h, 40h, 48h, 50h, 55h, 60h, 65h, 70h, 71h, 72h
Deng.
Further, in step 1), the isothermal reaction kettle reaction time is for 24 hours~60h；
Further, in step 1), the isothermal reaction kettle reaction time is 48h；
Further, in step 1), with milli-Q water surface residual debris impurity；
Further, in step 1), vacuum drying oven temperature is 30-75 DEG C；Such as 35 DEG C, 40 DEG C, 45 DEG C, 60 DEG C, 75 DEG C.
Further, in step 1), vacuum drying oven temperature is 35-50 DEG C；
Further, in step 1), vacuum drying oven temperature is 40 DEG C.
Further,
Chlorine in the step 1), bromine, iodine the concentration of oxyacid be 0.1-0.5mol/L, such as 0.1mol/L, 0.2mol/
L、0.3mol/L、0.4mol/L、0.45mol/L、0.46mol/L、0.47mol/L、0.48mol/L、0.49mol/L、0.5mol/
L。
Fenton reagent is 0.2-0.6mol/L Fe in the step 1)2+With the H of 30wt%2O2。
In the step 1) persulfate solution concentration be 0.1-0.5mol/L, such as 0.1mol/L, 0.2mol/L,
0.3mol/L、0.4mol/L、0.45mol/L、0.46mol/L、0.47mol/L、0.48mol/L、0.49mol/L、0.5mol/L。
In the step 1) potassium ferrate solution concentration be 0.1-0.5mol/L, such as 0.1mol/L, 0.2mol/L,
0.3mol/L、0.4mol/L、0.45mol/L、0.46mol/L、0.47mol/L、0.48mol/L、0.49mol/L、0.5mol/L。
Strong alkali solution is the KOH solution and/or 1-3mol/L NaOH solution of 1-3mol/L in the step 1).
Further, step 2) are as follows:
2) preparation of ferrite modification carbon cloth: step 1) is added when hydrothermal co-precipitation method prepares ferrite and obtains
Modified carbon fiber cloth, ultrasonic mixing, constant temperature blender with magnetic force effect under react a period of time, will load later ferritic
Carbon cloth drying is put into the tube furnace under inert gas atmosphere protection, roasting a period of time, and taking-up is cooling to obtain iron oxygen
Body modification carbon fiber cloth electrode；
Further, the ferrite of the step 2) is the single ferrite and/or spinel type ferrite of transition metal.
Further, the step 2) are as follows:
2) preparation of ferrite modification carbon cloth:
It is added into ultrapure water and contains Fe3+Salt and M2+Then salt uses magnetic stirrer so that it is uniformly mixed simultaneously
Be completely dissolved to obtain mixed solution, and be added thereto polyethylene glycol or ammonium fluoride and urea admixture (these substances plus
The purpose entered is to can be understood as following two situation herein for controlling grain size: 1, polyethylene glycol, which is added, can be used for
Control the size of crystal grain, 2, the mixture for being added ammonium chloride and urea can be used for the size of control crystal grain) continue stirring i.e.
, it is placed on reaction in isothermal reaction kettle later, cools down after completion of the reaction, washs, is placed in thermostatic drying chamber and dries, then
It is placed in electric tube furnace, is passed through inert gas as protection gas, roasts to get ferrite modification carbon cloth；Above-mentioned
In preparation method, the modified carbon fiber cloth is added in co-precipitation before being formed.
For example, in some embodiments, the modified carbon fiber cloth is added before co-precipitation is formed can be when following
Machine:
1, it is added into ultrapure water and contains Fe3+Salt and M2+(Fe is being added in salt3+Salt and M2+Add before or after salt
Enter modified carbon fiber cloth, modified carbon fiber cloth can also be with Fe3+Salt and M2+Salt is added simultaneously), then use magnetic stirring apparatus
It stirs so that it is uniformly mixed and is completely dissolved to obtain mixed solution, and polyethylene glycol or ammonium fluoride and urine are added thereto
Plain mixture continues to stir to obtain the final product, is placed on reaction in isothermal reaction kettle later, cools down after completion of the reaction, washs, be placed on perseverance
It dries, is subsequently placed in electric tube furnace in warm drying box, be passed through inert gas as protection gas, roasting is to get ferrite modification
Modified carbon fiber cloth.
2, it is added into ultrapure water and contains Fe3+Salt and M2+Then salt uses magnetic stirrer so that it is uniformly mixed
And it is completely dissolved to obtain mixed solution, and polyethylene glycol or ammonium fluoride and urea admixture are added thereto (in the poly- second of addition
It is added before glycol or ammonium fluoride and urea admixture) continue to stir to obtain the final product, it is placed on reaction in isothermal reaction kettle later,
It cools down after completion of the reaction, washs, be placed in thermostatic drying chamber and dry, be subsequently placed in electric tube furnace, be passed through inert gas work
To protect gas, roast to get ferrite modification carbon cloth.
3, it is added into ultrapure water and contains Fe3+Salt and M2+Then salt uses magnetic stirrer so that it is uniformly mixed
And it is completely dissolved to obtain mixed solution, and polyethylene glycol or ammonium fluoride and urea admixture are added thereto (in the poly- second of addition
It is added after glycol or ammonium fluoride and urea admixture) continue to stir to obtain the final product, it is placed on reaction in isothermal reaction kettle later,
It cools down after completion of the reaction, washs, be placed in thermostatic drying chamber and dry, be subsequently placed in electric tube furnace, be passed through inert gas work
To protect gas, roast to get ferrite modification carbon cloth.
The one or more of described M=Fe, Mn, Ni, Cu, Co；
Further, the Fe3+Salt and M2+The molar concentration rate of salt is 1-4；
Further, the Fe3+Salt and M2+The molar concentration rate of salt is 2.
Further, the degree of isothermal reaction kettle temperature described in step 2) is 20-140 DEG C；Further, perseverance described in step 2)
Warm temperature of reaction kettle is 40-130 DEG C；
Further, the reaction time is 2-100h in isothermal reaction kettle described in step 2)；Further, institute in step 2)
Stating the reaction time in isothermal reaction kettle is 12-72h；
Further, maturing temperature described in step 2) is 300-400 DEG C；Further, temperature is roasted described in step 2)
Degree is 350 DEG C；
Further, in step 2), the heating rate of electric tube furnace is 2-10 DEG C/min；Further, in step 2), pipe
The heating rate of formula electric furnace is 5 DEG C/min；
Further, calcining time described in step 2) is 0.5-3 hours；Further, when being roasted described in step 2)
Between be 1 hour.
There is no particular restriction for ferrite type and type in electrode production process of the present invention, and the prior art can be used
In common ferrite type and type, also there is no particular restriction for the mass ratio of ferrite and modified carbon fiber cloth material.
As optimal technical scheme, the mass ratio of ferrite and modified carbon fiber cloth material in the step 2) is 1:2
~1:8, such as it is 1:2,1:3,1:4,1:4.1,1:4.5,1:5,1:6,1:7,1:8 etc. that the two ratio, which can choose,.
The present invention also provides a kind of electrochemistry/ozone coupling water treatment system,
The electrochemistry/ozone coupling water treatment system includes the oxygen cylinder (1) being sequentially connected, oxygen flow meter (2), ozone
Generator (3), ozone detector (12), ac/Dc power (4) and reaction unit (7)；
The reaction unit (7) is also connected with peristaltic pump (13) and mother liquor tank (14), peristaltic pump (13) setting and mother
Between flow container (14) and reaction unit, forming circuit；Peristaltic pump (13) is for being pressurized the liquid in mother liquor tank (14), being increased
Speed makes the solution containing target contaminant enter reaction unit (7)
The reaction unit (7) includes exhaust outlet (6), anode (8), cathode (10), insulation silica gel pad (9), aeration dress
Set (11)；The anode (8) and cathode (10) are separately positioned on the top and the bottom of reaction unit (7), are oppositely arranged in parallel, described
Silica gel pad (9) setting insulate between anode (8) and cathode (10), the anode (8), cathode (10) and insulation silica gel pad
(9) it is arranged in parallel；The top of reaction unit is arranged in the exhaust outlet (6), is higher than the cathode (8) position；The aeration dress
(11) are set to be set at the air inlet of reaction unit (7)；Ozone, can be with micro-bubble after aerator (11)；
The anode (8) and cathode (10) of the ac/Dc power (4) are connected to ac/Dc power (4), shape
At circuit；
Further, the electrochemistry/ozone coupling water treatment system further includes exhaust gas processing device (5), the tail gas
Processing unit (5), the exhaust outlet (6) being connected on setting and reaction unit (7).
The cathode (10) is ferrite modification carbon fiber cloth electrode；
The anode (8) is original carbon fiber cloth, felt electrode, graphite electrode, stainless steel electrode, Ti electrode, noble metal
Any one of electrode or boron-doped diamond electrode；
Further, the anode (8) is original carbon cloth；
Further, the aerator (11) is set at cathode bottom (10) 0.1cm；
Further, aerator (11) aeration area is consistent with cathode size；
Further, aerator (11) Air Bubble Size is micro/nano level；
Further, the aerator (11) is microporous aeration disc, hydraulic flow emitter or duct type air and liquid mixer.
Under electrochemistry/ozone coupling catalytic action, which thoroughly degrades to POPs pollutant.
The invention also discloses a kind of ferrite modification carbon fiber cloth electrodes obtained by above-mentioned preparation method in electricity
Application in chemical cathode material or sewage treatment.
Further, above-mentioned application is to carry out sewage treatment, packet using above-mentioned electrochemistry/ozone coupling water treatment system
Include following steps:
It opens peristaltic pump (13), the solution containing target contaminant in mother liquor tank (14) is pressurized, speedup, made containing target
The solution of pollutant enters reaction unit (7), circuits sequentially and flows through cathode, between anode and cathode；Oxygen is through ozone generator
Ozone is generated, ozone is first passed through with micro-bubble after aerator (12) and enters liquid/solid behind cathode (10) bottom and connect
Contact layer (contact surface of electrode and liquid), enters back between anode and cathode solution, the liquid after reaction finally returns to mother liquor with water flow
In tank (14), the tail gas after reaction enters exhaust gas processing device (5) through exhaust outlet (6), handles heel row through exhaust gas processing device (5)
It puts.
Further, peristaltic pump (13) revolving speed is 0~100 rev/min.
The beneficial effects of the present invention are:
1) preparation method of ferrite modification carbon cloth electrochemical cathode of the invention.The preparation method raw material
Drawing materials, convenient, preparation process is simple, low in cost, catalytic activity is high, electrode performance is superior, is a kind of low energy consumption, high efficiency, dirt
Contaminate the complete water treatment technology of object mineralising.
2) modification is modified to modified carbon fiber cloth using ferrite, improves the activity of catalysis ozone and hydrogen peroxide,
Double carbon cloths can combine the filtering absorption of carbon cloth and catalytic degradation to be integrated, realize the efficient of object as anode and cathode
There is many advantages, such as treatment effeciency is high, occupied area is small, low energy consumption to have preferable application in terms of POPs is degraded in processing for degradation
Prospect.
3) the modified reusing of carbon cloth, stability and catalytic performance are all significantly improved, according to difference
It needs, different solution is selected to be modified carbon cloth, introducing different functional groups, (it is exactly logical for introducing different functional groups implementation
Different solutions progress carbon cloth is crossed to be modified to realize), realize directional catalyzing effect；Different catalysis can also be selected as needed
Agent, the Ferrite Material or photochemical catalyst that also more than one can be selected to be modified in same reaction unit, can also be in photocatalysis body
System realizes the degradation of specific pollutants.
4) oxide of transition metal be it is a kind of can simultaneously catalysis ozone and decomposing hydrogen dioxide solution generate OH one kind it is novel
Catalyst modifies carbon cloth using transition metal and particular functional group, can improve the degradation of system to greatest extent
Ability also can prepare the electrochemical cathode for being best suited for Fourier Series expansion technique, especially fit by optimizing selection to composition proportion
Close the POPs pollutant of processing composition component complexity.
5) ferrite modification carbon cloth electrochemical cathode helps to improve electrochemistry/O3Fourier Series expansion technique is to POPs dirt
The degradation property of object, metallic particles special crystal structure are contaminated, oxygen defect can be catalyzed reaction, can also provide for electron transmission logical
Road, while carbon cloth electrode has absorption property, forms absorption-catalytic degradation process, efficient degradation pollutant；Micro- aerator changes
It is apt to ozonation aerated aperture, improves reaction mass transfer efficiency.
Detailed description of the invention
1 ferrite modification carbon cloth electrochemical cathode preparation flow schematic diagram of attached drawing；
Mixing in attached drawing 1 with material, material refer to modified carbon nano tube cloth.
The micro- aerator of attached drawing 2 assists lower electrochemistry/ozone coupling water treatment system circulation degradation POPs pollutant to show
It is intended to；
Appended drawing reference: 1, oxygen cylinder；2, oxygen flow meter；3, ozone generator；4, ac/Dc power；5, at tail gas
Manage device；6, exhaust outlet；7, reaction unit；8, anode；9, insulate silica gel pad；10, cathode；11, aerator；12, ozone
Detector；13, peristaltic pump；14, mother liquor tank.
Attached drawing 3-1 original carbon fiber cloth scanning electron microscope (SEM) photograph.
Attached drawing 3-2 carbon cloth loads transmission electron microscope picture after ferrite.
The comparison of 4 different process removal rate of attached drawing.
In attached drawing 4, ozone is independent ozone (having statement in embodiment), i.e. ozone oxidation removes organic matter；
Modified carbon cloth are as follows: electrochemistry/O3Couple water treatment system (ferrite modification carbon fiber cloth electrode of the invention
As cathode)；
Original carbon cloth are as follows: electrochemistry/O3It couples water treatment system (original carbon fiber cloth is as cathode)；
Electrochemistry is independent electrochemistry (having statement in embodiment): i.e. electrochemistry removal organic matter (repair for ferrite by cathode
Adorn modified carbon fiber cloth electrode).
5 different process TOC of attached drawing degradation situation comparison.
In attached drawing 5, ozone is independent ozone (having statement in embodiment), i.e. ozone oxidation removes organic matter,
Modified carbon cloth are as follows: electrochemistry/O3Couple water treatment system (ferrite modification carbon fiber cloth electrode of the invention
As cathode)；
Original carbon cloth are as follows: electrochemistry/O3It couples water treatment system (original carbon fiber cloth is as cathode)；
Electrochemistry is independent electrochemistry (having statement in embodiment): i.e. electrochemistry removal organic matter (repair for ferrite by cathode
Adorn modified carbon fiber cloth electrode).
6 electrochemistry of attached drawing/O3Water treatment system is coupled to different POPs removal situation comparison.
7 electrochemistry of attached drawing/O3Water treatment system is coupled to the relational graph of POPs pollutants removal rate and reaction solution pH.
8 electrochemistry of attached drawing/O3Water treatment system is coupled to the relational graph of POPs pollutants removal rate and electrode access times.
Specific embodiment
Below by specific embodiment, the present invention is further described, it is noted that for the ordinary skill of this field
For personnel, without departing from the principle of the present invention, several variations and modifications can also be made, these also should be regarded as belonging to
Protection scope of the present invention.
The preparation of 1 ferrite modification carbon cloth electrochemical cathode of embodiment
1) original carbon cloth is cut into the circle of 3.5cm diameter, mass fraction is used to divide for 10% nitric acid and quality
The mixed liquor for the sulfuric acid solution (nitric acid: sulfuric acid volume ratio is 3:1) that number is 10% impregnated carbon cloth, by 30 minutes surpass
It after sonication, is reacted 48 hours in 50 DEG C of isothermal reaction kettle, after solution is cooling, for several times with milli-Q water, removes table
Face residue impurity is until cleaning solution pH to be neutral, is then sufficiently being dried in 40 DEG C of vacuum drying ovens, until reaching constant matter
Amount is to get modified carbon fiber cloth；
2) above-mentioned modified carbon fiber is arranged in ultrapure water and is impregnated, 0.4mol/L Fe is then added in ultrapure water
(NO3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O, ultrasound make it after mixing and are completely dissolved to be mixed for 1 hour
Solution, and addition ammonium fluoride and urea continue to stir thereto, are placed on reaction 12 hours in 120 DEG C of isothermal reaction kettles later,
The ferrite modification carbon cloth after washing is placed in 40 DEG C of thermostatic drying chambers after cooling and is dried, tubular type electricity is subsequently placed in
In furnace, inert gas is passed through as protection gas, is roasted 1 hour under the conditions of 350 DEG C, up to ferrite modification carbon after cooling
Fiber cloth electrode.The ferrite modification carbon fiber cloth electrode transmission electron microscope picture is as shown in attached drawing 3-2.
The preparation of 2 ferrite modification carbon cloth electrochemical cathode of embodiment
1) original carbon cloth is cut into the circle of 3.5cm diameter, takes the H of 1.5mL 30wt%2O2With the ultrapure water of 97mL
It is placed in 250mL conical flask, and is adjusted to the Fe of addition 1.5mL 0.2mol/L after pH to 32+Solution (can be ferrous sulfate or chlorine
Change ferrous solution), carbon cloth is impregnated, after 30 minutes ultrasonic treatments, it is small that 48 are reacted in 50 DEG C of isothermal reaction kettle
When, after solution is cooling, for several times with milli-Q water, surface residual debris impurity is removed until cleaning solution pH is neutrality, then 40
Sufficiently dry in DEG C vacuum drying oven, until reaching constant quality to get modified carbon fiber cloth；
2) above-mentioned modified carbon fiber is arranged in ultrapure water and is impregnated, 0.4mol/L Fe is then added in ultrapure water
(NO3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O, ultrasound make it after mixing and are completely dissolved to be mixed for 1 hour
Solution, and addition ammonium fluoride and urea continue to stir thereto, are placed on reaction 12 hours in 120 DEG C of isothermal reaction kettles later,
The ferrite modification carbon cloth after washing is placed in 40 DEG C of thermostatic drying chambers after cooling and is dried, tubular type electricity is subsequently placed in
In furnace, inert gas is passed through as protection gas, is roasted 1 hour under the conditions of 350 DEG C, up to ferrite modification carbon after cooling
Fiber cloth electrochemical cathode.
Embodiment 3
The difference from embodiment 1 is that by mass fraction be 10% nitric acid and mass fraction be 10% sulfuric acid solution
The mixed liquor replacement of (nitric acid: sulfuric acid volume ratio is 3:1) are as follows: the hypochlorous acid of 0.3mol/L, other are the same as embodiment 1.
Embodiment 4
The difference from embodiment 1 is that by mass fraction be 10% nitric acid and mass fraction be 10% sulfuric acid solution
The mixed liquor replacement of (nitric acid: sulfuric acid volume ratio is 3:1) are as follows: the sodium peroxydisulfate solution of 0.3mol/L, other are the same as embodiment 1.
Embodiment 5
The difference from embodiment 1 is that by mass fraction be 10% nitric acid and mass fraction be 10% sulfuric acid solution
The mixed liquor replacement of (nitric acid: sulfuric acid volume ratio is 3:1) are as follows: the potassium ferrate solution of 0.3mol/L, other are the same as embodiment 1.
Embodiment 6
The difference from embodiment 1 is that by mass fraction be 10% nitric acid and mass fraction be 10% sulfuric acid solution
The mixed liquor replacement of (nitric acid: sulfuric acid volume ratio is 3:1) are as follows: the KOH solution of 2mol/L, other are the same as embodiment 1.
Embodiment 7
The difference from embodiment 1 is that by mass fraction be 10% nitric acid and mass fraction be 10% sulfuric acid solution
The mixed liquor replacement of (nitric acid: sulfuric acid volume ratio is 3:1) are as follows: the NaOH solution of 2mol/L, other are the same as embodiment 1.
Embodiment 8
The difference from embodiment 1 is that by mass fraction be 10% nitric acid and mass fraction be 10% sulfuric acid solution
The mixed liquor replacement of (nitric acid: sulfuric acid volume ratio is 3:1) are as follows: the NaOH solution of 2mol/L and the KOH solution (2mol/L of 2mol/L
NaOH solution: the KOH solution volume ratio of 2mol/L be 1:1), other are the same as embodiment 1.
Embodiment 9 (opportunity is added in modified carbon fiber cloth: being added after molysite and other salt are added)
1) original carbon cloth is cut into the circle of 3.5cm diameter, mass fraction is used to divide for 10% nitric acid and quality
The mixed liquor for the sulfuric acid solution (nitric acid: sulfuric acid volume ratio is 3:1) that number is 10% impregnated carbon cloth, by 30 minutes surpass
It after sonication, is reacted 48 hours in 50 DEG C of isothermal reaction kettle, after solution is cooling, for several times with milli-Q water, removes table
Face residue impurity is until cleaning solution pH to be neutral, is then sufficiently being dried in 40 DEG C of vacuum drying ovens, until reaching constant matter
Amount is to get modified carbon fiber cloth；
2) 0.4mol/L Fe (NO is added in ultrapure water3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O, it is molten to its
Modified carbon fiber cloth is added in Xie Hou, and ultrasound makes it after mixing in 1 hour and is completely dissolved to obtain mixed solution, and thereto
Ammonium fluoride is added and urea continues to stir, is placed on reaction 12 hours in 120 DEG C of isothermal reaction kettles later, it will be after washing after cooling
Ferrite modification carbon cloth be placed in 40 DEG C of thermostatic drying chambers and dry, be subsequently placed in electric tube furnace, be passed through inertia
Gas roasts 1 hour under the conditions of 350 DEG C as protection gas, up to ferrite modification carbon fiber cloth electrode after cooling.
Embodiment 10 (opportunity is added in modified carbon fiber cloth: being added simultaneously with molysite and other salt)
1) original carbon cloth is cut into the circle of 3.5cm diameter, mass fraction is used to divide for 10% nitric acid and quality
The mixed liquor for the sulfuric acid solution (nitric acid: sulfuric acid volume ratio is 3:1) that number is 10% impregnated carbon cloth, by 30 minutes surpass
It after sonication, is reacted 48 hours in 50 DEG C of isothermal reaction kettle, after solution is cooling, for several times with milli-Q water, removes table
Face residue impurity is until cleaning solution pH to be neutral, is then sufficiently being dried in 40 DEG C of vacuum drying ovens, until reaching constant matter
Amount is to get modified carbon fiber cloth；
2) 0.4mol/L Fe (NO is added in ultrapure water3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O adds simultaneously
Enter modified carbon fiber cloth, ultrasound makes it after mixing in 1 hour and is completely dissolved to obtain mixed solution, and fluorination is added thereto
Ammonium and urea continue to stir, and reaction 12 hours in 120 DEG C of isothermal reaction kettles are placed on later, by the ferrite after washing after cooling
Modification carbon cloth is placed in 40 DEG C of thermostatic drying chambers and dries, and is subsequently placed in electric tube furnace, is passed through inert gas conduct
Gas is protected, is roasted 1 hour under the conditions of 350 DEG C, up to ferrite modification carbon fiber cloth electrode after cooling.
Embodiment 11 (opportunity is added in modified carbon fiber cloth: being added before ammonium fluoride and urea)
1) original carbon cloth is cut into the circle of 3.5cm diameter, mass fraction is used to divide for 10% nitric acid and quality
The mixed liquor for the sulfuric acid solution (nitric acid: sulfuric acid volume ratio is 3:1) that number is 10% impregnated carbon cloth, by 30 minutes surpass
It after sonication, is reacted 48 hours in 50 DEG C of isothermal reaction kettle, after solution is cooling, for several times with milli-Q water, removes table
Face residue impurity is until cleaning solution pH to be neutral, is then sufficiently being dried in 40 DEG C of vacuum drying ovens, until reaching constant matter
Amount is to get modified carbon fiber cloth；
2) 0.4mol/L Fe (NO is added in ultrapure water3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O, ultrasound 1
Hour makes it after mixing and is completely dissolved to obtain mixed solution, modified carbon fiber cloth is added, and ammonium fluoride is added thereto
Continue to stir with urea, is placed on reaction 12 hours in 120 DEG C of isothermal reaction kettles later, repairs the ferrite after washing after cooling
Decorations modified carbon fiber, which is arranged in 40 DEG C of thermostatic drying chambers, dries, and is subsequently placed in electric tube furnace, is passed through inert gas as guarantor
Gas is protected, is roasted 1 hour under the conditions of 350 DEG C, up to ferrite modification carbon fiber cloth electrode after cooling.
Embodiment 12 (opportunity is added in modified carbon fiber cloth: being added after ammonium fluoride and urea)
1) original carbon cloth is cut into the circle of 3.5cm diameter, mass fraction is used to divide for 10% nitric acid and quality
The mixed liquor for the sulfuric acid solution (nitric acid: sulfuric acid volume ratio is 3:1) that number is 10% impregnated carbon cloth, by 30 minutes surpass
It after sonication, is reacted 48 hours in 50 DEG C of isothermal reaction kettle, after solution is cooling, for several times with milli-Q water, removes table
Face residue impurity is until cleaning solution pH to be neutral, is then sufficiently being dried in 40 DEG C of vacuum drying ovens, until reaching constant matter
Amount is to get modified carbon fiber cloth；
2) 0.4mol/L Fe (NO is added in ultrapure water3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O, ultrasound 1
Hour makes it after mixing and is completely dissolved to obtain mixed solution, and ammonium fluoride is added thereto and urea continues to stir, then
Modified carbon fiber cloth is added, stirs evenly, is placed on reaction 12 hours in 120 DEG C of isothermal reaction kettles later, it will washing after cooling
Ferrite modification carbon cloth afterwards, which is placed in 40 DEG C of thermostatic drying chambers, dries, and is subsequently placed in electric tube furnace, is passed through lazy
Property gas as protection gas, roast 1 hour under the conditions of 350 DEG C, it is electrochemical up to ferrite modification carbon cloth after cooling
Learn cathode.
Embodiment 13
The difference from embodiment 1 is that " original carbon cloth is cut into the circle of 3.5cm diameter, " replace with " will be original
Carbon cloth be cut into the square of 4cm side length ", other are the same as embodiment 1.
Embodiment 14
The difference from embodiment 1 is that " original carbon cloth is cut into the circle of 3.5cm diameter, " replace with " will be original
Carbon cloth be cut into the rectangle of 3*4cm side length ", other are the same as embodiment 1.
Embodiment 15
The difference from embodiment 1 is that in step 2) " and then 0.4mol/L Fe (NO is added in ultrapure water3)3·9H2O
With 0.2mol/L Cu (NO3)2·3H2O " replace with " and then in ultrapure water be added 0.1mol/L Co (NO3)2·6H2O、
0.2mol/L Fe(NO3)3·9H2O、0.02mol/L NH4F and 0.05mol/L CO (NH2)2", other are the same as embodiment 1.
Embodiment 16
The difference from embodiment 1 is that in step 2) " and then 0.4mol/L Fe (NO is added in ultrapure water3)3·9H2O
With 0.2mol/L Cu (NO3)2·3H2O " replace with " and then in ultrapure water be added 0.03mol/L Fe (NO3)3With
0.015mol/LCu(NO3)2", other are the same as embodiment 1.
Embodiment 17
1) original carbon cloth is cut into the square of 4cm side length, takes the H of 1.5mL 30%2O2With the ultrapure water of 97mL
It is placed in 250mL conical flask, and is adjusted to the Fe of addition 1.5mL 0.2mol/L after pH to 32+Solution, reaction 48 is small under magnetic agitation
Shi Hou for several times with milli-Q water removes surface residual debris impurity until cleaning solution pH is neutrality, then in 40 DEG C of vacuum drying ovens
Sufficiently dry, until reaching constant quality to get modified carbon fiber cloth；
2) above-mentioned modified carbon fiber cloth is soaked in ultrapure water, 0.1mol/L Co (NO is then added3)2·6H2O、
0.2mol/L Fe(NO3)3·9H2O、0.02mol/L NH4F and 0.05mol/L CO (NH2)2, it is equal that ultrasound mixes it
It after even and is completely dissolved to obtain mixed solution, be reacted 24 hours under conditions of 45 DEG C under constant temperature blender with magnetic force effect, it is cooling
The ferrite modification carbon cloth after washing is placed in 40 DEG C of thermostatic drying chambers afterwards and is dried, electric tube furnace is subsequently placed in
In, nitrogen is passed through as protection gas, is roasted 1 hour under the conditions of 350 DEG C, up to ferrite modification carbon cloth after cooling
Electrochemical cathode.
Embodiment 18
Original carbon cloth is cut into 3x 4cm rectangle, is immersed in the KOH solution of 3mol/L, is reacted under 85 DEG C of magnetic agitations
After 8 hours, for several times with milli-Q water, surface residual debris impurity is removed until cleaning solution pH is neutrality, then in 40 DEG C of vacuum bakings
Sufficiently dry in case, until reaching constant quality to get modified carbon fiber cloth；
Preparation 100mL concentration is 0.03mol/L Fe (NO3)3With 0.015mol/LCu (NO3)2Mixed solution,
Above-mentioned modified carbon fiber cloth and the above-mentioned mixed solution of 100mL, ultrasound 1 hour are added in 500mL round-bottomed flask；It will be mixed after ultrasound
Solution is closed to react 24 hours under the conditions of 50 DEG C, 3 revs/min of revolving speed in constant temperature blender with magnetic force；Solution after reaction is cold
But afterwards with milli-Q water for several times, remove surface residual debris impurity until cleaning solution pH be neutrality；It is dry to be placed in 50 DEG C of electric heating constant temperatures
It dries 12 hours in case, is finally placed in electric tube furnace, be passed through nitrogen as protection gas, in 5 DEG C/min of heating rate, 350 DEG C
Lower roasting 1 hour, up to ferrite modification carbon fiber cloth electrode after cooling.
Original carbon cloth: being cut into the circle of 3.5cm diameter, as carbon fiber cloth electrode by comparative example 1,
Comparative example 2: the preparation of ferrite modification carbon cloth electrochemical cathode (carbon cloth is not pre-processed)
Original carbon fiber cloth is cut into the circle of 3.5cm diameter, is placed in ultrapure water and impregnates, is then added in ultrapure water
0.4mol/L Fe(NO3)3·9H2O and 0.2mol/L Cu (NO3)2·3H2O, ultrasound make it simultaneously complete after mixing for 1 hour
Dissolution obtains mixed solution, and addition ammonium fluoride and urea continue to stir thereto, are placed in 120 DEG C of isothermal reaction kettles later
Ferrite modification carbon cloth after washing is placed in 40 DEG C of thermostatic drying chambers after cooling and dries, so by reaction 12 hours
It is placed in electric tube furnace, is passed through inert gas as protection gas, is roasted 1 hour under the conditions of 350 DEG C, up to iron oxygen after cooling
Body modification carbon fiber cloth electrode.
Application Example (above embodiments and comparative example should all do application)
The ferrite modification carbon fiber cloth electrode that above-described embodiment 1 obtains makes transmission electron microscope picture, is specifically shown in attached drawing
Shown in 3-2.
The original carbon fiber cloth used in above-described embodiment carries out making scanning electron microscope detection, is specifically shown in shown in attached drawing 3-1.
Ferrite modification carbon fiber cloth electrode obtained above is used for following electrochemistry/ozone coupling water process system
System,
The electrochemistry/ozone coupling water treatment system includes the oxygen cylinder (1) being sequentially connected, oxygen flow meter (2), ozone
Generator (3), ozone detector (12), ac/Dc power (4) and reaction unit (7)；The reaction unit (7) is also connected with
There are peristaltic pump (13) and mother liquor tank (14) to be formed back between peristaltic pump (13) setting and mother liquor tank (14) and reaction unit
Road；Peristaltic pump (13) for being pressurized to the liquid in mother liquor tank (14), speedup, enter solution containing target contaminant anti-
Answer device (7)；The reaction unit (7) includes exhaust outlet (6), anode (8), cathode (10), insulation silica gel pad (9), aeration
Device (11)；The anode (8) and cathode (10) are separately positioned on the top and the bottom of reaction unit (7), are oppositely arranged in parallel, institute
It states insulation silica gel pad (9) to be arranged between anode (8) and cathode (10), the anode (8), cathode (10) and insulation silicagel pad
Piece (9) is arranged in parallel；The top of reaction unit is arranged in the exhaust outlet (6), is higher than the cathode (8) position；The aeration
Device (11) is set at the air inlet of reaction unit (7)；Ozone, can be with micro-bubble after aerator (11)；It is described
The anode (8) and cathode (10) of ac/Dc power (4) are connected to ac/Dc power (4), forming circuit；Wherein,
The electrochemistry/ozone coupling water treatment system further includes exhaust gas processing device (5), and the exhaust gas processing device (5) is connected to
It is arranged and the exhaust outlet (6) on reaction unit (7).
The cathode (10) is ferrite modification carbon fiber cloth electrode；The anode (8) is original carbon fiber cloth；
Further, the aerator (11) is microporous aeration disc, and aeration area is consistent with cathode size, is set to yin
At pole bottom (10) 0.1cm.
The cathode (6) is ferrite modification carbon fiber cloth electrode；The anode (7) is original carbon fiber cloth；?
Under electrochemistry/ozone coupling catalytic action, which thoroughly degrades to POPs pollutant.
In other embodiments, aerator can also be hydraulic flow emitter or duct type air and liquid mixer.
In other embodiments, anode may be felt electrode, graphite electrode, stainless steel electrode, Ti electrode, noble metal
Any one of electrode or boron-doped diamond electrode.
Electrochemistry/ozone coupling detects target contaminant test method:
Sewage treatment is carried out using above-mentioned electrochemistry/ozone coupling water treatment system, comprising the following steps:
POPs pollutant detects extensively in earth surface water source, and long-term preservation causes damages to aquatile.The present invention
Example is not limited to this pollutant using chlordene biphenyl, pentachlorodiphenyl, DDT and BETA- 5a,6,9,9a-hexahydro-6,9-methano-2,4 as target contaminant.
Take a certain amount of object to be added to methanol stock solution (in some embodiments, stock solution can also be acetonitrile or hydrochloric acid)
In 1000mg/L, opens peristaltic pump (13), the solution containing target contaminant in mother liquor tank (14) is pressurized, speedup, makes to contain
The solution of target contaminant enters reaction unit (7), circuits sequentially and flows through cathode, between anode and cathode；Oxygen is sent out through ozone
Raw device generates ozone, ozone after aerator (12), first passed through with micro-bubble enter behind cathode (10) bottom liquid/
Affixed contact layer enters back between anode and cathode solution, and the liquid after reaction finally returns in mother liquor tank (14) with water flow, after reaction
Tail gas enters exhaust gas processing device (5) through exhaust outlet (6), discharges after exhaust gas processing device (5) processing.
Specific testing conditions are as follows: initial concentration solution 100mg/L, reaction solution 2000mL, electrolyte 0.05mol/L
Na2SO4Solution, wriggling revolution speed 50r/min and degradation time 4min, ozone rate are 100mL/min, ozone generator pair
The gear answered is 70%, and the electric current of ozone generator is about 0.6A.Cathode-current density is 30mA/cm2, utilize high-efficient liquid phase color
The concentration of object, initial point concentration are Co in spectrum measurement reaction process, and sampling interval is 1 or 2min, and measuring concentration is C,
Removal rate is calculated as (Co-C)/Co.
Using the above test method, independent ozone, independent electrochemistry, electrochemistry/ozone coupling are investigated respectively to target dirt
The degradation for contaminating object removes situation, and cathode chooses the ferrite modification carbon fiber cloth electrode that embodiment is prepared, using original
Beginning, carbon cloth was as anode；
Meanwhile using the above test method, investigates electrochemistry/ozone coupling and situation is removed to the degradation of target contaminant,
Cathode replaces with original carbon fiber cloth electrode, and other conditions are constant.The results are shown in attached figure 4, and micro- aeration assists lower electrochemistry/O3Coupling
Water treatment system is significantly greater than the removal effect of independent ozone and independent electrochemistry, up to 96% to the removal rate of POPs.
TOC situation of change (Fig. 5), mineralization rate are also up to 85%；
Independent ozone:
Method for treating water is carried out using ozone and carries out sewage treatment, comprising the following steps:
It the difference is that only with above-mentioned electrochemistry/ozone coupling detection target contaminant test method: no power.
Independent electrochemistry:
It the difference is that only: not providing smelly with above-mentioned electrochemistry/ozone coupling detection target contaminant test method
Oxygen.
Respectively by the ferrite modification carbon fiber cloth electrode that embodiment 1-15 is obtained and the electrode that comparative example 1-2 is obtained
As application of the electrochemical cathode under micro- aeration auxiliary in terms of electrochemistry/ozone coupling water treatment system.
For example, in embodiment 1, for chlordene biphenyl, pentachlorodiphenyl, the removal that DDT and BETA- 5a,6,9,9a-hexahydro-6,9-methano-2,4 is target contaminant
Rate is up to 90% or more (Fig. 6).
By the electrode of embodiment 1, lower electrochemistry/O is assisted for micro- aeration3Couple the drop of water treatment system chlordene biphenyl
Solution, in different solutions pH value (1.0,3.0,7.0 and 11.0), chlordene biphenyl removal rate also reaches 70% or more (Fig. 7), shows
Electrode degradation effect in pH value 1.0-11.0 is all preferable, superior performance.
For the electrode of embodiment 1, ferrite modification carbon cloth electrochemical cathode stability is investigated, is made in electrode
When being respectively 1,5,10 and 30 with number, for the removal of chlordene biphenyl, ferrite modification carbon cloth electrochemical cathode
After using 30 times as a result removal rate is shown in attached in 5min up to 95% without too big variation, and to the removal rate of object
Fig. 8.
Respectively by the ferrite modification carbon fiber cloth electrode that embodiment 1-18 is obtained and the electrode that comparative example 1-2 is obtained
As application of the electrochemical cathode under micro- aeration auxiliary in terms of electrochemistry/ozone coupling water treatment system, for chlordene biphenyl,
Pentachlorodiphenyl, DDT and BETA- 5a,6,9,9a-hexahydro-6,9-methano-2,4 are target contaminant, and concrete outcome see the table below 1.
Removal rate of the electrode of the electrode of 1 embodiment 1-18 of table and comparative example 1-2 for 4 kinds of substances
It above are only the preferred embodiment of the invention, be not restricted to the present invention.Those skilled in the art is come
It says, other various forms of variations or variation can also be made on the basis of the above description.There is no need and unable to all
Embodiment illustrate.And the obvious changes or variations that thus scheme is extended out are still in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of ferrite modification carbon fiber cloth electrode, which comprises the following steps:
1) preparation of modified carbon fiber cloth: carrying out surface to carbon cloth with strong oxidizing solution or alkaline solution and be modified, dry
It is obtained by drying；
2) preparation of ferrite modification carbon cloth: what addition step 1) obtained when hydrothermal co-precipitation method prepares ferrite changes
Property carbon cloth, obtains ferrite modification carbon fiber cloth electrode.
2. a kind of preparation method of ferrite modification carbon fiber cloth electrode according to claim 1, which is characterized in that
Strong oxidizing solution described in step 1) are as follows: concentrated nitric acid, the concentrated sulfuric acid, chlorine, bromine, iodine oxyacid, Fenton reagent, persulfuric acid
Salting liquid, the one or more of potassium ferrate solution；
Alkaline solution described in step 1) is strong alkali solution,
Further, the strong alkali solution is KOH and/or NaOH；
Further, the preparation of step 1) modified carbon fiber cloth: carbon cloth is fully immersed in equipped in strong oxidizing solution,
Ultrasound is subsequently placed in isothermal reaction kettle and reacts, after surface residual debris impurity is washed with water, until pH, to neutrality, rear vacuum drying oven dries
Dry modified carbon fiber cloth to obtain the final product；
Further；The mass volume ratio of the carbon cloth and strong oxidizing solution or alkaline solution be 1.0g:(100~
300mL)；
Further, in step 1), isothermal reaction kettle reaction temperature is 35-80 DEG C；
Further, in step 1), isothermal reaction kettle reaction temperature is 40-60 DEG C；
Further, in step 1), isothermal reaction kettle reaction temperature is 50 DEG C；
Further, in step 1), the reaction time is 12h~72h in isothermal reaction kettle；
Further, in step 1), the reaction time is for 24 hours~60h in isothermal reaction kettle；
Further, in step 1), the reaction time is 48h in isothermal reaction kettle；
Further, in step 1), with milli-Q water surface residual debris impurity；
Further, in step 1), vacuum drying oven temperature is 30-75 DEG C；
Further, in step 1), vacuum drying oven temperature is 35-50 DEG C；
Further, in step 1), vacuum drying oven temperature is 40 DEG C.
3. a kind of preparation method of ferrite modification carbon fiber cloth electrode according to claim 2, which is characterized in that
Chlorine in the step 1), bromine, iodine the concentration of oxyacid be 0.1-0.5mol/L,
Fenton reagent is 0.2-0.6mol/L Fe in the step 1)2+With the H of 30wt%2O2,
Persulfate solution concentration is 0.1-0.5mol/L in the step 1),
Potassium ferrate solution concentration is 0.1-0.5mol/L in the step 1),
Strong alkali solution is the KOH solution and/or 1-3mol/L NaOH solution of 1-3mol/L in the step 1).
4. a kind of preparation method of ferrite modification carbon fiber cloth electrode according to claim 1, which is characterized in that
The step 2) are as follows:
2) preparation of ferrite modification carbon cloth: what addition step 1) obtained when hydrothermal co-precipitation method prepares ferrite changes
Property carbon cloth, ultrasonic mixing, constant temperature blender with magnetic force effect under react a period of time, ferritic carbon fiber will be loaded later
Wei Bu drying is put into the tube furnace under inert gas atmosphere is protected, roasting a period of time, and taking out cooling is to obtain ferrite to repair
Adorn modified carbon fiber cloth electrode；
The ferrite of the step 2) is the single ferrite and/or spinel type ferrite of transition metal；
Further,
The step 2) are as follows:
2) it the preparation of ferrite modification carbon cloth: is added into ultrapure water and contains Fe3+Salt and M2+Then salt uses magnetic force
Blender stirs so that it is uniformly mixed and is completely dissolved to obtain mixed solution, and polyethylene glycol is added thereto, or is fluorinated
Ammonium and urea composition continue to stir to obtain the final product, are placed on reaction in isothermal reaction kettle later, cool down after completion of the reaction, wash, after
It is placed in thermostatic drying chamber and dries, be subsequently placed in electric tube furnace, be passed through inert gas as protection gas, roast to get iron oxygen
Body modification carbon cloth；In the above preparation method, the modified carbon fiber cloth is added in co-precipitation before being formed；
The one or more of described M=Fe, Mn, Ni, Cu, Co；
Further, the Fe3+Salt and M2+The molar concentration rate of salt is 1-4；Further, the Fe3+Salt and M2+Salt
The molar concentration rate of class is 2；
Further, the degree of isothermal reaction kettle temperature described in step 2) is 20-140 DEG C；Further, constant temperature described in step 2) is anti-
Answering kettle temperature degree is 40-130 DEG C；
Further, the reaction time is 2-100h in isothermal reaction kettle described in step 2)；Further, perseverance described in step 2)
The reaction time is 12-72h in warm reaction kettle；
Further, maturing temperature described in step 2) is 300-400 DEG C；Further, maturing temperature described in step 2) is
350℃；
Further, in step 2), the heating rate of electric tube furnace is 2-10 DEG C/min；Further, in step 2), tubular type electricity
The heating rate of furnace is 5 DEG C/min；
Further, calcining time described in step 2) is 0.5-3 hours；Further, calcining time described in step 2) is 1
Hour.
5. a kind of preparation method of ferrite modification carbon fiber cloth electrode according to claim 1, which is characterized in that
The mass ratio of ferrite and modified carbon fiber cloth material in the step 2) is 1:2~1:8.
6. a kind of electrochemistry/ozone coupling water treatment system, characterized in that the electrochemistry/ozone coupling water treatment system includes
Oxygen cylinder (1), oxygen flow meter (2), ozone generator (3), the ozone detector (12), ac/Dc power being sequentially connected
(4) and reaction unit (7)；
The reaction unit (7) is also connected with peristaltic pump (13) and mother liquor tank (14), peristaltic pump (13) setting and mother liquor tank
(14) between reaction unit, forming circuit；
The reaction unit (7) includes exhaust outlet (6), anode (8), cathode (10), insulation silica gel pad (9), aerator
(11)；The anode (8) and cathode (10) are separately positioned on the top and the bottom of reaction unit (7), are oppositely arranged in parallel, described exhausted
Edge silica gel pad (9) is arranged between anode (8) and cathode (10), the anode (8), cathode (10) and insulation silica gel pad
(9) it is arranged in parallel；The top of reaction unit is arranged in the exhaust outlet (6), is higher than the cathode (8) position；The aeration dress
(11) are set to be set at the air inlet of reaction unit (7)；
The anode (8) and cathode (10) of the ac/Dc power (4) are connected to ac/Dc power (4), are formed back
Road；
Further, the electrochemistry/ozone coupling water treatment system further includes exhaust gas processing device (5), the vent gas treatment
Device (5), the exhaust outlet (6) being connected on setting and reaction unit (7).
7. electrochemistry according to claim 6/ozone coupling water treatment system, which is characterized in that
The cathode (10) is ferrite modification carbon fiber cloth electrode；
The anode (8) is original carbon fiber cloth, felt electrode, graphite electrode, stainless steel electrode, Ti electrode, noble metal electrode
Or any one of boron-doped diamond electrode；
Further, the anode (8) is original carbon cloth；
Further, the aerator (11) is set at cathode bottom (10) 0.1cm；
Further, aerator (11) aeration area is consistent with cathode size；
Further, aerator (11) Air Bubble Size is micro/nano level；
Further, the aerator (11) is microporous aeration disc, hydraulic flow emitter or duct type air and liquid mixer.
8. the ferrite modification carbon fiber cloth electrode that the described in any item preparation methods of Claims 1 to 5 obtain is in electrification
Learn the application in cathode material or sewage treatment.
9. application according to claim 8, which is characterized in that carry out sewage treatment, packet using the system of claim 7-8
Include following steps:
It opens peristaltic pump (13), the solution containing target contaminant in mother liquor tank (14) is pressurized, speedup, made containing target stains
The solution of object enters reaction unit (7), circuits sequentially and flows through cathode, between anode and cathode；Oxygen is generated through ozone generator
Ozone, ozone enter liquid/solid contact after first passing through cathode (10) bottom with micro-bubble after aerator (12)
Layer, enters back between anode and cathode solution, and the liquid after reaction finally returns in mother liquor tank (14) with water flow, the tail gas warp after reaction
Exhaust outlet (6) enters exhaust gas processing device (5), discharges after exhaust gas processing device (5) processing.
10. application according to claim 9, which is characterized in that peristaltic pump (13) revolving speed is 0~100 rev/min.
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| GB2582681A (en) * | 2019-06-26 | 2020-09-30 | Univ Central South | Method and device for sewage treatment |
| CN112678920A (en) * | 2019-06-10 | 2021-04-20 | 中南大学 | Electrochemistry/ozone coupling water treatment system |
| CN112908508A (en) * | 2021-01-12 | 2021-06-04 | 中国工程物理研究院材料研究所 | Method for treating radioactive analysis waste liquid by one-step method |
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| CN113979514A (en) * | 2021-10-22 | 2022-01-28 | 周口师范学院 | Ni-based CuFe2O4Preparation method of spinel coating electrode material |
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| CN110156119B (en) | 2021-01-08 |
| CN112678920B (en) | 2022-04-26 |
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