CN103241807A - Composite particle electrode for bipolar three-dimensional electrode reactor and preparation method of electrode - Google Patents
Composite particle electrode for bipolar three-dimensional electrode reactor and preparation method of electrode Download PDFInfo
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- CN103241807A CN103241807A CN2013101823618A CN201310182361A CN103241807A CN 103241807 A CN103241807 A CN 103241807A CN 2013101823618 A CN2013101823618 A CN 2013101823618A CN 201310182361 A CN201310182361 A CN 201310182361A CN 103241807 A CN103241807 A CN 103241807A
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Abstract
The invention belongs to the field of an electrochemical reactor, and relates to a composite particle electrode for a bipolar three-dimensional electrode reactor and a preparation method of the electrode. The composite particle electrode comprises active carbon particles and porous ceramic ring grains, wherein the active carbon particles account for 60 to 70 percent by weight of the gross of a grain electrode, and the porous ceramic ring grains account for 30 to 40 percent by weight of the gross of the grain electrode; and the active carbon particles and the porous ceramic ring grains are respectively loaded with different metal active components. The preparation method comprises the following steps of: (1) preprocessing the particles and the grains, (2) soaking and adsorbing, (3) heat treatment, and (4) roasting activation. The composite particle electrode has the characteristics that the preparation method is simple, investment is less, the industrialization is easy to realize, and utilization rate of the effective space of an electrolytic tank is high. The composite particle electrode can be used for preprocessing high-concentration persistent organic pollutants, can improve the biodegradability of the sewage, and also can be used for the further treatment of the low-concentration sewage of a sewage treatment plant, and the application prospect is promising.
Description
Technical field
The invention belongs to the electrochemical reactor field, be specifically related to a kind of composite particles electrode that is applied to the multipole 3 D electrode reactor and preparation method thereof.This composite particles electrode can be used for the improvement field of water environment pollution.
Background technology
Electrochemical method is administered waste water and generally be need not to add oxygenant, and equipment is simple, volume is little, and sludge quantity is few, and aftertreatment is simple, is commonly called the green oxidation technology of " environmental friendliness ".Late 1960s, along with developing rapidly of mass transfer theory, Materials science and power industry, the concept of three-diemsnional electrode has been proposed on the basis of conventional two-dimensional electrode.It is the granular working electrode material of filling between traditional two-dimentional electrolytic tank electrode, and to make the work materials surface charging that fills of dress and become the one new utmost point-the 3rd utmost point be granule electrode, in electrode material surface generation electrochemical reaction.Compare with traditional two-dimensional electrode, three-diemsnional electrode has increased countless microelectrodes in electrolyzer, can increase the face body ratio of electrolyzer, has shortened migration distance, the increase material mass transfer velocity of reactant, improves current efficiency and treatment effect.Therefore, three-diemsnional electrode demonstrates bigger advantage and bright development prospect in the electro-chemical water process field.
Three-diemsnional electrode can be divided into unipolarity three-diemsnional electrode and multipole three-diemsnional electrode by its polarity.The unipolarity 3 D electrode reactor is generally filled the less granule electrode material of impedance, has barrier film to exist between two main electrodes usually.When main electrode contacts with granule electrode, make the granule electrode surface with going up the electric charge identical with main electrode, electrochemical reaction is carried out separately in anode and cathode, and organism is oxidized at anode, and heavy metal ion is reduced at negative electrode.The multipole 3 D electrode reactor is generally filled the granule electrode material of high resistance, need not barrier film, make granule electrode turn to Bipolar Micro-Electrode because of the static induction multipole by the electric field between main electrode, be with positive and negative electric charge respectively at the particle two ends, each particle becomes an independently electrode, and electrochemical reaction is carried out simultaneously at each particle surface.Because need with barrier film main anode and cathode to be isolated during the work of unipolarity 3 D electrode reactor, the use of barrier film not only needs extra-pay, and increased the complicacy that engineering is used, therefore, research and the application of multipole 3 D electrode reactor enjoy favor.
Granule electrode is the key components of 3 D electrode reactor system, also is the key that improves reactor for treatment efficient.As electrode materials, particle filled composite should have good electrical conductivity, erosion resistance and electrocatalysis characteristic.In the multipole three-diemsnional electrode, the ideal conditions of granule electrode be the resistance of particle much smaller than solution resistance, be convenient to the particle repolarization, require between the particle insulated from each other again.Thereby the contact condition that improves granule electrode is the key that improves multipole 3 D electrode reactor electrolytic efficiency.
It is insulated particle that Chinese patent literature CN200610161243.9 has proposed with the cellulose acetate gac of filming, with the technology of conduction activated carbon granule constituent particle electrode; It is insulated particle that Chinese patent literature CN201110007347.5 has proposed with the polyvinyl alcohol gel gac of filming, with the technology of conduction activated carbon granule constituent particle electrode.Isolator in these two kinds of methods only plays the effect of isolate conductive particle, has reduced the effective working space of cell body.
Chinese patent literature CN200710067340.6 uses by Mn, Sn, Sb active ingredient and γ-Al
2O
3The active ceramic honey comb granule electrode of forming is handled and is contained chlorobenzene compound waste water, Chinese patent literature CN201110083945.0 has proposed to be prepared by aluminium oxide particles the technology of three dimensional particles electrode, and Chinese patent literature CN201210270047.0 has proposed with potter's clay and γ-Al
2O
3The technology of preparation multipole three-diemsnional electrode.Above-mentioned carrier is the high resistance carrier, the energy consumption height, and the application in low salinity waste water is restricted, simultaneously, γ-Al
2O
3The particle resistance to acids and bases is relatively poor, easily efflorescence when being applied to than strongly-acid or alkaline industrial waste water processing.
Summary of the invention
The objective of the invention is to overcome the technical problem that above-mentioned granule electrode exists, method is made in the composite particles electrode and the preparation thereof that propose that a kind of specific surface area is big, space availability ratio is high, catalytic performance is strong, can be applicable to the multipole 3 D electrode reactor.
The composite particles electrode that is applied to the multipole 3 D electrode reactor of the present invention is made up of activated carbon grain sub-electrode and porous porcelain ring granule electrode; Described activated carbon grain sub-electrode is the activated carbon granule that load has metal active constituent tin, antimony and iron, and described porous porcelain ring granule electrode is the porous porcelain ring particle that load has metal active constituent cerium, manganese and cobalt.
Further, the activated carbon granule particle diameter in the composite particles electrode described in the present invention is 3-8mm.
Further, the porous porcelain ring particle in the composite particles electrode described in the present invention is round tube shape structure, and the pipe diameter of described round tube shape structure is 25mm, and pipe length is 25mm, and thickness of pipe is 2.0mm; 4-8 slot along the circumferential direction is set on the tube wall, divides two rows to be staggered, the wide of slot is 3-7mm, the long 8-10mm of being, the mother metal of slot folds into pipe inside.
Further, in the composite particles electrode described in the present invention, the mass ratio of activated carbon grain sub-electrode and porous porcelain ring granule electrode is 6:4-7:3.
The present invention also comprises a kind of preparation method, and the composite particles electrode for the preparation of being applied to the multipole 3 D electrode reactor comprises the steps:
The pre-treatment of step 1.1, activated carbon granule:
Step 1.1.1, with activated carbon granule with distilled water flushing after, put into the hydrochloric acid that concentration is 1.0-2.0mol/L, boil 30-60 minute after, activated carbon granule is taken out and is washed till neutrality;
Step 1.1.2, the activated carbon granule after step 1.1.1 handles is put into NaOH or the KOH alkali lye that concentration is 1.0-2.0mol/L, boil 30-60 minute after, take out and be washed till neutrality;
Step 1.1.3, will the activated carbon granule elimination moisture after step 1.1.2 handles after, oven dry is stand-by down at 100-105 ℃;
Step 1.2, the absorption of activated carbon granule dipping:
With SnCl
45H
2O, SbCl
3And FeCl
3Be mixed with the steeping fluid of activated carbon granule, SnCl in the steeping fluid
45H
2O concentration is 0.5-0.6mol/L, SbCl
3Concentration is 0.1-0.2mol/L, FeCl
3Concentration is 0.3mol/L; The activated carbon granule that will obtain after step 1.1 pre-treatment is immersed in dipping absorption 2-4 hour of vibrating in the above-mentioned steeping fluid;
Step 1.3, thermal treatment: the activated carbon granule after the dipping absorption of will vibrating takes out, and drying is 3 hours under 80-90 ℃;
Step 1.4, calcination activation: activated carbon granule that will be is after heat treatment put into retort furnace, is warming up to 300-400 ℃ from room temperature by 5 ℃/minute temperature rise rate, be incubated taking-up after 2-3 hour, naturally cools to room temperature;
Step 1.5, with the activated carbon granule that obtains according to step 1.2 to step 1.4 circular treatment 3-4 time, acquisition is loaded with the activated carbon grain sub-electrode of metal active constituent;
The pre-treatment of step 2.1 porous porcelain ring particle:
Step 2.1.1, with after the porous porcelain ring particle water flushing, after the hydrochloric acid soln of putting into concentration and be 0.1-0.3mol/L boils 60-80 minute, take out porous porcelain ring particle and also be washed till neutrality;
Step 2.1.2, the porous porcelain ring particle after step 2.1.1 handles is put into concentration is 0.1-0.3mol/L NaOH or KOH alkali lye, boil 60-80 minute after, take out and be washed till neutrality;
Step 2.1.3, will the porous porcelain ring particle elimination moisture after step 2.1.2 handles after, oven dry is stand-by down at 100-105 ℃;
Step 2.2, the absorption of porous porcelain ring particle dipping:
With Ce (NO
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The water-soluble solution of O is mixed with the steeping fluid of porous porcelain ring particle, Ce (NO in the steeping fluid
3)
36H
2O concentration is 0.2-0.4mol/L, Mn (NO
3)
2Concentration is 0.2-0.4mol/L, Co (NO
3)
26H
2O concentration is 0.2-0.4mol/L, and the porous porcelain ring particle that will obtain after step 2.1 pre-treatment is immersed in and carries out ultrasonic immersing absorption 40-60 minute in the above-mentioned steeping fluid;
Step 2.3, thermal treatment: the porous porcelain ring particle after the ultrasonic immersing absorption is taken out, and drying is 4 hours under 110-120 ℃;
Step 2.4, calcination activation: porous porcelain ring particle that will be is after heat treatment put into retort furnace, is warming up to 400-500 ℃ from room temperature by 5 ℃/minute temperature rise rate, is incubated 3-4 hour, naturally cools to room temperature;
Step 2.5, with the porous porcelain ring particle that obtains according to step 2.2 to step 2.4 circular treatment 2 times, obtain to be loaded with the porous porcelain ring granule electrode of metal active constituent;
The preparation of step 3, composite particles electrode:
The activated carbon grain sub-electrode that is loaded with metal active constituent with step 1 acquisition, the porous porcelain ring granule electrode that is loaded with metal active constituent with step 2 acquisition, ratio according to mass ratio 6:4-7:3 is evenly mixed, and namely obtains to be applied to the composite particles electrode of multipole 3 D electrode reactor.
Further, the composite particles electrode preparation method that is applied to the multipole 3 D electrode reactor among the present invention in above-mentioned method, also can be operated: step 1.2, the absorption of activated carbon granule dipping: prepare SnCl respectively as follows
45H
2O concentration is 0.5-0.6mol/L, SbCl
3Concentration is 0.1-0.2mol/L, FeCl
3Concentration is the steeping fluid of three kinds of activated carbon granules of 0.3mol/L, and the activated carbon granule that will obtain after step 1.1 pre-treatment is immersed in three kinds of above-mentioned steeping fluids one by one, and dipping absorption 2-4 hour of vibrating respectively.
Further, the composite particles electrode preparation method that is applied to the multipole 3 D electrode reactor among the present invention in above-mentioned method, also can be operated: step 2.2, the absorption of porous porcelain ring particle dipping: prepare Ce (NO respectively as follows
3)
36H
2O concentration is 0.2-0.4mol/L, Mn (NO
3)
2Concentration is 0.2-0.4mol/L, Co (NO
3)
26H
2O concentration is the steeping fluid of three kinds of porous porcelain ring particles of 0.2-0.4mol/L, and the porous porcelain ring particle that will obtain after step 2.1 pre-treatment is immersed in three kinds of above-mentioned steeping fluids one by one, and carries out ultrasonic immersing absorption 40-60 minute respectively.
The positively effect that the present invention has:
(1) activated carbon granule not only has well acidproof, alkali resistance, and has the basis of good electrochemical properties and sewage disposal industrial applications, is a kind of economical and practical granule electrode material, is convenient to industrial applications and popularization.
(2) there is the ash content height in common activated carbon granule, specific surface area is little and the shortcoming of adsorptive power difference, the present invention adopts acid solution and alkali lye that gac is carried out pre-treatment, the ash content of gac is reduced greatly, increased the specific surface area of gac, improved the adsorption activity of gac, the load of metal active constituent has strengthened the oxidation capacity of activated carbon grain sub-electrode.
(3) pottery has many characteristics such as physical strength height, resistance to acids and bases are strong, good stability, and porous porcelain ring particle is easy to make, and is cheap and easy to get.
(4) replace insulating particle with porous porcelain ring particle, and load little metal active ingredient, the porcelain ring surface becomes coarse because of load, the mass transfer that not only is conducive to electrolytic solution, and can be by repolarization, give full play to the effective working space of 3 D electrode reactor, reduced electrolytical dosage in the 3 D electrode reactor operational process.
(5) the present invention adopts the activated carbon granule that is loaded with metal active constituent and the porous porcelain ring particle that is loaded with metal active constituent to form the composite particles electrode, porous porcelain loop resistance height, voidage is big, the branch wing is many, be conducive to low-impedance activated carbon particles is disperseed, insulated from each other, make that each particle can both repolarization, the supporting role of porcelain electrode simultaneously helps to prevent that activated carbon particles is under pressure and pulverize, the generation of activated carbon particles and different sorts insulating material generation demixing phenomenon when having avoided operation has been avoided in the gac of filming after the long-time running insulating film to come off and has been caused the generation of failure of insulation phenomenon.
(6) after composite particles electrode of the present invention is filled in the multipole 3 D electrode reactor, both can be used as the pre-treatment of high-concentration difficult-degradation organic sewage, destroy hardly degraded organic substance, improve the biodegradability of sewage, the advanced treatment that also can be used for sewage work's low concentration wastewater is to guarantee sewage qualified discharge or reuse.
(7) the present invention adopts pickling process loaded metal active ingredient on activated carbon granule and porcelain ring particle, easy, the easy handling of method, and the metal active constituent load is firm, realizes industrialization easily.
Description of drawings
Fig. 1 is the synoptic diagram of round tube shape structure porous porcelain ring particle.The material of particle is porcelain, and the pipe diameter is 25mm, and pipe length is 25mm, and thickness of pipe is 2.0mm; 4-8 slot along the circumferential direction is set on the tube wall, divides two rows to be staggered, the wide of slot is 3-7mm, the long 8-10mm of being, the mother metal of slot folds into pipe inside.
Fig. 2 is that the composite particles electrode is filled synoptic diagram in the multipole 3 D electrode reactor.Wherein 1 is 3 D electrode reactor, 2 is the main anode plate, 3 is the main cathode plate, 4 is the composite particles electrode, porous cylindrical body is the porous porcelain ring of metal active ingredient, is filled in the reactor to huddle form, and black particles is the activated carbon granule that is loaded with metal active constituent that is scattered in the porcelain ring, 5 is the porous aeration board, and 6 is aeration tube.
Fig. 3 is the electrolytic efficiency comparison diagram of different granule electrodes.Wherein transverse axis is degradation time, unit: minute; The left side longitudinal axis is rest COD value in the waste water, unit: mg/L; The right longitudinal axis is the COD clearance, unit: %;-■-represent composite particles electrolysis rest COD ,-▲-representative contrast granule electrode electrolysis rest COD ,--represent composite particles electrolysis COD clearance ,-△-representative contrasts granule electrode electrolysis COD clearance.
Embodiment
A. be loaded with the preparation of the activated carbon granule of metal active constituent
(1) pre-treatment of activated carbon granule: with particle diameter be the 3-5mm activated carbon granule with distilled water flushing after, putting into concentration is after the 1.0mol/L hydrochloric acid soln boils 60 minutes, activated carbon granule is taken out and is washed till neutrality, putting into concentration again is after 1.0mol/L NaOH alkali lye boils 60 minutes, take out and be washed till neutrality, elimination moisture, oven dry is stand-by down at 100-105 ℃;
(2) dipping absorption: with SnCl
45H
2O, SbCl
3And FeCl
3Be mixed with the steeping fluid of activated carbon granule, SnCl in the steeping fluid
45H
2The concentration of O is 0.6mol/L, SbCl
3Concentration be 0.1mol/L, FeCl
3Concentration be 0.3mol/L.The activated carbon granule that will obtain after pre-treatment is immersed in the dipping absorption 2 hours of vibrating in the above-mentioned steeping fluid;
(3) thermal treatment: the activated carbon granule after the dipping absorption of will vibrating takes out, and drying is 3 hours under 80-90 ℃;
(4) calcination activation: activated carbon granule that will be is after heat treatment put into retort furnace, is warming up to 300 ℃ from room temperature by 5 ℃/minute temperature rise rate, be incubated taking-up after 3 hours, naturally cools to room temperature.
(5) with the activated carbon granule that obtains according to step (2) to (4) circular treatment 3 times, namely obtain to be loaded with the activated carbon grain sub-electrode of metal active constituent.
B. be loaded with the preparation of the porous porcelain ring particle of metal active constituent
(1) pre-treatment of porous porcelain ring particle: with Kong Kuanwei 3-4mm, after the 8 hole porcelain ring particle water flushings of Kong Changwei 8mm, after the hydrochloric acid soln of putting into concentration and be 0.3mol/L boils 60 minutes, take out porous porcelain ring particle and be washed till neutrality, putting into concentration again is 0.3mol/L NaOH alkali lye, boil 60 minutes after, take out and be washed till neutrality, elimination moisture, oven dry is stand-by down at 100-105 ℃;
(2) dipping absorption: with Ce (NO
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The water-soluble solution of O is mixed with the steeping fluid of porous porcelain ring particle, Ce (NO in the steeping fluid
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The concentration of O is 0.4mol/L, and the porous porcelain ring particle that will obtain after pre-treatment is immersed in and carries out ultrasonic immersing absorption 40 minutes in the above-mentioned steeping fluid;
(3) thermal treatment: the porous porcelain ring particle after the ultrasonic immersing absorption is taken out, and drying is 4 hours under 110-120 ℃;
(4) calcination activation: porous porcelain ring particle that will be is after heat treatment put into retort furnace, is warming up to 400 ℃ from room temperature by 5 ℃/minute temperature rise rate, is incubated 4 hours, naturally cools to room temperature.
(5) with the porous porcelain ring particle that obtains according to step (2) to (4) circular treatment 2 times, namely obtain to be loaded with the porous porcelain ring granule electrode of metal active constituent.
C. the preparation of composite particles electrode
The activated carbon grain sub-electrode that is loaded with metal active constituent with the steps A acquisition, the porous porcelain ring granule electrode that is loaded with metal active constituent with step B acquisition, ratio according to mass ratio 60:40 is evenly mixed, and namely obtains to be applied to the composite particles electrode of multipole 3 D electrode reactor.
The composite particles electrode that obtains is applied to the multipole 3 D electrode reactor, and electrocatalysis degraded COD is the Potassium Hydrogen Phthalate waste water of 400mg/L.The electrocatalysis degraded is in the time of 30 minutes, and COD is down to 38.7mg/L, and the COD clearance reaches 90.3%.
A. be loaded with the preparation of the activated carbon granule of metal active constituent
(1) pre-treatment of activated carbon granule: with particle diameter be the 4-6mm activated carbon granule with distilled water flushing after, putting into concentration is after the 1.5mol/L hydrochloric acid soln boils 40 minutes, activated carbon granule is taken out and is washed till neutrality, after the KOH alkali lye of putting into concentration again and be 1.5mol/L boils 40 minutes, take out and be washed till neutrality, elimination moisture, oven dry is stand-by down at 100-105 ℃;
(2) dipping absorption: with SnCl
45H
2O, SbCl
3And FeCl
3Be mixed with the steeping fluid of activated carbon granule, SnCl in the steeping fluid
45H
2The concentration of O is 0.55mol/L, SbCl
3Concentration be 0.15mol/L, FeCl
3Concentration be 0.3mol/L.The activated carbon granule that will obtain after pre-treatment is immersed in the dipping absorption 3 hours of vibrating in the above-mentioned steeping fluid;
(3) thermal treatment: the activated carbon granule after the dipping absorption of will vibrating takes out, and drying is 3 hours under 80-90 ℃;
(4) calcination activation: activated carbon granule that will be is after heat treatment put into retort furnace, is warming up to 350 ℃ from room temperature by 5 ℃/minute temperature rise rate, be incubated taking-up after 2.5 hours, naturally cools to room temperature.
(5) with the activated carbon granule that obtains according to step (2) to (4) circular treatment 3 times, namely obtain to be loaded with the activated carbon grain sub-electrode of metal active constituent.
B. be loaded with the preparation of the porous porcelain ring particle of metal active constituent
(1) pre-treatment of porous porcelain ring particle: with Kong Kuanwei 4-5mm, after the 6 hole porcelain ring particle water flushings of Kong Changwei 9mm, after the hydrochloric acid soln of putting into concentration and be 0.2mol/L boils 70 minutes, take out porous porcelain ring particle and be washed till neutrality, putting into concentration again is 0.2mol/L KOH alkali lye, boil 70 minutes after, take out and be washed till neutrality, elimination moisture, oven dry is stand-by down at 100-105 ℃;
(2) dipping absorption: with Ce (NO
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The water-soluble solution of O is mixed with the steeping fluid of porous porcelain ring particle, Ce (NO in the steeping fluid
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The concentration of O is 0.3mol/L, and the porous porcelain ring particle that will obtain after pre-treatment is immersed in and carries out ultrasonic immersing absorption 50 minutes in the above-mentioned steeping fluid;
(3) thermal treatment: the porous porcelain ring particle after the ultrasonic immersing absorption is taken out, and drying is 4 hours under 110-120 ℃;
(4) calcination activation: porous porcelain ring particle that will be is after heat treatment put into retort furnace, is warming up to 450 ℃ from room temperature by 5 ℃/minute temperature rise rate, is incubated 3.5 hours, naturally cools to room temperature.
(5) with the porous porcelain ring particle that obtains according to step (2) to (4) circular treatment 2 times, namely obtain to be loaded with the porous porcelain ring granule electrode of metal active constituent.
C. the preparation of composite particles electrode
The activated carbon grain sub-electrode that is loaded with metal active constituent with the steps A acquisition, the porous porcelain ring granule electrode that is loaded with metal active constituent with step B acquisition, ratio according to mass ratio 65:35 is evenly mixed, and namely obtains to be applied to the composite particles electrode of multipole 3 D electrode reactor.
The composite particles electrode that obtains is applied to the multipole 3 D electrode reactor, and electrocatalysis degraded COD is the Potassium Hydrogen Phthalate waste water of 400mg/L.The electrocatalysis degraded is in the time of 30 minutes, and COD is down to 41.2mg/L, and the COD clearance reaches 89.7%.
A. be loaded with the preparation of the activated carbon granule of metal active constituent
(1) pre-treatment of activated carbon granule: with particle diameter be the 6-8mm activated carbon granule with distilled water flushing after, putting into concentration is after the 2.0mol/L hydrochloric acid soln boils 30 minutes, activated carbon granule is taken out and is washed till neutrality, putting into concentration again is after 2.0mol/L NaOH alkali lye boils 30 minutes, take out and be washed till neutrality, elimination moisture, oven dry is stand-by down at 100-105 ℃;
(2) dipping absorption: with SnCl
45H
2O, SbCl
3And FeCl
3Be mixed with the steeping fluid of activated carbon granule, SnCl in the steeping fluid
45H
2The concentration of O is 0.5mol/L, SbCl
3Concentration be 0.2mol/L, FeCl
3Concentration be 0.3mol/L.The activated carbon granule that will obtain after pre-treatment is immersed in the dipping absorption 4 hours of vibrating in the above-mentioned steeping fluid;
(3) thermal treatment: the activated carbon granule after the dipping absorption of will vibrating takes out, and drying is 3 hours under 80-90 ℃;
(4) calcination activation: activated carbon granule that will be is after heat treatment put into retort furnace, is warming up to 400 ℃ from room temperature by 5 ℃/minute temperature rise rate, be incubated taking-up after 2 hours, naturally cools to room temperature.
(5) with the activated carbon granule that obtains according to step (2) to (4) circular treatment 4 times, namely obtain to be loaded with the activated carbon grain sub-electrode of metal active constituent.
B. be loaded with the preparation of the porous porcelain ring particle of metal active constituent
(1) pre-treatment of porous porcelain ring particle: with Kong Kuanwei 6-7mm, after the 4 hole porcelain ring particle water flushings of Kong Changwei 10mm, after the hydrochloric acid soln of putting into concentration and be 0.1mol/L boils 80 minutes, take out porous porcelain ring particle and be washed till neutrality, putting into concentration again is 0.1mol/L KOH alkali lye, boil 80 minutes after, take out and be washed till neutrality, elimination moisture, oven dry is stand-by down at 100-105 ℃;
(2) dipping absorption: with Ce (NO
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The water-soluble solution of O is mixed with the steeping fluid of porous porcelain ring particle, Ce (NO in the steeping fluid
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The concentration of O is 0.2mol/L, and the porous porcelain ring particle that will obtain after pre-treatment is immersed in and carries out ultrasonic immersing absorption 60 minutes in the above-mentioned steeping fluid;
(3) thermal treatment: the porous porcelain ring particle after the ultrasonic immersing absorption is taken out, and drying is 4 hours under 110-120 ℃;
(4) calcination activation: porous porcelain ring particle that will be is after heat treatment put into retort furnace, is warming up to 500 ℃ from room temperature by 5 ℃/minute temperature rise rate, is incubated 3 hours, naturally cools to room temperature.
(5) with the porous porcelain ring particle that obtains according to step (2) to (4) circular treatment 2 times, namely obtain to be loaded with the porous porcelain ring granule electrode of metal active constituent.
C. the preparation of composite particles electrode
The activated carbon grain sub-electrode that is loaded with metal active constituent with the steps A acquisition, the porous porcelain ring granule electrode that is loaded with metal active constituent with step B acquisition, ratio according to mass ratio 70:30 is evenly mixed, and namely obtains to be applied to the composite particles electrode of multipole 3 D electrode reactor.
The composite particles electrode that obtains is applied to the multipole 3 D electrode reactor, and electrocatalysis degraded COD is the Potassium Hydrogen Phthalate waste water of 400mg/L.The electrocatalysis degraded is in the time of 30 minutes, and COD is down to 39.4mg/L, and the COD clearance reaches 90.2%.
The composite particles electrode that obtains is applied to the multipole 3 D electrode reactor, and electrocatalysis degraded COD is the Potassium Hydrogen Phthalate waste water of 400mg/L.The electrocatalysis degraded is in the time of 30 minutes, and COD is down to 35.8mg/L, and the COD clearance reaches 91.1%.
The composite particles electrode that obtains is applied to the multipole 3 D electrode reactor, and electrocatalysis degraded COD is the Potassium Hydrogen Phthalate waste water of 400mg/L.The electrocatalysis degraded is in the time of 30 minutes, and COD is down to 40.6mg/L, and the COD clearance reaches 89.8%.
The composite particles electrode that obtains is applied to the multipole 3 D electrode reactor, and electrocatalysis degraded COD is the Potassium Hydrogen Phthalate waste water of 400mg/L.The electrocatalysis degraded is in the time of 30 minutes, and COD is down to 36.2mg/L, and the COD clearance reaches 90.9%.
Embodiment 7
Embodiment 8
Embodiment 9
The waste water that the composite particles electrode that embodiment 6 is prepared discharges after by the identical method advanced treatment textile industry garden sewage work biochemical treatment of embodiment 7.This sewage work adopts activated sludge process to focus on the various waste water that produce in each printing and dyeing enterprise production process in the industry park.The colourity of this waste water sample (extension rate) is 52 times, COD is 113mg/L, and when electrocatalysis degraded in the time of 20 minutes, colourity is reduced to 27 times, COD reduces to 41.8mg/L, reaches " urban wastewater treatment firm pollutant emission standard " (GB18918-2002) A standard-required of primary standard.
Claims (7)
1. a composite particles electrode that is applied to the multipole 3 D electrode reactor is characterized in that: be made up of activated carbon grain sub-electrode and porous porcelain ring granule electrode; Described activated carbon grain sub-electrode is the activated carbon granule that load has metal active constituent tin, antimony and iron, and described porous porcelain ring granule electrode is the porous porcelain ring particle that load has metal active constituent cerium, manganese and cobalt.
2. a kind of composite particles electrode that is applied to the multipole 3 D electrode reactor according to claim 1, it is characterized in that: described activated carbon granule particle diameter is 3-8mm.
3. a kind of composite particles electrode that is applied to the multipole 3 D electrode reactor according to claim 1, it is characterized in that: described porous porcelain ring particle is round tube shape structure, the pipe diameter of described round tube shape structure is 25mm, and pipe length is 25mm, and thickness of pipe is 2.0mm; 4-8 slot along the circumferential direction is set on the tube wall, divides two rows to be staggered, the wide of slot is 3-7mm, the long 8-10mm of being, the mother metal of slot folds into pipe inside.
4. a kind of composite particles electrode that is applied to the multipole 3 D electrode reactor according to claim 1, it is characterized in that: the mass ratio of activated carbon grain sub-electrode and porous porcelain ring granule electrode is 6:4-7:3.
5. a composite particles electrode preparation method that is applied to the multipole 3 D electrode reactor is characterized in that comprising the steps:
Step 1, be loaded with the preparation of the activated carbon granule of metal active constituent:
The pre-treatment of step 1.1, activated carbon granule:
Step 1.1.1, with activated carbon granule with distilled water flushing after, put into the hydrochloric acid that concentration is 1.0-2.0mol/L, boil 30-60 minute after, activated carbon granule is taken out and is washed till neutrality;
Step 1.1.2, the activated carbon granule after step 1.1.1 handles is put into NaOH or the KOH alkali lye that concentration is 1.0-2.0mol/L, boil 30-60 minute after, take out and be washed till neutrality;
Step 1.1.3, will the activated carbon granule elimination moisture after step 1.1.2 handles after, oven dry is stand-by down at 100-105 ℃;
Step 1.2, the absorption of activated carbon granule dipping:
With SnCl
45H
2O, SbCl
3And FeCl
3Be mixed with the steeping fluid of activated carbon granule, SnCl in the steeping fluid
45H
2O concentration is 0.5-0.6mol/L, SbCl
3Concentration is 0.1-0.2mol/L, FeCl
3Concentration is 0.3mol/L; The activated carbon granule that will obtain after step 1.1 pre-treatment is immersed in dipping absorption 2-4 hour of vibrating in the above-mentioned steeping fluid;
Step 1.3, thermal treatment: the activated carbon granule after the dipping absorption of will vibrating takes out, and drying is 3 hours under 80-90 ℃;
Step 1.4, calcination activation: activated carbon granule that will be is after heat treatment put into retort furnace, is warming up to 300-400 ℃ from room temperature by 5 ℃/minute temperature rise rate, be incubated taking-up after 2-3 hour, naturally cools to room temperature;
Step 1.5, with the activated carbon granule that obtains according to step 1.2 to step 1.4 circular treatment 3-4 time, acquisition is loaded with the activated carbon grain sub-electrode of metal active constituent;
Step 2, be loaded with the preparation of the porous porcelain ring particle of metal active constituent:
The pre-treatment of step 2.1 porous porcelain ring particle:
Step 2.1.1, with after the porous porcelain ring particle water flushing, after the hydrochloric acid soln of putting into concentration and be 0.1-0.3mol/L boils 60-80 minute, take out porous porcelain ring particle and also be washed till neutrality;
Step 2.1.2, the porous porcelain ring particle after step 2.1.1 handles is put into concentration is 0.1-0.3mol/L NaOH or KOH alkali lye, boil 60-80 minute after, take out and be washed till neutrality;
Step 2.1.3, will the porous porcelain ring particle elimination moisture after step 2.1.2 handles after, oven dry is stand-by down at 100-105 ℃;
Step 2.2, the absorption of porous porcelain ring particle dipping:
With Ce (NO
3)
36H
2O, Mn (NO
3)
2And Co (NO
3)
26H
2The water-soluble solution of O is mixed with the steeping fluid of porous porcelain ring particle, Ce (NO in the steeping fluid
3)
36H
2O concentration is 0.2-0.4mol/L, Mn (NO
3)
2Concentration is 0.2-0.4mol/L, Co (NO
3)
26H
2O concentration is 0.2-0.4mol/L, and the porous porcelain ring particle that will obtain after step 2.1 pre-treatment is immersed in and carries out ultrasonic immersing absorption 40-60 minute in the above-mentioned steeping fluid;
Step 2.3, thermal treatment: the porous porcelain ring particle after the ultrasonic immersing absorption is taken out, and drying is 4 hours under 110-120 ℃;
Step 2.4, calcination activation: porous porcelain ring particle that will be is after heat treatment put into retort furnace, is warming up to 400-500 ℃ from room temperature by 5 ℃/minute temperature rise rate, is incubated 3-4 hour, naturally cools to room temperature;
Step 2.5, with the porous porcelain ring particle that obtains according to step 2.2 to step 2.4 circular treatment 2 times, obtain to be loaded with the porous porcelain ring granule electrode of metal active constituent;
The preparation of step 3, composite particles electrode:
The activated carbon grain sub-electrode that is loaded with metal active constituent with step 1 acquisition, the porous porcelain ring granule electrode that is loaded with metal active constituent with step 2 acquisition, ratio according to mass ratio 6:4-7:3 is evenly mixed, and namely obtains to be applied to the composite particles electrode of multipole 3 D electrode reactor.
6. the composite particles electrode preparation method that is applied to the multipole 3 D electrode reactor according to claim 5 is characterized in that: step 1.2, the absorption of activated carbon granule dipping: prepare SnCl respectively
45H
2O concentration is 0.5-0.6mol/L, SbCl
3Concentration is 0.1-0.2mol/L, FeCl
3Concentration is the steeping fluid of three kinds of activated carbon granules of 0.3mol/L, and the activated carbon granule that will obtain after step 1.1 pre-treatment is immersed in three kinds of above-mentioned steeping fluids one by one, and dipping absorption 2-4 hour of vibrating respectively.
7. the composite particles electrode preparation method that is applied to the multipole 3 D electrode reactor according to claim 5 is characterized in that: step 2.2, the absorption of porous porcelain ring particle dipping: prepare Ce (NO respectively
3)
36H
2O concentration is 0.2-0.4mol/L, Mn (NO
3)
2Concentration is 0.2-0.4mol/L, Co (NO
3)
26H
2O concentration is the steeping fluid of three kinds of porous porcelain ring particles of 0.2-0.4mol/L, and the porous porcelain ring particle that will obtain after step 2.1 pre-treatment is immersed in three kinds of above-mentioned steeping fluids one by one, and carries out ultrasonic immersing absorption 40-60 minute respectively.
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