CN109626514A - A kind of carbon ceramics core-shell type three dimensional particles electrode and preparation method thereof - Google Patents
A kind of carbon ceramics core-shell type three dimensional particles electrode and preparation method thereof Download PDFInfo
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- 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
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses a kind of carbon ceramics core-shell type three dimensional particles electrodes and preparation method thereof, including by anode plate, electrolytic cell, cathode plate, carbon ceramics core-shell type three dimensional particles electrode, the three-dimensional electrocatalysis oxidation apparatus of peristaltic pump and power supply composition, carbon ceramics core-shell type three dimensional particles electrode is placed in electrolytic cell, the two sides of the carbon ceramics core-shell type three dimensional particles electrode of accumulation are attached in anode plate and cathode plate, anode plate is connected to the anode of power supply, cathode plate is connected to the cathode of power supply, electrolytic cell connects peristaltic pump by conduit, carbon ceramics core-shell type three dimensional particles electrode includes clay 15wt%-30wt%, the heap density of coal dust is 0.45t/m3‑0.5t/m3, content be coal dust 1wt%-9wt% metal salt.Carbon ceramics core-shell type three dimensional particles electrode catalyst activity is high, the energy consumption of unit COD is low, active component not easily runs off, it is long that the service life is used continuously for this, and preparation process is simple, cheap, strong applicability, the waste water especially suitable for bio-refractory.
Description
Technical field
The present invention relates to environmental technology field, in particular to a kind of carbon ceramics core-shell type three dimensional particles electrode and its preparation side
Method.
Background technique
With the rapid development of economy in China, especially in chemical field, the waste of generation also increases therewith, to environment
Caused by pollute and also get worse, especially some high concentrations, bio-refractory, the organic pollutant for having acute or chronic toxicity
And it is irreversible that the discharge amount of high-concentration ammonia nitrogenous wastewater, which sharply increases pollution on the environment,.
Traditional wastewater treatment method mainly has: physical method, chemical method and bioanalysis.Wherein physical method mainly includes absorption
Method and extraction are that easy to operate, applied widely, processing cost is low with the advantages of physical method processing waste water, but are difficult to thorough
Secondary pollution is managed and be easy to cause in bottom, is restricted in terms of the waste water of processing high density pollution object；Chemical method mainly wraps
Oxidizing process and reduction method, traditional chemical oxidization method are included, although may finally reach processing intent, processing cost is high and grasps
Make complicated；Bioanalysis is processing method most economical, that treatment effeciency is higher and environmentally friendly, but it is only suitable for for handling bio-compatible
Property organic matter, but most of industrial wastewaters have bio-toxicity, directly processing be restricted.
Electrochemical oxidation process is a kind of high-level oxidation technology, with without secondary pollution, controllability is relatively strong, low energy consumption, reaction
Equipment and its it is easy to operate and with air bearing, flocculation, sterilization the effects of, be known as environmental-friendly green technology, just get over
To be more taken seriously.
Electro-catalytic oxidation technology is when handling industrial wastewater, without adding other medicaments, can by hardly degraded organic substance or
Bio-toxicity pollutant is converted into biodegradable or innocuous substance, improves the biodegradability of waste water, to be conducive to subsequent life
Object processing.Its mechanism, mainly by generating the active group with strong oxidizing property such as hydroxyl radical free radical to the pollution in waste water
Object carries out oxidative degradation, and short processing time is easy to operate.To sum up, electrocatalytic oxidation water treatment technology is in processing high concentration, difficult life
Have the characteristics that in terms of changing degradation industrial wastewater green and efficient.
Electrochemical oxidation process is divided into traditional two-dimensional electrode method and new Based on Three-dimensional Electrode Method, three-diemsnional electrode electrocatalytic oxidation skill
The core of art is electrode material, and the performance of three-diemsnional electrode determines the treatment effeciency and cost of electrocatalytic oxidation.Therefore, at present
The research emphasis of electro-catalytic oxidation technology is to explore and prepare the electrocatalysis material of good combination property.The resistance of conventional electrode materials
It is larger, conductivity is low, be used in actual waste water processing in, keep current efficiency sinking low, stability is poor, the service life is short, electrode material
Preparation process is complicated and preparation cost is higher, furthermore absorbent charcoal material, although treatment effect is preferable, because it is expensive, and function
It is single, its practical application in the treatment of waste water is also limited, therefore, exploratory development and prepares a kind of novel three-dimensional electrode material
It is the key that solve the problems, such as.
Summary of the invention
Invention is designed to provide a kind of carbon ceramics core-shell type three dimensional particles electrode and preparation method thereof, the carbon ceramics shell
Caryogram three dimensional particles electrode catalyst activity is high, the energy consumption of unit COD is low, active component not easily runs off, the service life is used continuously
Long, preparation method process is simple, cheap, strong applicability, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of carbon ceramics core-shell type three dimensional particles electrode, packet
Include the three-dimensional electricity being made of anode plate, electrolytic cell, cathode plate, carbon ceramics core-shell type three dimensional particles electrode, peristaltic pump and power supply
Catalytic oxidizing equipment, carbon ceramics core-shell type three dimensional particles electrode are placed in electrolytic cell, the carbon ceramics core-shell type three-dimensional grain of accumulation
The two sides of sub-electrode are attached in anode plate and cathode plate, and anode plate is connected to the anode of power supply, and cathode plate is connected to power supply
Cathode, the electrolytic cell connect peristaltic pump by conduit；
Carbon ceramics core-shell type three dimensional particles electrode include clay 15wt%-30wt%, coal dust heap density be 0.45t/m3-
0.5t/m3, content be coal dust 1wt%-9wt% metal salt.
Further, the metal salt is zinc 7wt%-30wt%, copper 3wt%-30wt%, nickel 5wt%-20wt%, cerium
1wt%-20wt%, cobalt 7wt%-15wt%, iron 11wt%-30wt%, tin 1wt%-5wt%, antimony 3wt%-5wt%, each group
Dividing the sum of weight percent is 100%.
Further, the carbon ceramics core-shell type three dimensional particles electrode is the spherical particle of diameter 5-10mm.
Further, the anode plate is the titanium steel plate for plating ruthenium, iridium, tantalum, and cathode plate is titanium steel plate, and size is 100mm
× 100mm × 1mm, electrolytic cell are the self-control of thickness 10mm polypropylene, and power supply is pulse dc power.
The present invention provides a kind of another technical solution: preparation method of carbon ceramics core-shell type three dimensional particles electrode, including
Following steps:
Step 1 is first uniformly mixed by the metal salt of the 1wt%-9wt% of quality of pc in granule machine；
Step 2, the viscous glutinous agent of sprinkling, make it at the spherical particle of 5-10mm, then spray viscous glutinous agent, and the viscous glutinous agent made is uniform
The surface for being attached to spherical particle；
Step 3, the clay that 15wt%-30wt% is added, finally make clay uniformly be attached to the surface of spherical particle, do
Dry, roasting,.
Further, the addition form of zinc is one of zinc nitrate, zinc sulfate, zinc chloride or zinc oxide in metal salt,
The addition form of copper is one of copper nitrate, copper chloride, copper carbonate or copper sulphate, and the addition form of nickel is nickel oxide, sulfuric acid
One of nickel, nickel chloride or nickel nitrate, the addition form of cerium are one in cerous nitrate, cerous sulfate, cerium oxide or cerous chlorate
Kind, the addition form of cobalt is one of cobalt nitrate, cobaltous sulfate, cobalt chloride or cobalt oxide, the addition form of iron be ferrous sulfate,
One of ferric sulfate, frerrous chloride, iron chloride or iron oxide, the addition form of tin are stannous sulfate, stannic chloride, the addition of antimony
Form is one of antimony chloride or antimony oxide.
Further, the viscous glutinous agent is certain density non-ionic polyacrylamide aqueous solution.
Further, drying temperature is 80 DEG C -120 DEG C, drying time 12h-24h.
Further, maturing temperature is 900 DEG C -1200 DEG C, calcining time 1h-3h.
Compared with prior art, the beneficial effects of the present invention are: carbon ceramics core-shell type three dimensional particles proposed by the present invention are electric
Pole and preparation method thereof is mixed in coal dust using by metal component, and coal dust is uniformly mixed in granule machine with metal salt；Spray
Viscous glutinous agent is spilt, its spheronizing particle is made, then sprays and sticks agent with certain density non-ionic polyacrylamide aqueous solution is viscous, is made
Viscous glutinous agent is uniformly attached to the surface of spherical particle；Clay is added, clay is finally made uniformly to be attached to the surface of spherical particle,
It is dry in baking oven, then in Muffle kiln roasting, manufactured carbon ceramics core-shell type three dimensional particles electrode compares more two-dimentional electricity
Pole has many advantages, such as that catalytic activity is high, active component not easily runs off, it is long that the service life is used continuously, and its preparation process is simple, valence
Lattice are cheap, strong applicability, especially suitable for the waste water of bio-refractory, treated wastewater to reach standard or can achieve and can give birth to
Change the standard of processing.
Detailed description of the invention
Fig. 1 is three-dimensional electrocatalysis oxidation apparatus schematic diagram of the invention；
Fig. 2 is the effect contrast figure of two and three dimensions electrode Electro-catalytic Oxidation Process organic matter of the invention.
In figure: 1, anode plate；2, electrolytic cell；3, cathode plate；4, carbon ceramics core-shell type three dimensional particles electrode；5, peristaltic pump；
6, power supply.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 15wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 1wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 1wt% of coal dust, and wherein the amount of zinc nitrate is total metal
The amount of salt is 20wt%, and the amount of copper sulphate is that the amount of total metal salt is 25wt%, and the amount of nickel oxide is the amount of total metal salt
It is 15wt%, the amount of cobaltous sulfate is that the amount of total metal salt is 10wt%, and the amount of ferrous sulfate is that the amount of total metal salt is
20wt%, the amount of stannous sulfate are that the amount of total metal salt is 5%, and the amount of antimony oxide is that the amount of total metal salt is 5wt%, will
Coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with one
Determine the viscous glutinous agent of non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made is uniformly attached to the surface of spherical particle；It is added
The clay of 15wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 800 DEG C of temperature calcination 2h,.
Embodiment 2
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 20wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 3wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 3wt% of coal dust, and wherein the amount of zinc sulfate is total metal
The amount of salt is 20wt%, and the amount of copper chloride is that the amount of total metal salt is 25wt%, and the amount of nickel sulfate is the amount of total metal salt
It is 15wt%, the amount of cobalt nitrate is that the amount of total metal salt is 10wt%, and the amount of ferrous sulfate is that the amount of total metal salt is
20wt%, the amount of stannous sulfate are that the amount of total metal salt is 5%, and the amount of antimony oxide is that the amount of total metal salt is 5wt%, will
Coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with one
Determine the viscous glutinous agent of non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made is uniformly attached to the surface of spherical particle；It is added
The clay of 20wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 800 DEG C of temperature calcination 2h,.
Embodiment 3
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 20wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 5wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 5wt% of coal dust, and wherein the amount of zinc sulfate is total metal
The amount of salt is 20wt%, and the amount of copper chloride is that the amount of total metal salt is 25wt%, and the amount of nickel sulfate is the amount of total metal salt
It is 15wt%, the amount of cobalt nitrate is that the amount of total metal salt is 10wt%, and the amount of ferrous sulfate is that the amount of total metal salt is
20wt%, the amount of stannous sulfate are that the amount of total metal salt is 5%, and the amount of antimony oxide is that the amount of total metal salt is 5wt%, will
Coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with one
Determine the viscous glutinous agent of non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made is uniformly attached to the surface of spherical particle；It is added
The clay of 20wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 800 DEG C of temperature calcination 2h,.
Embodiment 4
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 25wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 7wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 7wt% of coal dust, and wherein the amount of zinc chloride is total metal
The amount of salt is 20wt%, and the amount of copper carbonate is that the amount of total metal salt is 25wt%, and the amount of nickel chloride is the amount of total metal salt
It is 15wt%, the amount of cobalt chloride is that the amount of total metal salt is 10wt%, and the amount of ferric sulfate is that the amount of total metal salt is
20wt%, the amount of stannic chloride are that the amount of total metal salt is 5%, and the amount of antimony chloride is that the amount of total metal salt is 5wt%, by coal
Powder is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with certain
The viscous glutinous agent of the non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made are uniformly attached to the surface of spherical particle；It is added
The clay of 25wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 800 DEG C of temperature calcination 2h,.
Embodiment 5
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 25wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 9wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 9wt% of coal dust, and wherein the amount of zinc oxide is total metal
The amount of salt is 20wt%, and the amount of copper sulphate is that the amount of total metal salt is 25wt%, and the amount of nickel nitrate is the amount of total metal salt
It is 15wt%, the amount of cobaltous sulfate is that the amount of total metal salt is 10wt%, and the amount of ferric sulfate is that the amount of total metal salt is
20wt%, the amount of stannous sulfate are that the amount of total metal salt is 5%, and the amount of antimony chloride is that the amount of total metal salt is 5wt%, will
Coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with one
Determine the viscous glutinous agent of non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made is uniformly attached to the surface of spherical particle；It is added
The clay of 25wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 800 DEG C of temperature calcination 2h,.
Embodiment 6
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 30wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 5wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 9wt% of coal dust, and wherein the amount of zinc chloride is total metal
The amount of salt is 20wt%, and the amount of copper sulphate is that the amount of total metal salt is 25wt%, and the amount of nickel nitrate is the amount of total metal salt
It is 15wt%, the amount of cobaltous sulfate is that the amount of total metal salt is 10wt%, and the amount of iron oxide is that the amount of total metal salt is
20wt%, the amount of stannous sulfate are that the amount of total metal salt is 5%, and the amount of antimony chloride is that the amount of total metal salt is 5wt%, will
Coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with one
Determine the viscous glutinous agent of non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made is uniformly attached to the surface of spherical particle；It is added
The clay of 30wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 1000 DEG C of temperature calcination 2h,.
Embodiment 7
Heap density of the carbon ceramics core-shell type three dimensional particles electrode 4 including clay 30wt%, coal dust is 0.45t/m3-0.5t/
m3, content be coal dust 1wt% metal salt.
A kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode, includes the following steps:
It mixes metal component to enter in coal dust, the content of metal salt is the 1wt% of coal dust, and wherein the amount of zinc chloride is total metal
The amount of salt is 20wt%, and the amount of copper chloride is that the amount of total metal salt is 25wt%, and the amount of nickel nitrate is the amount of total metal salt
It is 15wt%, the amount of cobalt oxide is that the amount of total metal salt is 10wt%, and the amount of ferric sulfate is that the amount of total metal salt is
20wt%, the amount of stannous sulfate are that the amount of total metal salt is 5%, and the amount of antimony oxide is that the amount of total metal salt is 5wt%, will
Coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes it at the spherical particle of 5-10mm, then spray with one
Determine the viscous glutinous agent of non-ionic polyacrylamide aqueous solution of concentration, the viscous glutinous agent made is uniformly attached to the surface of spherical particle；It is added
The clay of 30wt% finally makes clay uniformly be attached to the surface of spherical particle, dry for 24 hours with 100 DEG C of temperature in an oven,
Again in Muffle furnace with 1000 DEG C of temperature calcination 1h,.
A kind of carbon ceramics core-shell type three dimensional particles electrode, including by anode plate 1, electrolytic cell 2, cathode plate 3, carbon ceramics shell core
The three-dimensional electrocatalysis oxidation apparatus (such as Fig. 1) that type three dimensional particles electrode 4, peristaltic pump 5 and power supply 6 form, carbon ceramics core-shell type
Three dimensional particles electrode 4 is placed in electrolytic cell 2, and carbon ceramics core-shell type three dimensional particles electrode 4 is the spherical particle of diameter 5-10mm,
The two sides of the carbon ceramics core-shell type three dimensional particles electrode 4 of accumulation are attached on anode plate 1 and cathode plate 3, and anode plate 1 is connected to electricity
The anode in source 6, cathode plate 3 are connected to the cathode of power supply 6, are that anode plate 1 and cathode plate 3 are powered by power supply 6, make carbon ceramics shell
Caryogram three dimensional particles electrode 4 generates electrolysis in electrolytic cell 2, and anode plate 1 is the titanium steel plate for plating ruthenium, iridium, tantalum, and cathode plate 3 is titanium
Steel plate, size are 100mm × 100mm × 1mm, and electrolytic cell 2 is the self-control of thickness 10mm polypropylene, and power supply 6 is pulse direct current
Source, electrolytic cell 2 connect peristaltic pump 5 by conduit, provide electrolyte by peristaltic pump 5 for electrolytic cell 2 and control its flow.
It selects the titanium steel plate of plating ruthenium, iridium, tantalum pentoxide as anode, selects titanium steel plate as cathode, three will prepared
Dimension electrode filler is filled between cathode-anode plate, forms three-dimensional electrocatalytic oxidation system (referring to Fig. 1).It is 15V in tank voltage, exposes
Tolerance is 1L/min, and initial pH of intaking reacts 120min, every 30min sampling carries out COD in 6-7crDetection and analysis.To TPAOH
Simulated wastewater, CODcrFor 1424.26mg/L.Wherein the pole plate of two-dimensional electrode equally selects the titanium steel plate of plating ruthenium, iridium, tantalum pentoxide
As anode, selects titanium steel plate as cathode, TPAOH simulated wastewater is handled under identical condition.
Above-mentioned treatment effect is shown in Fig. 2, compared with traditional two-dimentional electro-catalysis, the various embodiments described above three-diemsnional electrode is added and fills out
Expect the three-dimensional electrocatalytic oxidation system formed, although treatment effect is variant between respectively, all shows better processing
Effect.
Such as Fig. 2, horizontal axis indicates reaction time, unit are as follows: min；The longitudinal axis indicates waste water CODcrRemoval rate, unit are as follows: %；—
■-represents the COD of the electrocatalytic oxidation system of two-dimensional electrodecrRemoval rate；- ●-represent 1 three-diemsnional electrode electricity filler of embodiment
The COD of the three-dimensional electrodes system of compositioncrRemoval rate；- ▲-represents the three-diemsnional electrode of 2 three-diemsnional electrode electricity filler of embodiment composition
The COD of systemcrRemoval rate；- ★-represents the COD of the three-dimensional electrodes system of 3 three-diemsnional electrode electricity filler of embodiment compositioncrRemoval
Rate；- ◆-represent 4 three-diemsnional electrode electricity filler of embodiment composition three-dimensional electrodes system CODcrRemoval rate；- ☆-representative is real
Apply the COD of the three-dimensional electrodes system of 5 three-diemsnional electrode electricity filler of example compositioncrRemoval rate；- ◇-represents embodiment 6 three-diemsnional electrode electricity
The COD of the three-dimensional electrodes system of filler compositioncrRemoval rate；- zero-represents the three-dimensional of 7 three-diemsnional electrode electricity filler of embodiment composition
The COD of electrode systemcrRemoval rate.
Into 150min is crossed, treated that change of water quality is shown in Table 1
1 TPAOH simulated wastewater of table treated water quality
| Two dimension | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| CODcr(mg/L) | 982.5 | 664.3 | 459.6 | 260.3 | 264.5 | 263.3 | 302.0 | 594.4 |
As can be seen from the above table, two-dimensional electrode electro-catalysis treatment effect is bad, CODcrStill very high, place far can not be reached
Reason standard；And the three-dimensional electro-catalysis system of three-diemsnional electrode filler formation is added, CODcrIt reduces very much, and in the shorter time
Inside reach the standard that can be discharged.
In conclusion carbon ceramics core-shell type three dimensional particles electrode proposed by the present invention and preparation method thereof, using by metal
Component is mixed in coal dust, and coal dust is uniformly mixed in granule machine with metal salt；The viscous glutinous agent of sprinkling, makes its spheronizing grain
Son, then spray with the viscous glutinous agent of certain density non-ionic polyacrylamide aqueous solution, the viscous glutinous agent made is uniformly attached to pelletoid
The surface of son；Clay is added, so that clay is uniformly attached to the surface of spherical particle, dries in an oven, then in Muffle furnace
Middle roasting, manufactured carbon ceramics core-shell type three dimensional particles electrode 4 compares two-dimensional electrode, has that catalytic activity is high, activity
The advantages that component not easily runs off, that the service life is used continuously is long, and its preparation process is simple, cheap, strong applicability, it is especially suitable
For the waste water of bio-refractory, treated wastewater to reach standard or the standard that can achieve biochemical processing.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of carbon ceramics core-shell type three dimensional particles electrode, including by anode plate (1), electrolytic cell (2), cathode plate (3), carbon ceramics
The three-dimensional electrocatalysis oxidation apparatus of core-shell type three dimensional particles electrode (4), peristaltic pump (5) and power supply (6) composition, feature exist
In carbon ceramics core-shell type three dimensional particles electrode (4) is placed in electrolytic cell (2), the carbon ceramics core-shell type three dimensional particles electricity of accumulation
The two sides of pole (4) are attached on anode plate (1) and cathode plate (3), and anode plate (1) is connected to the anode of power supply (6), cathode plate
(3) it is connected to the cathode of power supply (6), the electrolytic cell (2) connects peristaltic pump (5) by conduit；
Carbon ceramics core-shell type three dimensional particles electrode (4) include clay 15wt%-30wt%, coal dust heap density be 0.45t/m3-
0.5t/m3, content be coal dust 1wt%-9wt% metal salt.
2. a kind of carbon ceramics core-shell type three dimensional particles electrode according to claim 1, which is characterized in that the metal salt is
Zinc 7wt%-30wt%, copper 3wt%-30wt%, nickel 5wt%-20wt%, cerium 1wt%-20wt%, cobalt 7wt%-15wt%, iron
11wt%-30wt%, tin 1wt%-5wt%, antimony 3wt%-5wt%, the sum of each component weight percent are 100%.
3. a kind of carbon ceramics core-shell type three dimensional particles electrode according to claim 1, which is characterized in that the carbon ceramics shell
Caryogram three dimensional particles electrode (4) is the spherical particle of diameter 5-10mm.
4. a kind of carbon ceramics core-shell type three dimensional particles electrode according to claim 1, which is characterized in that the anode plate
It (1) is plating ruthenium, the titanium steel plate of iridium, tantalum, cathode plate (3) is titanium steel plate, and size is 100mm × 100mm × 1mm, electrolytic cell (2)
For the self-control of thickness 10mm polypropylene, power supply (6) is pulse dc power.
5. a kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode according to claim 1-4, special
Sign is, includes the following steps:
S1, it is first uniformly mixed by the metal salt of the 1wt%-9wt% of quality of pc in granule machine；
S2, the viscous glutinous agent of sprinkling, make it at the spherical particle of 5-10mm, then spray viscous glutinous agent, and the viscous glutinous agent made is uniformly attached to
The surface of spherical particle；
S3, the clay that 15wt%-30wt% is added finally make clay uniformly be attached to the surface of spherical particle, and drying roasts,
?.
6. a kind of carbon ceramics core-shell type three dimensional particles electrode according to claim 5, which is characterized in that zinc in metal salt
Addition form is one of zinc nitrate, zinc sulfate, zinc chloride or zinc oxide, and the addition form of copper is copper nitrate, copper chloride, carbon
One of sour copper or copper sulphate, the addition form of nickel are one of nickel oxide, nickel sulfate, nickel chloride or nickel nitrate, cerium
Addition form is one of cerous nitrate, cerous sulfate, cerium oxide or cerous chlorate, the addition form of cobalt be cobalt nitrate, cobaltous sulfate,
One of cobalt chloride or cobalt oxide, the addition form of iron are ferrous sulfate, ferric sulfate, frerrous chloride, iron chloride or iron oxide
One of, the addition form of tin is stannous sulfate, stannic chloride, and the addition form of antimony is one of antimony chloride or antimony oxide.
7. a kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode according to claim 5, which is characterized in that institute
Stating viscous glutinous agent is certain density non-ionic polyacrylamide aqueous solution.
8. a kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode according to claim 5, which is characterized in that dry
Dry temperature is 80 DEG C -120 DEG C, drying time 12h-24h.
9. a kind of preparation method of carbon ceramics core-shell type three dimensional particles electrode according to claim 5, which is characterized in that roasting
Burning temperature is 900 DEG C -1200 DEG C, calcining time 1h-3h.
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