CN110395859B - Anode material suitable for electrochemical sludge treatment and preparation method thereof - Google Patents

Anode material suitable for electrochemical sludge treatment and preparation method thereof Download PDF

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CN110395859B
CN110395859B CN201910671561.7A CN201910671561A CN110395859B CN 110395859 B CN110395859 B CN 110395859B CN 201910671561 A CN201910671561 A CN 201910671561A CN 110395859 B CN110395859 B CN 110395859B
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titanium
titanium substrate
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CN110395859A (en
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李晓良
郑兴
路思佳
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Xian University of Technology
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/006Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/30Electroplating: Baths therefor from solutions of tin
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/60Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/38Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00Electrolytic coating other than with metals
    • C25D9/04Electrolytic coating other than with metals with inorganic materials
    • C25D9/06Electrolytic coating other than with metals with inorganic materials by anodic processes

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Abstract

The invention discloses a novel anode material suitable for electrochemical sludge treatment and a preparation method thereof, which comprises the steps of firstly carrying out high-temperature oxidation on a titanium substrate in an oxygen-deficient environment to form a titanium oxide layer with oxygen vacancy in an amorphous state, and carrying out cathode reduction on the titanium oxide layer by adopting an electrochemical method to form a substrate layer with good conductivity; then, Sb-SnO is loaded in a secondary electrodeposition-thermal oxidation mode2The intermediate layer is used for enhancing the conductivity and stability of the electrode and the adhesive force between the substrate and the surface layer; finally, the strongly hydrophobic nano particles are doped in the PbO in a codeposition mode2Coating to obtain a high-stability PbO with hydrophobic surface2And modifying the electrode. The electrode prepared by the method has longer reinforced service life and hydrophobicity, and can inhibit the adhesion of sludge to electrode reaction sites and improve the dewatering reduction effect of the sludge in the sludge treatment process.

Description

Anode material suitable for electrochemical sludge treatment and preparation method thereof
Technical Field
The invention belongs to the technical field of sludge electrochemical treatment, and particularly relates to an anode material suitable for electrochemical sludge treatment and a preparation method of the anode material.
Background
In recent years, China has made great progress in the field of sewage treatment, and the sludge treatment is far behind the expected target. According to the statistics of the Ministry of housing and construction, by 2018 and 6 months, more than 3802 county-level sewage treatment plants are shared in China, and the annual treatment total capacity reaches 588 hundred million m3The treatment rate reaches over 86 percent. The treatment rate of 3250 ten thousand tons of municipal sludge (with the water content of 80%) generated in 2018 is only close to 6%, the phenomenon of 'heavy water and light mud' is serious, and the sludge is positionedDisposal and disposal have become the greatest problem in sewage treatment plants.
Compared with the traditional sludge treatment technology, the electrochemical technology has the advantages of cleanness, high efficiency, simple operation, mild reaction condition, economy and the like. Electrochemical sludge treatment is a green process, can realize the purposes of sludge lysis reduction and dehydration, and has been reported for many times at present. Meanwhile, patents related to electrochemical sludge treatment technologies also appear correspondingly.
The great thesis of Li YuTing of Hunan university, namely the research on electrochemical oxidation method reduction of sludge in sewage plant and plate-and-frame filter-pressing dehydration test, aims at sludge reduction, researches the dehydration performance of the sludge pretreated by the electrochemical oxidation method and the experiment research on electrolyzing and refluxing partial residual sludge in a sequencing batch activated sludge process SBR sewage treatment system to a biological reaction tank from two aspects of source reduction and terminal reduction, and proves the feasibility of the electrochemical oxidation method on sludge dehydration and sludge reduction.
The Chinese invention patent "electrochemical sludge reduction treatment method" (published: CN109081539A application No. 201811039230.3, published: 20181225) discloses an electrochemical sludge reduction treatment method, which provides a treatment process that sludge can be extracted from a secondary sedimentation tank, sent into an electric treatment reactor, discharged to a sludge dehydration center after electrochemical cell dissolution, and supernatant after dehydration flows back to the front end of a biochemical tank. The method can improve the sludge treatment capacity of the sewage plant, and can reduce the sludge of the whole system while reducing the energy consumption, thereby finally achieving the aims of reduction and digestion.
The core of electrochemical sludge treatment is the anode used, the traditional anode has the problems of electrode pollution, low efficiency and the like in the sludge treatment process, and meanwhile, the research on the anode material in the sludge treatment aspect is less, so that the development of a novel anode suitable for the electrochemical treatment of the sludge is very important in the face of the increasingly severe sludge treatment situation.
Disclosure of Invention
The invention aims to provide an anode material suitable for electrochemical sludge treatment, and solves the problems of short service life and low efficiency of the traditional anode in the sludge treatment process in the prior art.
Another object of the present invention is to provide a method for preparing the above anode material.
The technical scheme adopted by the invention is that the anode material suitable for electrochemical sludge treatment comprises a substrate layer, an intermediate layer and a hydrophobic catalysis layer from inside to outside, wherein the substrate layer is titanium subjected to surface treatment, and the titanium surface layer is titanium hydroxide; the middle layer is Sb-SnO2(ii) a The hydrophobic catalytic layer is PbO containing hydrophobic material2
The invention adopts another technical scheme that a preparation method of an anode material suitable for electrochemical sludge treatment is implemented according to the following steps:
step 1, treating the surface of a titanium substrate to obtain a material A with a titanium hydroxide surface;
step 2, carrying out electrodeposition and thermal oxidation on the material A to load the intermediate layer to obtain a material B;
and 3, co-depositing the material B to load a hydrophobic catalytic layer to obtain the anode material suitable for electrochemical sludge treatment.
The preparation method of the anode material suitable for electrochemical sludge treatment is also characterized in that:
the step 1 is implemented according to the following steps:
step 1.1, polishing and cleaning a titanium substrate:
polishing a titanium substrate, putting the polished titanium substrate into a mixed solution consisting of acetone and NaOH solution in a volume ratio of 1:1, heating and ultrasonically treating the polished titanium substrate, wherein the mass concentration of NaOH is 5-10%;
step 1.2, etching the titanium substrate:
placing the titanium substrate treated in the step 1.1 into an oxalic acid solution with the temperature of 90-98 ℃ and the mass concentration of 5-10% for etching, then washing with deionized water, and airing;
step 1.3, heat treatment of the titanium substrate:
placing the titanium substrate treated in the step 1.2 in a pressure environment consisting of oxygen and nitrogen, heating the titanium substrate to 150-350 ℃ from room temperature, and then carrying out heat treatment for 30 min;
step 1.4, electrochemical treatment of the titanium substrate:
the titanium substrate treated by the step 1.3 is treated at 15-30 mA-cm-2And carrying out electrochemical reduction for 15-30 min under the current density to obtain the material A with the titanium hydroxide on the surface layer.
Heating the mixed solution to 50-90 ℃ in the step 1.1, and carrying out ultrasonic treatment for 10-15 min; in the step 1.2, the etching time in the oxalic acid solution is 90-150 min; in the step 1.3, the oxygen concentration in the pressure environment is 5-15%, the pressure is not less than 0.5bar, and the heating rate is 1-5 ℃/min.
The step 2 is implemented according to the following steps:
step 2.1, primary electrodeposition:
adopting a two-electrode system, taking the material A as a cathode and an insoluble conductive material as an anode, wherein the concentration of the two-electrode system is 0.5-1.5 mol.L-1SnCl4、0.1~0.2mol·L-1SbCl3、0.01~0.02mol·L-1NaF、0.05~0.15mol·L- 1HNO3、0.005~0.015mol·L-1Electrodepositing for 10-15 min in glycol solution of citric acid, wherein the cathode current density is 10-15 mA-cm-2After the electroplating is finished, putting the material A into an oven for drying;
step 2.2, secondary electrodeposition:
adopting a two-electrode system, wherein the material A treated in the step 2.1 is a cathode, the insoluble conductive material is an anode, and the concentration of the insoluble conductive material is 0.3-0.6 mol.L-1SnCl2、0.01~0.02mol·L-1NaF、0.05~0.15mol·L-1HNO3、0.005~0.015mol·L-1Electrodepositing for 15-20 min in glycol solution of citric acid, wherein the cathode current density is 5-10 mA-cm-2After the secondary electroplating is finished, putting the material A into an oven for drying;
step 2.3, thermal oxidation:
and (3) placing the material A treated in the step (2.2) in heating equipment, heating to 450-550 ℃ from room temperature, calcining for 50-70 min, and naturally cooling to room temperature to obtain a material B.
In steps 2.1 and 2.2, the insoluble conductive material is one of graphite, a DSA electrode or a Pt electrode; in the step 2.3, the heating rate is 1-5 ℃/min.
Step 3 is specifically implemented according to the following steps:
a two-electrode system is adopted, a material B is taken as an anode, a conductive material with the same size as the anode is taken as a cathode, and the current density is 5-200 mA-cm-1Electrodepositing for 5-120 min under the condition that the electrolyte is 0.3-0.6 mol.L-1Pb(NO3)2、0.01~0.02mol·L-1NaF、0.1~0.25mol·L-1Cu(NO3)2、0.05~0.15mol·L-1HNO3And electroplating an acidic organic solution consisting of hydrophobic nano particles at the temperature of 50-75 ℃, and finally cleaning the anode with deionized water to obtain the anode material suitable for electrochemical sludge treatment.
The hydrophobic nano-particles are one of polyolefin, polycarbonate, polyamide, polyacrylonitrile, polyester and fluorine/silicon materials.
The solvent in the organic solution is one of dimethyl sulfoxide, dimethylformamide, dichloromethane, tetrahydrofuran and alcohols.
The invention has the beneficial effects that: the invention adopts a simpler preparation mode, provides a high-performance electrocatalytic anode suitable for sludge treatment, and the prepared electrode has longer service life and better hydrophobicity, can effectively improve the effective utilization rate of HO-oxidized groups generated in the operation process of the electrode, inhibit the adhesion pollution of viscous substances such as sludge and the like to electrode reaction sites, and greatly improve the wall-breaking decrement effect and the dehydration performance of the sludge. Through the electrode effect of the invention, the dehydration performance of the sludge is greatly improved, the capillary water absorption time is reduced from the initial 14s to 7.5s, the wall breaking effect is obvious, the dry weight reduction of the residual sludge can reach more than 25 percent, the electrode performance is efficient and stable in the treatment process, and the operation cost is low.
Drawings
FIG. 1 is an SEM image of the surface of a material A in a preparation method of an anode material suitable for electrochemical sludge treatment according to the invention;
FIG. 2 is an XRD pattern of the surface of material A in a method for preparing an anode material suitable for electrochemical sludge treatment according to the present invention;
FIG. 3 is an SEM image of a hydrophobic catalytic layer of anode material suitable for electrochemical sludge treatment according to the present invention;
FIG. 4 is an XRD pattern of a hydrophobic catalytic layer of anode material suitable for electrochemical sludge treatment according to the present invention;
FIG. 5 is a contact angle diagram of a hydrophobic catalytic layer before modification and before non-modification in the preparation method of the anode material suitable for electrochemical sludge treatment;
FIG. 6 is a graph of enhanced life of an anode material suitable for electrochemical sludge treatment according to the present invention;
FIG. 7 shows the effect of an anode material suitable for electrochemical sludge treatment on sludge reduction at different times according to the present invention;
FIG. 8 is a capillary water absorption time trend graph of the anode material applied to the electrochemical sludge treatment in different time periods when the anode material acts on the sludge.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to an anode material suitable for electrochemical sludge treatment, which is respectively provided with a substrate layer, an intermediate layer and a hydrophobic catalysis layer from inside to outside, wherein the substrate layer is titanium subjected to surface treatment, and the titanium surface layer is titanium hydroxide; the middle layer is Sb-SnO2(ii) a The hydrophobic catalytic layer is PbO containing hydrophobic material2
Wherein, the titanium hydroxide is titanium oxide TiO with immature crystal form formed by titanium through anoxic oxidationxThen electrochemically reduced to form TiO with H atoms occupying part of the O atom positionsxH。
The preparation method is implemented according to the following steps:
step 1, treating the surface of a titanium substrate to obtain a material A with a titanium hydroxide surface, and specifically, the method comprises the following steps:
step 1.1, polishing and cleaning a titanium substrate:
polishing a titanium substrate, putting the polished titanium substrate into a mixed solution composed of acetone and NaOH solution in a volume ratio of 1:1, heating to 50-90 ℃, and carrying out ultrasonic treatment for 10-15 min to remove organic matters on the surface layer of the titanium substrate, wherein the mass concentration of NaOH is 5-10%;
step 1.2, etching the titanium substrate:
placing the titanium substrate treated in the step 1.1 into an oxalic acid solution with the temperature of 90-98 ℃ and the mass fraction of 5-10% for etching for 90-150 min, then washing with deionized water, and airing for later use;
step 1.3, heat treatment of the titanium substrate:
placing the titanium substrate treated in the step 1.2 in a pressure environment consisting of oxygen and nitrogen, heating the titanium substrate to 150-350 ℃ from room temperature at a heating rate of 1-5 ℃/min, and then carrying out heat treatment for 30min, wherein the pressure is not less than 0.5bar, the oxygen concentration is 5-15%, a layer of golden yellow titanium oxide film with an undeveloped crystal form is generated on the surface of the titanium substrate after heat treatment, and the conductivity is reduced after oxidation;
step 1.4, electrochemical treatment of the titanium substrate:
the titanium substrate treated by the step 1.3 is treated at 15-30 mA-cm-2Electrochemically reducing for 15-30 min under current density to form a high-conductivity black reduced titanium oxyhydrogen film matrix, and increasing the conductivity after reduction to obtain a material A with a titanium oxyhydrogen surface layer;
step 2, carrying out electrodeposition and thermal oxidation on the material A to load the intermediate layer to obtain a material B, and specifically carrying out the following steps:
step 2.1, primary electrodeposition:
adopting a two-electrode system, taking the material A as a cathode and an insoluble conductive material as an anode, wherein the concentration of the two-electrode system is 0.5-1.5 mol.L-1SnCl4、0.1~0.2mol·L-1SbCl3、0.01~0.02mol·L-1NaF、0.05~0.15mol·L- 1HNO3、0.005~0.015mol·L-1Electrodepositing for 10-15 min in glycol solution of citric acid, wherein the cathode current density is 10-15 mA-cm-2Drying the cathode after the electroplating is finished;
wherein the insoluble conductive material is one of graphite, a DSA electrode and a Pt electrode;
step 2.2, secondary electrodeposition:
adopting a two-electrode system, taking the material A treated in the step 2.1 as a cathode, taking insoluble conductive materials such as graphite and the like as an anode, and respectively adopting the concentration of the material A to the concentration of 0.3-0.6 mol.L-1SnCl2、0.01~0.02mol·L-1NaF、0.05~0.15mol·L- 1HNO3、0.005~0.015mol·L-1Electrodepositing for 15-20 min in glycol solution of citric acid, wherein the cathode current density is 5-10 mA-cm-2After the secondary electroplating is finished, the cathode is placed into an oven to be dried;
step 2.3, thermal oxidation:
heating the material A treated in the step 2.2 from room temperature to 450-550 ℃ at a heating rate of 1-5 ℃/min, calcining for 50-70 min, and naturally cooling to room temperature to obtain a material B;
and 3, codepositing the material B to load a hydrophobic catalytic layer to obtain the anode material suitable for electrochemical sludge treatment, which is specifically implemented according to the following steps:
a two-electrode system is adopted, a material B is taken as an anode, a conductive material with the same size as the anode is taken as a cathode, and the current density is 5-200 mA-cm-1Performing lower electrodeposition for 5-120 min, wherein the electrolyte is 0.3-0.6 mol.L-1Pb(NO3)2、0.01~0.02mol·L-1NaF、0.1~0.25mol·L-1Cu(NO3)2、0.05~0.15mol·L-1HNO3And an acidic organic solution composed of hydrophobic nano particles, wherein the temperature is 50-75 ℃, and after electroplating is finished, an anode is cleaned by deionized water to obtain the anode material suitable for electrochemical sludge treatment.
The hydrophobic nano-particles are one of polyolefin, polycarbonate, polyamide, polyacrylonitrile, polyester and fluorine/silicon materials.
The solvent in the organic solution is one of dimethyl sulfoxide, dimethylformamide, dichloromethane, tetrahydrofuran and alcohols.
The invention relates to an anode material suitable for electrochemical sludge treatment and a preparation method thereof, wherein the preparation method comprises the following steps:
the function of the step 1: carrying out high-temperature oxidation on a titanium substrate in an oxygen-deficient environment to form an oxygen-vacancy titanium oxide layer in an amorphous state, and carrying out cathode reduction on the titanium oxide layer by adopting an electrochemical method to form a substrate layer with good conductivity;
the function of the step 2: then, Sb-SnO is loaded in a secondary electrodeposition-thermal oxidation mode2The intermediate layer is used for enhancing the conductivity and stability of the electrode and the adhesive force between the substrate and the surface layer;
the function of the step 3: finally, the strongly hydrophobic nano particles are doped in the PbO in a codeposition mode2In the method, a hydrophobic catalytic layer is formed to obtain the high-stability PbO with hydrophobic surface2The modified electrode can inhibit the adhesion of sludge to electrode reaction sites and improve the dewatering and reducing effects of the sludge in the sludge treatment process.
Example 1
An anode material suitable for electrochemical sludge treatment comprises a substrate layer, an intermediate layer and a hydrophobic catalyst layer from inside to outside, wherein the substrate layer, the intermediate layer and the hydrophobic catalyst layer from inside to outside are respectively, the substrate layer is titanium subjected to surface treatment, and the titanium surface layer is titanium hydroxide; the middle layer is Sb-SnO2(ii) a The hydrophobic catalytic layer is PbO containing hydrophobic material2
The preparation method comprises the following steps:
step 1, treating the surface of a titanium substrate to obtain a material A with a titanium hydroxide surface, and specifically, the method comprises the following steps:
step 1.1, polishing and cleaning a titanium substrate: polishing a titanium substrate, putting the polished titanium substrate into a mixed solution of acetone and NaOH solution with the mass concentration of 5% in a volume ratio of 1:1, heating to 50 ℃, and carrying out ultrasonic treatment for 15min to remove organic matters on the surface layer of the titanium substrate;
step 1.2, etching the titanium substrate: placing the titanium substrate treated in the step 1.1 into oxalic acid solution with the temperature of 98 ℃ and the mass fraction of 5% for etching for 90min, then washing with deionized water, and airing for later use;
step 1.3, heat treatment of the titanium substrate: carrying out heat treatment on the titanium substrate treated in the step 1.2 at 150 ℃ for 30min in a nitrogen environment with the pressure of 1.5bar and the oxygen concentration of 10%, wherein the heating rate is 2 ℃/min;
step 1.4, electrochemical treatment of the titanium substrate: the titanium matrix treated by the step 1.3 is at 15mA cm-2Carrying out electrochemical reduction for 15min under the current density to obtain a material A with a titanium hydroxide surface layer;
step 2, carrying out electrodeposition and thermal oxidation on the material A to load the intermediate layer to obtain a material B, and specifically carrying out the following steps:
step 2.1, primary electrodeposition: adopting a two-electrode system, taking the material A as a cathode and graphite as an anode, and controlling the concentration to be 0.5 mol.L-1SnCl4、0.1mol·L-1SbCl3、0.02mol·L-1NaF、0.15mol·L-1HNO3、0.015mol·L-1Performing electrodeposition in ethylene glycol solution of citric acid for 10min, wherein the cathode current density is 15 mA-cm-2Drying the cathode after the electroplating is finished;
step 2.2, secondary electrodeposition:
adopting a two-electrode system, taking the material A treated in the step 2.1 as a cathode and graphite as an anode, wherein the concentrations are respectively 0.6 mol.L-1SnCl2、0.02mol·L-1NaF、0.15mol·L-1HNO3、0.015mol·L-1Electrodepositing for 15min in ethylene glycol solution of citric acid, wherein the cathode current density is 10 mA-cm-2Drying the cathode after finishing the secondary electroplating;
step 2.3, thermal oxidation:
the material A processed in the step 2.2 is heated to 450 ℃ from room temperature at the heating rate of 2 ℃/min, then calcined for 70min, and naturally cooled to room temperature to prepare a material B;
and 3, codepositing the material B to load a hydrophobic catalytic layer to obtain the anode material suitable for electrochemical sludge treatment, which is specifically implemented according to the following steps:
adopting a two-electrode system, taking the material B as an anode and a conductive material with the same size as the anode as a cathode, and performing a reaction at a current density of 200 mA-cm-1Performing electrodeposition for 5min, wherein the electrolyte is 0.3 mol.L-1Pb(NO3)2、0.01mol·L-1NaF、0.25mol·L-1Cu(NO3)2、0.15mol·L-1HNO3And polyolefin at 50 deg.c, and deionized water to clean the anode to obtain the anode material suitable for electrochemical sludge treatment.
The scanning electron microscope picture of the surface of the material A is shown in figure 1, and as can be seen from figure 1, the titanium matrix surface after high-temperature oxidation and electrochemical reduction processes has a hollow pitted surface structure, uniform and uniform nicks, increases the roughness of the matrix and is more favorable for the adhesion of a later-stage coating; the X-ray diffraction pattern of the surface of the material A is shown in FIG. 2, and it can be seen from FIG. 2 that TiH is detected in the XRD pattern of the surface of the material A after oxidation-electrochemical reductionxThe presence of diffraction peaks, indicating TiOxThe layer is reduced at the cathode to form a reduced titanium substrate.
As can be seen from fig. 3, the surface of the anode material modified by the hydrophobic catalytic layer shows a typical "rectangular pyramid" morphology, and through further careful observation, some unknown particles are gradually attached to the coating surface.
XRD of the anode material is shown in figure 4, and the main diffraction peak of the anode material is beta-PbO according to figure 42Meanwhile, a characteristic diffraction peak of the hydrophobic polyolefin is detected, which indicates that the hydrophobic nanoparticles are successfully doped in the electrode coating. SnO was not found2、Sb2O3Diffraction peak with Ti, indicating that it is PbO2The layers are well covered.
As shown in fig. 5, it can be seen from fig. 5 that the contact angle of the anode material is increased from the initial 62.5 ° to 125.5 ° by the modification of the hydrophobic nanoparticles, which indicates that the hydrophobicity of the modified electrode is greatly increased, so that the adhesion of sludge to the surface of the electrode can be inhibited, the utilization efficiency of HO and radicals of the electrode can be improved, and the sludge reduction effect can be improved.
As can be seen from FIG. 6, the prepared anode material was placed at 3 mol. L-1H2SO4Electrolyte (35 +/-2 ℃) and 500mA cm-2The electrolysis was carried out at an anodic current density and had a lifetime of 545 h.
As can be seen from FIG. 7, when the prepared anode material is used for treating sludge, the sludge reduction effect with the water content of 98% is obvious, and the dry weight (MLSS) and the wet weight are reduced within 180min to 32% and 83% respectively.
As can be seen from FIG. 8, when the prepared anode material is used for treating sludge, the dehydration performance of the sludge with the water content of 98% is obviously improved, the capillary water absorption time CST is reduced from the initial 13.4s to 7.2s within 180min, and the pressure is relieved for the subsequent sludge treatment link.
Example 2
An anode material suitable for electrochemical sludge treatment comprises a substrate layer, an intermediate layer and a hydrophobic catalytic layer from inside to outside, wherein the substrate layer is titanium subjected to surface treatment, and the titanium surface layer is titanium hydroxide; the middle layer is Sb-SnO2(ii) a The hydrophobic catalytic layer is PbO containing hydrophobic material2
The preparation method comprises the following steps:
step 1, treating the surface of a titanium substrate to obtain a material A with a titanium hydroxide surface, and specifically, the method comprises the following steps:
step 1.1, polishing a titanium substrate: polishing a titanium substrate, putting the titanium substrate into a mixed solution of acetone and NaOH solution with the mass concentration of 8% in a volume ratio of 1:1, heating to 70 ℃, and carrying out ultrasonic treatment for 12min to remove organic matters on the surface layer of the titanium substrate;
step 1.2, etching the titanium substrate: placing the titanium substrate treated in the step 1.1 into oxalic acid solution with the temperature of 94 ℃ and the mass fraction of 8% for etching for 120min, then washing with deionized water, and airing for later use;
step 1.3, heat treatment of the titanium substrate: carrying out high-temperature heat treatment on the titanium matrix treated in the step 1.2 at 250 ℃ for 30min in a nitrogen environment with the pressure of 2.0bar and the oxygen concentration of 15%, wherein the heating rate is 5 ℃/min;
step 1.4, electrochemical treatment of the titanium substrate: the titanium substrate treated by the step 1.3 is treated at 15-30 mA-cm-2Electrochemically reducing for 25min under current density, wherein the surface layer is a material A of titanium hydroxide;
step 2, carrying out electrodeposition and thermal oxidation on the material A to load the intermediate layer to obtain a material B, and specifically carrying out the following steps:
step 2.1, primary electrodeposition: adopts a two-electrode system, takes the material A as a cathode and the DSA electrode as an anode, and has the concentration of 1.0 mol.L-1SnCl4、0.15mol·L-1SbCl3、0.015mol·L-1NaF、0.10mol·L-1HNO3、0.01mol·L-1Electrodepositing for 125min in electroplating solution containing citric acid and ethylene glycol solution, wherein the cathode current density is 13 mA-cm-2Then, the cathode is dried after the electroplating;
step 2.2, secondary electrodeposition:
adopting a two-electrode system, taking the material A treated in the step 2.1 as a cathode, taking a DSA electrode as an anode, and respectively adopting the concentrations of 0.5 mol.L-1SnCl2、0.01mol·L-1NaF、0.1mol·L-1HNO3、0.01mol·L-1Electrodepositing for 18min in glycol solution of citric acid with a cathode current density of 8 mA-cm-2Drying the cathode after the secondary electroplating is finished;
step 2.3, thermal oxidation:
the material A processed in the step 2.2 is heated to 500 ℃ from room temperature at the heating rate of 5 ℃/min, then calcined for 60min, and naturally cooled to room temperature to prepare a material B;
and 3, codepositing the material B to load a hydrophobic catalytic layer to obtain the anode material suitable for electrochemical sludge treatment, which is specifically implemented according to the following steps:
adopting a two-electrode system, taking the material obtained in the step 2 as an anode, taking a conductive material with the same size as the anode as a cathode, and carrying out electrochemical reaction at a current density of 100 mA-cm-1Electrodepositing for 25min, wherein the electrolyte is 0.4 mol.L-1Pb(NO3)2、0.015mol·L-1NaF、0.20mol·L-1Cu(NO3)2、0.10mol·L-1HNO3And polycarbonate nano particles, at 65 ℃, washing with deionized water after electroplating to obtain the anode material suitable for electrochemical sludge treatment.
Placing the anode material at 3 mol.L-1H2SO4Electrolyte (35 +/-2 ℃), and,500mA·cm-2The electrolysis is carried out under the anode current density, and the service life of the electrolysis reaches 496 h.
The prepared anode material is used for treating sludge, the sludge decrement effect with the water content of 98 percent is obvious, and the dry weight (MLSS) and the wet weight are respectively reduced to 28 percent and 79 percent within 180 min.
The prepared anode material is used for treating sludge, the dehydration performance of the sludge with the water content of 98 percent is obviously improved, the capillary water absorption time CST is reduced from the initial 13.4s to 7.5s within 180min, and the pressure is relieved for the subsequent sludge treatment link.
Example 3
An anode material suitable for electrochemical sludge treatment comprises a substrate layer, an intermediate layer and a hydrophobic catalytic layer from inside to outside, wherein the substrate layer is titanium subjected to surface treatment, and the titanium surface layer is titanium hydroxide; the middle layer is Sb-SnO2(ii) a The hydrophobic catalytic layer is PbO containing hydrophobic material2
The preparation method comprises the following steps:
step 1, treating the surface of a titanium substrate to obtain a material A with a titanium hydroxide surface, and specifically, the method comprises the following steps:
step 1.1, polishing and cleaning a titanium substrate: polishing a titanium substrate, putting the polished titanium substrate into a mixed solution of acetone and NaOH solution with the volume ratio of 1:1 and the mass concentration of 10%, heating to 90 ℃, and carrying out ultrasonic treatment for 10min to remove organic matters on the surface layer of the titanium substrate;
step 1.2, etching the titanium substrate: placing the titanium substrate treated in the step 1.1 into an oxalic acid solution with the temperature of 90 ℃ and the mass fraction of 10% for etching for 150min, then washing with deionized water, and airing for later use;
step 1.3, performing high-temperature heat treatment on the titanium substrate: carrying out high-temperature heat treatment on the titanium matrix treated in the step 1.2 at 350 ℃ for 30min in a nitrogen environment with the pressure of 3.0bar and the oxygen concentration of 5%, wherein the heating rate is 5 ℃/min;
step 1.4, electrochemical treatment of the titanium substrate: the titanium substrate treated by the step 1.3 is treated at 15-30 mA-cm-2Carrying out electrochemical reduction for 30min under the current density to obtain a material A with a titanium hydroxide surface layer;
step 2, carrying out electrodeposition and thermal oxidation on the material A to load the intermediate layer to obtain a material B, and specifically carrying out the following steps:
step 2.1, primary electrodeposition: adopts a two-electrode system, takes a material A cathode and a Pt electrode as an anode, and has the concentration of 1.5 mol.L-1SnCl4、0.2mol·L-1SbCl3、0.01mol·L-1NaF、0.05mol·L-1HNO3、0.005mol·L-1Electrodepositing for 15min in ethylene glycol solution of citric acid, wherein the cathode current density is 10 mA-cm-2Drying the cathode after the electroplating is finished; (ii) a
Step 2.2, secondary electrodeposition:
adopting a two-electrode system, taking the material A treated in the step 2.1 as a cathode and a Pt electrode as an anode, and respectively adopting the concentration of 0.3 mol.L-1SnCl2、0.15mol·L-1NaF、0.05mol·L-1HNO3、0.005mol·L-1Performing electrodeposition in ethylene glycol solution of citric acid for 20min, wherein the cathode current density is 5 mA-cm-2Drying the cathode after the secondary electroplating is finished; (ii) a
Step 2.3, thermal oxidation:
the material A processed in the step 2.2 is heated from room temperature to 550 ℃ at the heating rate of 1 ℃/min, then is calcined for 50min, and is naturally cooled to room temperature, so that a material B is prepared;
and 3, codepositing the material B to load a hydrophobic catalytic layer to obtain the anode material suitable for electrochemical sludge treatment, which is specifically implemented according to the following steps:
adopting a two-electrode system, taking the material B as an anode and a conductive material with the same size as the anode as a cathode, and controlling the current density to be 5 mA-cm-1Performing bottom electrodeposition for 120min, wherein the electrolyte is 0.6 mol.L-1Pb(NO3)2、0.02mol·L-1NaF、0.1mol·L-1Cu(NO3)2、0.05mol·L-1HNO3And acid tetrahydrofuran composed of polyacrylonitrile nano particles at 75 ℃, and washing with deionized water after electroplating to obtain the anode material suitable for electrochemical sludge treatment.
Anode materialPlacing the material in a container with the concentration of 3 mol.L-1H2SO4Electrolyte (35 +/-2 ℃) and 500mA cm-2The anode current density is used for electrolysis, and the service life of the anode current density reaches 506 h.
The prepared anode material is used for treating sludge, the sludge decrement effect with the water content of 98 percent is obvious, and the dry weight (MLSS) and the wet weight are respectively decremented by 25 percent and 76 percent within 180 min.
The prepared anode material is used for treating sludge, the dehydration performance of the sludge with the water content of 98 percent is obviously improved, the capillary water absorption time CST is reduced from the initial 13.4s to 7.8s within 180min, and the pressure is relieved for the subsequent sludge treatment link.

Claims (3)

1. A preparation method of an anode material suitable for electrochemical sludge treatment is characterized by comprising the following steps:
step 1, treating the surface of a titanium substrate to obtain a material A with a titanium hydroxide surface; the titanium hydroxide is titanium oxide TiO with immature crystal form formed by titanium through anoxic oxidationxThen electrochemically reduced to form TiO with H atoms occupying part of the O atom positionsxH;
The step 1 is specifically implemented according to the following steps:
step 1.1, polishing and cleaning a titanium substrate:
polishing a titanium substrate, putting the polished titanium substrate into a mixed solution consisting of acetone and NaOH solution in a volume ratio of 1:1, heating and ultrasonically treating the polished titanium substrate, wherein the mass concentration of NaOH is 5-10%;
heating the mixed solution to 50-90 ℃ in the step 1.1, and carrying out ultrasonic treatment for 10-15 min;
step 1.2, etching the titanium substrate:
placing the titanium substrate treated in the step 1.1 into an oxalic acid solution with the temperature of 90-98 ℃ and the mass concentration of 5-10% for etching, then washing with deionized water, and airing;
in the step 1.2, the etching time in the oxalic acid solution is 90-150 min;
step 1.3, heat treatment of the titanium substrate:
placing the titanium substrate treated in the step 1.2 in a pressure environment consisting of oxygen and nitrogen, heating the titanium substrate to 150-350 ℃ from room temperature, and then carrying out heat treatment for 30 min;
in the step 1.3, the oxygen concentration in the pressure environment is 5-15%, the pressure is more than or equal to 0.5bar, and the heating rate is 1-5 ℃/min;
step 1.4, electrochemical treatment of the titanium substrate:
taking the titanium substrate treated in the step 1.3 as a cathode, and carrying out treatment at 15-30 mA-cm-2Carrying out electrochemical reduction for 15-30 min under the current density to obtain a material A with a titanium hydroxide surface layer;
step 2, carrying out electrodeposition and thermal oxidation on the material A to load the intermediate layer to obtain a material B;
the step 2 is implemented according to the following steps:
step 2.1, primary electrodeposition:
adopting a two-electrode system, taking the material A as a cathode and an insoluble conductive material as an anode, wherein the concentration of the two-electrode system is 0.5-1.5 mol.L-1 SnCl4、0.1~0.2 mol·L-1 SbCl3、0.01~0.02 mol·L-1 NaF、0.05~0.15 mol·L-1HNO3、0.005~0.015 mol·L-1Electrodepositing for 10-15 min in glycol solution of citric acid, wherein the cathode current density is 10-15 mA-cm-2After the electroplating is finished, putting the material A into an oven for drying;
step 2.2, secondary electrodeposition:
adopting a two-electrode system, wherein the material A treated in the step 2.1 is a cathode, the insoluble conductive material is an anode, and the concentration of the insoluble conductive material is 0.3-0.6 mol.L-1 SnCl2、0.01~0.02 mol·L-1 NaF、0.05~0.15mol·L-1 HNO3、0.005~0.015 mol·L-1Electrodepositing for 15-20 min in glycol solution of citric acid, wherein the cathode current density is 5-10 mA-cm-2After the secondary electroplating is finished, putting the material A into an oven for drying;
step 2.3, thermal oxidation:
placing the material A treated in the step 2.2 in heating equipment, heating the material A to 450-550 ℃ from room temperature, calcining the material A for 50-70 min, and naturally cooling the material A to room temperature to obtain a material B;
in steps 2.1 and 2.2, the insoluble conductive material is one of graphite, a DSA electrode or a Pt electrode; in the step 2.3, the heating rate is 1-5 ℃/min;
3, co-depositing the material B to load a hydrophobic catalysis layer to obtain an anode material suitable for electrochemical sludge treatment;
step 3 is specifically implemented according to the following steps:
a two-electrode system is adopted, a material B is taken as an anode, a conductive material with the same size as the anode is taken as a cathode, and the current density is 5-200 mA-cm−1Electrodepositing for 5-120 min under the condition that the electrolyte is 0.3-0.6 mol.L-1 Pb(NO3)2、0.01~0.02 mol·L-1 NaF、0.1~0.25 mol·L-1 Cu(NO3)2、0.05~0.15mol·L-1 HNO3And carrying out electrodeposition on an acidic organic solution consisting of hydrophobic nano particles at the temperature of 50-75 ℃, and finally cleaning the anode with deionized water to obtain the anode material suitable for electrochemical sludge treatment.
2. The method for preparing anode material suitable for electrochemical sludge treatment according to claim 1, wherein the hydrophobic nanoparticles are one of polyolefin, polycarbonate, polyamide, polyacrylonitrile, polyester, fluorine/silicon material.
3. The method according to claim 1, wherein the solvent in the organic solution is one of dimethyl sulfoxide, dimethylformamide, dichloromethane, tetrahydrofuran and alcohols.
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