CN107585833B - Preparation method and application of zero-valent cobalt activated carbon-based catalytic particle electrode - Google Patents
Preparation method and application of zero-valent cobalt activated carbon-based catalytic particle electrode Download PDFInfo
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Abstract
The invention relates to the field of sewage and wastewater treatment, in particular to a preparation method and application of a zero-valent cobalt activated carbon-based catalytic particle electrode. The catalytic particle electrode comprises activated carbon powder, a binder and a zero-valent cobalt catalyst loaded on the activated carbon powder, wherein the mass of the loaded zero-valent cobalt accounts for 8-10 wt% of the mass of the activated carbon. The method comprises the steps of activated carbon powder pretreatment, cobalt salt solution preparation, catalyst loading, binder preparation, particle electrode preparation and roasting activation. The zero-valent cobalt activated carbon-based catalytic particle electrode prepared by the invention has the advantages of simple preparation method operation, low energy consumption, good conductivity, low raw material cost, high cobalt loading and high catalytic activity, and can efficiently degrade and remove toxic and harmful organic matters in water under the conditions of lower current and voltage when being applied to a three-dimensional electro-catalytic reaction system.
Description
Technical Field
The invention relates to the field of sewage and wastewater treatment, in particular to a preparation method of a zero-valent cobalt catalytic particle electrode loaded with catalytic metal elements and degradation removal of toxic and harmful organic matters in water.
Technical Field
Toxic and harmful organic matters have complex components, exist in various sewage, waste water and water in large quantity, and seriously affect the environmental safety and the human health. Because of the toxicity of toxic and harmful substances, the substances are generally difficult to biodegrade, and are usually degraded and removed by adopting an advanced oxidation technology. The three-dimensional electrocatalytic oxidation method is one of advanced oxidation technologies, and has attracted extensive attention due to the characteristics of high pollutant removal efficiency, small occupied area, strong selectivity and the like.
Cobalt is a transition metal, and is widely used in heterogeneous catalytic systems due to its small atomic radius and special electronic structure. Generally, the cobalt catalyst exists in the form of cobalt oxide and zero-valent cobalt simple substance, and needs to be supported on a carrier for use. At present, the methods for loading and preparing the zero-valent cobalt catalyst mainly comprise: liquid phase reduction, immersion, thermal decomposition, pulsed current deposition, and the like. The liquid phase reduction method is a method for directly reducing raw material substances into zero-valent cobalt particles after certain electrolysis or chemical reaction in a liquid phase or in a state close to the liquid phase, common reducing agents comprise hydrazine hydrate, borohydride, hypophosphite, polyhydric alcohol and the like, but the method needs strong addition of the reducing agent during preparation, and the prepared catalyst has large particle size and poor particle stability and performance in general conditions. The thermal decomposition method means that organic compounds of cobalt are decomposed at high temperature to generate cobalt atoms, and then zero-valent cobalt particle materials are generated from the cobalt atoms, but expensive organic ligands and a large amount of organic reagents are needed in the decomposition process, and the generated powder is easy to agglomerate, needs to be subjected to secondary crushing, and has high cost. The pulse current deposition method uses electroplating technology to plate catalyst on the surface of carrier, and has the advantages of uniform catalyst distribution, low probability of falling off, and high energy consumption and strict requirement for carrier. The impregnation method is to immerse the catalyst carrier in cobalt solution with a certain concentration, oscillate and adsorb for a certain time, take out and dry, and then calcine at high temperature, and the method has simple and convenient operation process and low energy consumption, but the cobalt catalyst prepared by the impregnation method loading usually exists in the form of cobalt oxide, is mostly powder samples and is easy to run off.
Therefore, the invention adopts an excess impregnation method, uses polyvinyl alcohol and carboxylic acid as binders for granulation, is roasted at high temperature under the protection of nitrogen, prepares the zero-valent cobalt activated carbon-based catalytic particle electrode by physical mixing and one-step roasting, and is applied to a three-dimensional electro-catalytic treatment system. The preparation method has the advantages of simple operation, low energy consumption, good conductivity, low raw material cost, high cobalt loading and high catalytic activity, and can efficiently degrade and remove toxic and harmful organic matters in water under the conditions of lower current and voltage.
Disclosure of Invention
The invention aims to combine the adsorption performance of an activated carbon base and the catalytic performance of zero-valent cobalt, and provides a zero-valent cobalt activated carbon base catalytic particle electrode and a preparation method thereof, so that the zero-valent cobalt activated carbon base catalytic particle electrode has the characteristics of high pollutant degradation removal rate, high catalytic activity, high adsorption performance of the particle electrode, low energy consumption and the like, and the preparation method is simple.
The invention further aims to provide the granular electrode material which is applied to a three-dimensional electrocatalytic reaction system and is used for efficiently treating toxic and harmful substances in water.
The invention provides a preparation method of an active carbon-based catalytic particle electrode loaded with zero-valent cobalt, which comprises the following steps:
(1) pretreatment of activated carbon powder: washing the activated carbon powder with water, oscillating, separating, drying, and cooling to room temperature;
(2) preparing a cobalt salt solution: dissolving cobalt nitrate or cobalt sulfate in water, wherein the molar concentration of cobalt ions is 0.3-0.7 mol/L;
(3) loading a catalyst: soaking the activated carbon powder in the step (1) in a cobalt salt solution (2) according to the mass volume ratio of 1g: 5-8L, oscillating, centrifuging, drying, and cooling to room temperature;
(4) preparing a binder: dissolving polyvinyl alcohol in water under the condition of water bath, adding carboxylic acid and a catalyst simultaneously after the polyvinyl alcohol is completely dissolved, carrying out crosslinking reaction, and cooling to room temperature;
(5) preparing a particle electrode: uniformly mixing the activated carbon powder in the step (3) and the binder in the step (4) according to the mass volume ratio of 1g: 1-2L, granulating and drying;
(6) roasting and activating: mixing the granules prepared in (5) with N2And (4) roasting at high temperature under protection, and cooling to room temperature.
The cleaning conditions with the activated carbon powder in the step (1) are as follows: and separating the active carbon powder after the conductivity of the supernatant is consistent with that of the deionized water.
Furthermore, the drying temperature of the activated carbon powder in the step (1) is 100-105 ℃, and the drying time is 24-48 h.
In the oscillation reaction in the step (3), the oscillation temperature is 20-30 ℃, and the oscillation reaction time is 4-12 h.
Furthermore, the drying temperature in the step (4) is 100-105 ℃, and the drying time is 24-48 h.
The mass concentration of the polyvinyl alcohol solution in the step (4) is 8-12% (m/v).
Furthermore, the water bath conditions for preparing the polyvinyl alcohol solution in the step (4) are sequentially stirring for 20-40 min at 50-70 ℃, stirring for 25-35 min at 75-85 ℃, stirring for 50-70 min at 90-100 ℃, and stirring for 20-40 min at 50-70 ℃.
Furthermore, the carboxylic acid in the step (4) is maleic acid or citric acid, and the mass concentration is 4-10% (m/v).
Further, the catalyst in the step (4) is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated phosphoric acid.
Furthermore, after the carboxylic acid and the catalyst are added in the step (4), the volume ratio of the polyvinyl alcohol to the carboxylic acid to the catalyst is 1: 0.2-0.3: 0.01-0.1.
Furthermore, the crosslinking reaction temperature of the binder in the step (4) is 50-70 ℃, and the reaction time is 1-1.5 h.
And (5) drying at the temperature of 100-105 ℃ for 24-48 h.
And (4) roasting at the temperature of 450-800 ℃ for 1-6 h in the step (6).
The average particle size of the granular electrode prepared according to the invention is 2-7 mm, and the mass of the loaded zero-valent cobalt accounts for 8-10 wt% of the mass of the activated carbon.
According to the particle electrode prepared by the invention, when the particle electrode is applied to degrading and removing toxic and harmful organic substances in water, the particle electrode is filled between a positive electrode plate and a negative electrode plate to form a three-dimensional particle electrode reaction system for use; the anodes of the two electrode plates are ruthenium-titanium (RuO) electrodes2and/Ti), the cathode is a titanium electrode.
According to the preparation method of the catalytic particle electrode, the polyvinyl alcohol has double functions of bonding and protecting to generate zero-valent cobalt. Polyvinyl alcohol and carboxylic acid are used as binders, after the materials are prepared into particles, the carboxylic acid with a polycarboxyl structure is esterified with hydroxyl on the polyvinyl alcohol through high-temperature calcination, the carboxylic acid is grafted to a polyvinyl alcohol macromolecular chain, and crosslinking is formed inside the materials, so that the water resistance of the materials can be improved, and the mechanical property of the materials can also be improved due to the esterification and crosslinking; in addition, carboxyl on the carboxylic acid and hydroxyl on the polyvinyl alcohol can form a strong hydrogen bond, so that the intermolecular interaction is increased, and the mechanical property and the thermal stability are further improved. Therefore, under the condition of nitrogen protection, oxygen is further isolated, the formation of cobalt oxide is avoided, and the formation of a zero-valent cobalt catalytic active component is facilitated.
Compared with the existing method of preparing catalyst and then granulating, the method for preparing the catalytic particle electrode solves the problem of Chemical Oxygen Demand (COD) rise caused by dissolution of the binder of effluent water applied in a three-dimensional electro-catalytic reaction system, and enhances the strength and the conductivity of the particles because the binder is removed by calcination after granulation and carbonized.
The preparation method of the catalytic particle electrode has the following advantages and prominent technical effects:
(1) the preparation method of the particle is simple to operate, and the zero-valent cobalt activated carbon-based particle catalyst is prepared by adopting an excess impregnation method through physical mixing and a one-step calcination method;
(2) the efficiency of degrading toxic organic substances is high, when the organic substance degrading agent is used for treating wastewater containing toxic and harmful organic pollutants, the removal rate of organic substances is greatly improved, and the removal rate of Chemical Oxygen Demand (COD) reaches more than 90%;
(3) the prepared zero-valent cobalt activated carbon-based particles are applied to a three-dimensional electro-catalysis treatment system, the retention time is short, and toxic and harmful substances in wastewater can be efficiently degraded and removed;
(4) the loading capacity is large, the average particle size of the prepared granular electrode is 2-7 mm, and the weight of the loaded zero-valent cobalt accounts for 8-10 wt% of the weight of the activated carbon;
(5) the prepared particles are used for treating wastewater containing toxic and harmful organic pollutants, all electrocatalytic chemical reactions run under the condition of low current and voltage, and the energy consumption is low.
In conclusion, the preparation method of the zero-valent cobalt activated carbon-based granular catalyst has the advantages of simple operation, low energy consumption, good conductivity, low raw material cost, high cobalt loading and high catalytic activity, and can efficiently degrade and remove toxic and harmful organic matters in water under the conditions of lower current and lower voltage.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
Soaking the cleaned and dried activated carbon powder in 0.3mol/L cobalt sulfate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt sulfate solution is 1g:5L, and oscillating at the constant temperature of 20 ℃ for 12 h; in the preparation of the binder, the mass concentration of the polyvinyl alcohol solution is 8 percent, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, is stirred for 35min under 75 ℃, is stirred for 70min under 90 ℃ and is stirred for 40min under 50 ℃, and simultaneously, maleic acid with the mass concentration of 5 percent (m/v) and concentrated sulfuric acid with certain volume are added to ensure that the volume of the polyvinyl alcohol, the maleic acid and the concentrated sulfuric acid is equal to the volume of the polyvinyl alcohol, the maleic acid and the concentrated sulfuric acidThe reaction is carried out for 1.5h at 50 ℃ with the ratio of 1:0.2: 0.03; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 1.5L, drying for 48h at 100 ℃, and cooling to room temperature; in N2Protecting and roasting at 600 ℃ for 4 h.
The obtained zero-valent cobalt activated carbon-based granular electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based granular electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, simulated rhodamine B wastewater is treated, the treatment is carried out under the conditions that the COD of inlet water is 80-110mg/L and the current is 0.2A, the outlet water is stable after 10min, and the removal rate of the COD reaches 96.2%.
Example 2
Soaking the cleaned and dried activated carbon powder in 0.4mol/L cobalt sulfate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt sulfate solution is 1g:6L, and oscillating at the constant temperature of 25 ℃ for 8 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 8 percent, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, is stirred for 35min under 75 ℃, is stirred for 70min under 90 ℃, is stirred for 40min under 50 ℃, and simultaneously maleic acid with the mass concentration of 6 percent (m/v) and concentrated sulfuric acid with certain volume are added, so that the volume ratio of the polyvinyl alcohol to the maleic acid to the concentrated sulfuric acid is 1:0.25:0.05, and the reaction is carried out for 1h under 60 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 1.5L, drying for 24h at 105 ℃, and cooling to room temperature; in N2Protecting and roasting at 700 ℃ for 3 h.
The obtained zero-valent cobalt activated carbon-based particle electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based particle electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, the simulated acid red B dye wastewater is treated, the treatment is carried out under the conditions that the COD of inlet water is 100-plus-material/L and the current is 0.1A, the outlet water is stable after 20min, and the removal rate of the COD reaches 95.7%.
Example 3
Soaking the washed and dried activated carbon powder in 0.3mol/L cobalt nitrate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt nitrate solution is 1g:5L, and oscillating at the constant temperature of 20 ℃ for 12 h; in the preparation of adhesivesIn the preparation, the mass concentration of the polyvinyl alcohol solution is 8%, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, is stirred for 35min under 75 ℃, is stirred for 70min under 90 ℃, is stirred for 40min under 50 ℃, and is added with citric acid with the mass concentration of 5% (m/v) and concentrated sulfuric acid with certain volume at the same time, so that the volume ratio of the polyvinyl alcohol to the citric acid to the concentrated sulfuric acid is 1:0.2:0.03, and is reacted for 1.5h under 50 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 1.5L, drying for 24h at 105 ℃, and cooling to room temperature; in N2Protecting and roasting at 600 ℃ for 4 h.
The obtained zero-valent cobalt activated carbon-based particle electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based particle electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, the simulated petroleum refining wastewater is treated, the treatment is carried out under the conditions that the COD of inlet water is 100-plus-120 mg/L and the current is 0.3A, the outlet water is stable after 20min, and the removal rate of the COD reaches 97.2%.
Example 4
Soaking the washed and dried activated carbon powder in 0.5mol/L cobalt nitrate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt nitrate solution is 1g:5L, and oscillating at the constant temperature of 25 ℃ for 8 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 10 percent, the polyvinyl alcohol solution is stirred for 30min under the condition of water bath at 60 ℃, the polyvinyl alcohol solution is stirred for 30min under 80 ℃, the polyvinyl alcohol solution is stirred for 60min under 98 ℃, the polyvinyl alcohol solution is stirred for 30min under 60 ℃, meanwhile, maleic acid with the mass concentration of 6 percent (m/v) and concentrated sulfuric acid with certain volume are added, the volume ratio of the polyvinyl alcohol to the maleic acid to the concentrated sulfuric acid is 1:0.2:0.03, and the reaction is carried out for 1.5h at 50 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 1.5L, drying for 30h at 102 ℃, and cooling to room temperature; in N2Protecting and roasting at 600 ℃ for 4 h.
The obtained zero-valent cobalt activated carbon-based granular electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based granular electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, simulated polyacrylamide wastewater is treated, the treatment is carried out under the conditions that the COD (chemical oxygen demand) of inlet water is 70-100mg/L and the current is 0.2A, the outlet water is stable after 30min, and the removal rate of the COD reaches 98.4%.
Example 5
Soaking the cleaned and dried activated carbon powder in 0.7mol/L cobalt sulfate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt sulfate solution is 1g:8L, and oscillating at the constant temperature of 20 ℃ for 12 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 8 percent, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, is stirred for 35min under 75 ℃, is stirred for 70min under 90 ℃, is stirred for 40min under 50 ℃, and simultaneously maleic acid with the mass concentration of 5 percent (m/v) and concentrated hydrochloric acid with a certain volume are added, so that the volume ratio of the polyvinyl alcohol to the maleic acid to the concentrated hydrochloric acid is 1:0.2:0.03, and the reaction is carried out for 1.5h under 50 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 2L, drying for 30h at 102 ℃, and cooling to room temperature; in N2Protecting and roasting at 700 ℃ for 3 h.
The obtained zero-valent cobalt activated carbon-based particle electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based particle electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, the simulated acid orange 7 wastewater is treated, the treatment is carried out under the conditions that the COD of inlet water is 100-plus-material 120mg/L and the current is 0.1A, the outlet water is stable after 20min, and the removal rate of the COD reaches 99.5%.
Example 6
Soaking the washed and dried activated carbon powder in 0.6mol/L cobalt nitrate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt nitrate solution is 1g:5L, and oscillating at constant temperature of 30 ℃ for 4 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 12%, the polyvinyl alcohol solution is stirred for 20min under the condition of 70 ℃ water bath, is stirred for 25min under 85 ℃, is stirred for 60min under 98 ℃, is stirred for 30min under 60 ℃, and simultaneously maleic acid with the mass concentration of 6% (m/v) and concentrated hydrochloric acid with a certain volume are added, so that the volume ratio of the polyvinyl alcohol to the maleic acid to the concentrated hydrochloric acid is 1:0.2:0.1, and the reaction is carried out for 1.5h at 50 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 1.5L, drying for 30h at 102 ℃, and cooling to room temperature; in N2Protecting and roasting at 600 ℃ for 4 h.
The obtained zero-valent cobalt activated carbon-based particle electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based particle electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, the simulated humic acid wastewater is treated under the conditions that the COD of inlet water is 180-fold and 220mg/L and the current is 0.1A, the outlet water is stable after 20min, and the removal rate of the COD reaches 98.2%.
Example 7
Soaking the cleaned and dried activated carbon powder in 0.5mol/L cobalt sulfate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt sulfate solution is 1g:6L, and oscillating at constant temperature of 30 ℃ for 4 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 10%, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, stirred for 35min under 75 ℃, stirred for 70min under 90 ℃ and stirred for 40min under 50 ℃, meanwhile, maleic acid with the mass concentration of 6% (m/v) and concentrated sulfuric acid with a certain volume are added, the volume ratio of the polyvinyl alcohol to the maleic acid to the concentrated sulfuric acid is 1:0.25:0.1, and the reaction is carried out for 1h under 60 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 2L, drying for 24 hours at 105 ℃, and cooling to room temperature; in N2Protecting and roasting at 700 ℃ for 3 h.
The obtained zero-valent cobalt activated carbon-based granular electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based granular electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, the wastewater containing the organochlorine insecticide is treated, the treatment is carried out under the conditions that the COD (chemical oxygen demand) of the inlet water is 50-80mg/L and the current is 0.3A, the outlet water is stable after 20min, and the removal rate of the COD reaches 94.7%.
Example 8
Soaking the washed and dried activated carbon powder in 0.4mol/L cobalt nitrate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt nitrate solution is 1g:5L, and oscillating at the constant temperature of 20 ℃ for 12 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 8 percent, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, is stirred for 35min under 75 ℃, is stirred for 70min under 90 ℃, is stirred for 40min under 50 ℃, and simultaneously maleic acid with the mass concentration of 5 percent (m/v) and concentrated sulfuric acid with certain volume are added, so that the volume ratio of the polyvinyl alcohol to the citric acid to the concentrated sulfuric acid is 1:0.23:0.06, and the reaction is carried out for 1.5h under 50 ℃; according to the binding of the activated carbon powderMixing and granulating the mixture with the mass volume ratio of 1g to 1.5L, drying the mixture for 24 hours at 105 ℃, and cooling the mixture to room temperature; in N2Protecting and roasting at 600 ℃ for 4 h.
The obtained zero-valent cobalt activated carbon-based granular electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based granular electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, organophosphorus pesticide wastewater is treated, the treatment is carried out under the conditions that the COD (chemical oxygen demand) of inlet water is 50-80mg/L and the current is 0.2A, the outlet water is stable after 40min, and the removal rate of the COD reaches 96.6%.
Example 9
Soaking the cleaned and dried activated carbon powder in 0.6mol/L cobalt sulfate solution, wherein the mass volume ratio of the activated carbon powder to the cobalt sulfate solution is 1g:7L, and oscillating at constant temperature of 30 ℃ for 4 h; in the preparation of the binder, the mass concentration of a polyvinyl alcohol solution is 12%, the polyvinyl alcohol solution is stirred for 40min under the condition of 50 ℃ water bath, stirred for 35min under 75 ℃, stirred for 70min under 90 ℃ and stirred for 40min under 50 ℃, meanwhile, maleic acid with the mass concentration of 6% (m/v) and concentrated sulfuric acid with certain volume are added, the volume ratio of the polyvinyl alcohol to the maleic acid to the concentrated sulfuric acid is 1:0.27:0.09, and the reaction is carried out for 1.5h under 50 ℃; mixing and granulating the activated carbon powder and the binder according to the mass volume ratio of 1g to 1.8L, drying for 30h at 100 ℃, and cooling to room temperature; in N2Protecting and roasting at 700 ℃ for 3 h.
The obtained zero-valent cobalt activated carbon-based particle electrode material is applied to a three-dimensional electrode reactor, a titanium mesh electrode and a ruthenium-titanium electrode are respectively used as a cathode and an anode, the zero-valent cobalt activated carbon-based particle electrode is filled between the cathode and the anode to form a three-dimensional electrode reaction system, the simulated coking wastewater is treated under the conditions that the water inlet COD is 100-plus-150 mg/L and the current is 0.2A, the effluent is stable after 40min, and the removal rate of the COD reaches 96.2%.
Comparative example 1
Respectively applying different particle electrode materials (particles (self-made in a laboratory) prepared from coal-based activated carbon with the diameter of 4mm, coal-based activated carbon with the diameter of 1.5mm, coconut shell activated carbon, shell activated carbon and shell activated carbon powder and zero-valent cobalt activated carbon-based catalytic particles) to a three-dimensional electrode reactorThe method comprises the steps of taking a ruthenium-titanium electrode as an anode, taking a titanium mesh electrode as a cathode, filling particle electrode materials between the anode and the cathode to form a three-dimensional electrode system, and treating simulated wastewater containing humic acid by adopting a continuous water inlet and outlet mode, wherein the inlet water COD is 180-220mg/L and UV is254＝7.8-8.1，A4002.3-2.6 percent, the current is 0.1A, the flow is 3mL/min, the hydraulic retention time is 30min, the effluent is stable after 20min, and the removal rates of COD are respectively 18 percent, 21 percent, 24 percent, 33 percent, 54 percent and 97 percent; UV (ultraviolet) light254The removal rates of (a) are 21%, 25%, 29%, 40%, 72% and 98%, respectively; the removal rates of the chromaticities were 22%, 26%, 30%, 39%, 63%, and 98%, respectively. Obviously, when particles made of shell activated carbon powder and self-made in a laboratory are used as particle electrodes, the treatment effect of the three-dimensional electrode is obviously superior to that of other commercial activated carbon, namely COD (chemical oxygen demand) and UV (ultraviolet)254、A400The removal rate of the catalyst is obviously improved. A zero-valent cobalt active carbon-based catalytic particle electrode formed by loading catalytic metal on the shell active carbon powder and used for treating COD and UV254The removal rate of the chromaticity is further improved, wherein the removal rate of COD is improved to 97 percent from 54 percent before loading, and the removal rate of UV is improved254The removal rate of the color and the removal rate of the chroma are respectively improved to 98 percent and 98 percent.
Comparative example 2
Preparing catalytic particle electrodes loaded with different metal elements by using activated carbon powder as a carrier of the metal elements, sequentially carrying out loading of the metal elements according to a mode of no-load metal elements, Fe, Mn, Ni and Co, carrying out the same preparation steps except the loaded metal elements, filling the prepared catalytic particle electrodes between a cathode and an anode to form a three-dimensional electrode oxidation system, and respectively treating simulated wastewater containing humic acid by adopting a continuous water inlet mode, wherein the inlet water COD is 180-charge 220mg/L and UV is UV254＝7.8-8.1，A4002.3-2.6 percent, the current is 0.1A, the flow is 3mL/min, the hydraulic retention time is 30min, the effluent is stable after 20min, and the removal rates of COD are 40 percent, 39 percent, 45 percent, 68 percent and 97 percent respectively; UV (ultraviolet) light254The removal rates of (a) are respectively 37%, 35%, 47%, 70% and 98%; the removal rates of the chromaticities were 36%, 32%, 46%, 71%, and 98%, respectively.
Claims (7)
1. A preparation method of a zero-valent cobalt activated carbon-based catalytic particle electrode is characterized by comprising the following steps:
(1) pretreatment of activated carbon powder: washing the activated carbon powder with water, oscillating, separating, drying, and cooling to room temperature;
(2) preparing a cobalt salt solution: dissolving cobalt nitrate or cobalt sulfate in water, wherein the molar concentration of cobalt ions is 0.3-0.7 mol/L;
(3) loading a catalyst: soaking the activated carbon powder in the step (1) in a cobalt salt solution (2) according to the mass volume ratio of 1g: 5-8L, oscillating, centrifuging, drying, and cooling to room temperature;
(4) preparing a binder: dissolving polyvinyl alcohol in water under the condition of water bath, adding carboxylic acid and a catalyst simultaneously after the polyvinyl alcohol is completely dissolved, carrying out crosslinking reaction, and cooling to room temperature;
(5) preparing a particle electrode: uniformly mixing the activated carbon powder in the step (3) and the binder in the step (4) according to the mass volume ratio of 1g: 1-2L, granulating and drying;
(6) roasting and activating: mixing the granules prepared in (5) with N2And (4) roasting at high temperature under protection, and cooling to room temperature.
2. The preparation method of the zero-valent cobalt activated carbon-based catalytic particle electrode according to claim 1, wherein the drying temperature in the steps (1), (3) and (5) is 100-105 ℃, and the drying time is 24-48 h.
3. The method for preparing the zero-valent cobalt activated carbon-based catalytic particle electrode according to claim 1, wherein the polyvinyl alcohol in the step (4) is added into water at a mass concentration of 8-12% (m/v); the water bath conditions for dissolving the polyvinyl alcohol solution are as follows in sequence: stirring for 20-40 min at 50-70 ℃, stirring for 25-35 min at 75-85 ℃, stirring for 50-70 min at 90-100 ℃, and stirring for 20-40 min at 50-70 ℃; the carboxylic acid is maleic acid or citric acid with the mass concentration of 4-10% (m/v); the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated phosphoric acid; after the carboxylic acid and the catalyst are added into the polyvinyl alcohol solution, the volume ratio of the polyvinyl alcohol to the carboxylic acid to the catalyst is 1: 0.2-0.3: 0.01-0.1; the crosslinking reaction temperature is 50-70 ℃, and the reaction time is 1-1.5 h.
4. The preparation method of the zero-valent cobalt activated carbon-based catalytic particle electrode according to claim 1, wherein the roasting temperature in the step (6) is 450-800 ℃, and the roasting time is 1-6 h.
5. A zero-valent cobalt activated carbon-based catalytic particle electrode prepared by the preparation method according to any one of claims 1 to 4, characterized in that: the average particle size of the particle electrode is 2-7 mm, and the mass of the loaded zero-valent cobalt accounts for 8-10 wt% of the mass of the activated carbon.
6. Use of a zero-valent cobalt activated carbon-based catalytic particulate electrode prepared according to the method of any one of claims 1 to 4 for the degradation and removal of toxic and harmful organic substances in water.
7. The application of claim 6, wherein the particle electrode is filled between the cathode plate and the anode plate to form a three-dimensional particle electrode reaction system; the anode is a ruthenium-titanium electrode (RuO)2and/Ti), the cathode is a titanium electrode.
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