CN109052575B - Gamma-Al2O3Preparation method and application of (E) -Ti- (Ag/W) three-dimensional particle electrode - Google Patents
Gamma-Al2O3Preparation method and application of (E) -Ti- (Ag/W) three-dimensional particle electrode Download PDFInfo
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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Abstract
The invention provides gamma-Al2O3Preparation method and application of-Ti- (Ag/W) three-dimensional particle electrode, wherein gamma-Al is selected in the method2O3Loading Ti, Ag and W elements on a carrier by a sol-gel method and an immersion method as a precursor carrier, and bonding the loading elements on the carrier in the form of a metal oxide film by a temperature programming method to prepare the novel particle electrode gamma-Al2O3Ti- (Ag/W), and degrading the coal chemical wastewater in a three-dimensional microporous aeration reactor (shown in figures 1 and 2). The preparation method of the three-dimensional particle electrode is simple, the operation is simple and convenient, the catalytic activity is high, and the three-dimensional reactor treats the coal chemical wastewater in a micropore aeration mode, so that the effect of efficiently degrading sewage is achieved.
Description
Technical Field
The invention belongs to the field of environment-friendly water treatment, and relates to gamma-Al2O3A preparation method and application of a-Ti- (Ag/W) three-dimensional particle electrode, in particular to a method for synthesizing gamma-Al by matching a sol-gel method with a dipping method2O3-Ti- (Ag/W) three-dimensional particle electrode and degrading coal chemical industry wastewater in a three-dimensional reactor.
Background
Coal energy is used as an important component of the energy structure in China, and plays a vital role in ensuring the energy supply safety in China. Reports show that with the increasing shortage of petroleum and natural gas supply in China, the trend of the domestic chemical industry towards the coal chemical industry appears. In the process of processing and utilizing coal, a large amount of water is needed, and simultaneously, a large amount of wastewater with incredible quantity can be generated, and a large amount of wastewater in the coal chemical industry is high-pollution wastewater, can cause serious damage to the environment and ecology, and also threatens the drinking water safety of people. The coal chemical wastewater has high organic matter content, and many organic matters are difficult to biodegrade, even many pollutants such as cyanide, heterocyclic compounds and the like in the coal chemical wastewater are extremely unfavorable for the survival of microorganisms, so the coal chemical wastewater has poor biodegradability and high toxicity. In addition, the coal chemical industry wastewater has high chroma, the raw water has very dark color and even blackens, even if the chroma of the effluent is high, the color of the effluent is light, and the color is light yellow. Therefore, the coal chemical industry wastewater is industrial wastewater which has poor biochemical property, is very difficult to treat and has great harm to the environment. At present, the treatment of coal chemical wastewater at home and abroad is mainly in a three-stage treatment mode: the first-stage physicochemical pretreatment, the second-stage biochemical treatment and the third-stage physicochemical advanced treatment are adopted. However, the three-stage processing mode requires a long processing flow and processing time, and is expensive. Therefore, how to treat the coal chemical industry wastewater quickly, stably and with low energy consumption becomes a hotspot and a difficulty in the field of coal chemical industry wastewater treatment.
The electrochemical water treatment technology has the incomparable advantages of multiple functions, high flexibility, easy automation, no secondary pollution and the like, is a hot subject of domestic and foreign treatment technology research, particularly has high efficiency for removing three-cause carcinogenic, teratogenic and mutagenic organic pollutants which are difficult to biochemically degrade and have great harm to human health, and can save a large amount of energy. Therefore, electrochemical water treatment technology has become a very active research field in the world water treatment technology in recent years, and has received wide attention at home and abroad.
Three-dimensional electrodes (Three-dimensional electrodes) were proposed by Backhurst J.R at the end of the 60 s, and are also known as bed electrodes (bed electrodes) or particle electrodes (particle electrodes). Compared with a two-dimensional degradation system, the three-dimensional degradation system is an electrochemical reactor which fills particle particles between a cathode plate and an anode plate of the two-dimensional system so as to form a new one pole, namely a third pole. The particle particles are filled, so that the three-dimensional electrode has larger specific surface area, and the distance between the electrode plates is shortened by the particle particles, thereby improving the mass transfer process, improving the utilization efficiency of current and ensuring the treatment effect of the three-dimensional electrolysis technology on organic pollutants. The core of three-dimensional electrolysis is the particle electrode. Because the three-dimensional electrode can not only utilize the cathode and the anode for direct electrocatalysis, the filled particle electrode can also degrade organic pollutants. Therefore, the three-dimensional electrolysis can greatly improve the electrolysis efficiency and the current efficiency and reduce the reaction energy consumption. At present, the particle electrode material is various, and different substrate materials can load and dope various elements. However, the current electrode materials have the following problems: low catalytic activity of the electrode, poor stability of the particle electrode, low mechanical strength and the like.
Disclosure of Invention
Aiming at the problems and defects of the existing three-dimensional particle electrode, the invention provides a preparation method for preparing a high-activity ion electrode.
It is another object of the present invention to provide gamma-Al prepared according to the method2O3-a Ti- (Ag/W) three-dimensional particle electrode.
It is still another object of the present invention to provide the gamma-Al2O3Application of the-Ti- (Ag/W) three-dimensional particle electrode in degrading coal chemical industry wastewater.
The purpose of the invention can be realized by the following technical scheme:
Gamma-Al2O3-a method for preparing a Ti- (Ag/W) three-dimensional particle electrode, comprising the steps of:
first, the carrier particles are treated with gamma-Al2O3Pre-treating, weighing quantitative carrier particles, and putting the carrier particles into an etching solution for rinsing; then, treating the particles by using an acetone solution, and repeatedly washing the particle electrodes by using distilled water after washing until the particles are neutral; finally, placing the pretreated particles into an oven for drying for later use;
secondly, mixing absolute ethyl alcohol and deionized water, and adjusting the pH value to 2-3 by using an HCl solution to prepare a solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature for 5min after mixing, and standing to obtain TiO2Preparing gel; subsequently soaking the support particles in the prepared TiO2Fully reacting in the gel for 1-4 h on a shaking table; will be impregnated withTaking out the carrier particles of the good Ti metal salt solution and drying the carrier particles in an oven; respectively putting the dried particles into a muffle furnace, and roasting and activating for 1-4 h at 100-800 ℃; repeating the steps for 2-5 times to prepare the needed Ti-loaded metal oxide particles;
thirdly, preparing AgNO with certain concentration3+H2WO4Ethanol solution; putting the Ti-loaded metal oxide particles prepared in the second step into an immersion liquid AgNO3+H2WO4Fully reacting in an ethanol solution on a shaking table for a period of time; then taking out the Ti-loaded metal oxide particles soaked in the Ag/W metal salt solution, putting the Ti-loaded metal oxide particles into an oven, and drying the Ti-loaded metal oxide particles for more than 12 hours at the temperature of 80 ℃ for later use; then, respectively putting the dried particles into muffle furnaces, and roasting and activating for 1-4 h at 100-800 ℃; repeating the steps for 2-5 times to obtain the gamma-Al2O3-a Ti- (Ag/W) three-dimensional particle electrode.
The etching solution in the first step is 40ml/L HF and 2g/L NH4F, according to a volume ratio of 1: 4-8 of mixed solution. In the first step gamma-Al2O3The mass-to-volume ratio of the particles to the etching solution is 1: 2-5 (g: ml).
The volume ratio of the absolute ethyl alcohol to the deionized water in the second step is 1-3: 1, and preferably 2: 1.
The volume ratio of the absolute ethyl alcohol to the glacial acetic acid in the second step is 1: 1-2, preferably 1:1: 1; the concentration of tetrabutyl titanate in the solution of absolute ethyl alcohol and glacial acetic acid is 0.5-10.5 mol/L.
The second step of carrier particles and TiO2The mass-to-volume ratio of the gel is 1: 2-5, preferably 1: 3.
Said third step AgNO3+H2WO4AgNO in ethanol solution3Has a concentration of 0.5mol/L, H2WO4The concentration of (2) was 0.05 mol/L.
In the second step and the third step, a heating method in the muffle furnace adopts a programmed heating mode, and the temperature is increased to 100-800 ℃ at the speed of 10-25 ℃/min.
γ-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode is further preferableComprises the following steps:
firstly, pretreating carrier particles, weighing quantitative carrier particles, putting the carrier particles into etching solution (BOE), and rinsing the carrier particles in a water-area shaking table; then, soaking and rinsing the particles by using an acetone solution, and repeatedly rinsing the particle electrodes by using distilled water after cleaning until the particles are neutral; finally, placing the pretreated particles into a drying oven at 105 ℃ for drying for 12 hours for later use;
secondly, mixing absolute ethyl alcohol and deionized water (the volume ratio is 2:1), and adjusting the pH value to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (the volume ratio is 1:1: 1), and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring for a period of time at room temperature after the mixing is finished, and then standing for 1h to finish TiO2Preparing gel; subsequently, a defined amount of the support particles is immersed in the TiO thus obtained2In the gel, the mass ratio of the carrier particles to the tetrabutyl titanate is 1:3, and then the gel is fully reacted for 4 hours on a shaking table; taking out the carrier particles soaked with the Ti metal salt solution, putting the carrier particles into an oven, and drying the carrier particles for 12 hours at the temperature of 105 ℃; respectively putting the dried particles into a muffle furnace, and roasting and activating for a period of time at 100-800 ℃; repeating the steps for n times to prepare the needed Ti-loaded metal oxide particle electrode;
and thirdly, preparing the electrode loaded with Ag/W metal oxide particles. AgNO with 0.5mol/L configuration3+0.05mol/LH2WO4Ethanol solution; putting the carrier-Ti prepared in the second step into an impregnation solution (the mass/volume is 1:4), and fully reacting for 4 hours on a shaking table; then taking out Ti-loaded particles immersed in the Ag/W metal salt solution, putting the particles in an oven, and drying the particles for more than 12 hours at the temperature of 80 ℃ for later use; then, respectively putting the dried particles into a muffle furnace, and roasting and activating for 1-4 h at the temperature of 100-; repeating the steps for n times to obtain the required load carrier-Ti- (Ag/W) metal oxide particle electrode.
The particle carrier in the first step is gamma-Al2O3At present, the carrier material of the three-dimensional particle electrode has a porous structureArtificial zeolite, activated carbon, glass beads, and the like. gamma-Al2O3Has the advantages of high porosity, large specific surface area, high mechanical strength, strong chemical stability and the like, so that the gamma-Al is selected2O3As a carrier for the loading element.
Further, the first etching solution selects HF and NH4And the etching speed of the BOE (buffered oxide etching solution) mixed solution consisting of F is about 10nm per second, wherein HF is the main etching solution.
The first load element selected in the second step is Ti, and Ti and O are at high temperature2React to generate anatase, rutile and brookite TiO with three crystal forms2And forming TiO with anatase as main crystal form in the subsequent roasting2Has high catalytic activity. Commonly used load elements mainly include: noble metals, rare metals, and transition metals. The noble metal and rare metal catalysts have high activity, strong applicability, long service life and wide applicable range, but the noble metal and rare metal catalysts are high in price and difficult to be applied to large-scale industrialization. The transition metal also has stronger catalytic activity, but has the problems of easy loss of active components, relatively short service life and the like.
In the second step, the Ti element is loaded by utilizing a sol-gel method, namely a method for solidifying a compound containing high chemical activity components through solution, sol and gel and then carrying out heat treatment to obtain an oxide or other compound solid. In recent years, sol-gel technology has been successfully applied to the synthesis of glass, oxide coatings and functional ceramic powders, especially composite oxide materials and high critical temperature (P) oxide superconducting materials which are difficult to prepare by the traditional method.
Furthermore, the second secondary elements loaded in the second step are Ag and W, and AgNO is prepared by using an impregnation method3And H2WO4Mixing, and soaking in gamma-Al2O3-a particle electrode surface of Ti. The impregnation method can ensure that Ag and W are uniformly distributed on the surface of the particle carrier to play a role of mutual synergy. And the supported metal is oxidized by using the particle electrode prepared by the post-dipping methodThe material film will be in gamma-Al2O3The surfaces are distributed sequentially from inside to outside, so that a plurality of elements cannot play a catalytic role together.
And meanwhile, roasting the load particles in the second step in a muffle furnace in a temperature programmed manner (the temperature rise speed is 10-25 ℃/min). In order to simplify the preparation process of the particle electrode, the supported particles are generally roasted by a direct roasting mode, and the programmed temperature rise is beneficial to the existence of the supported elements on the surface of the carrier in a crystal form oxide with the highest activity.
Gamma-Al prepared by the preparation method of the invention2O3-a Ti- (Ag/W) three-dimensional particle electrode.
The gamma-Al of the invention2O3Application of the-Ti- (Ag/W) three-dimensional particle electrode in degrading coal chemical industry wastewater.
The application is preferably that the cathode and anode plates are firstly placed in the clamping grooves of the three-dimensional reactor, the distance between the cathode and anode plates is set to be 5cm, and the three-dimensional reactor is externally connected with a power supply; a certain amount of gamma-Al is placed between the cathode plate and the anode plate2O3-Ti- (Ag/W) three-dimensional particle electrode, taking coal chemical wastewater in a three-dimensional reactor; and opening the aeration device and the power supply, and regulating the aeration quantity and the current intensity to degrade the wastewater.
Firstly, placing a positive electrode plate and a negative electrode plate into a clamping groove of a three-dimensional reactor, setting a certain distance (5-8cm) between the positive electrode plate and the negative electrode plate, and connecting an external power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and placing 500ml of wastewater in a three-dimensional reactor; and opening the aeration device and the power supply, carrying out microporous aeration, and regulating the aeration quantity and the current intensity to degrade the wastewater.
The three-dimensional electrode reactor is preferably a self-made microporous aeration reactor, and the structure is shown in figure 1. At present, bubbling technologies such as aeration, air flotation and the like in a water treatment area have the problems of low mass transfer efficiency, high energy consumption and the like, so that a microbubble technology needs to be deeply researched and better applied to an actual water treatment technology. The microbubble technology has attracted commercial attention in recent years as a leading-edge scientific technology with wide application prospect, and the research and application of the microbubble technology in the fields of medicine, environment, agriculture, aquaculture and the like have gained encouraging results. The micro bubbles have excellent characteristics of underwater rupture, generation of free radicals during rupture and the like.
Compared with the prior art, the invention has the following advantages:
1. the invention selects gamma-Al2O3As a load carrier, the material has the characteristics of strong adsorption performance and high mechanical strength.
2. Gamma-Al prepared by the invention2O3The novel-Ti- (Ag/W) three-dimensional ion electrode has the advantages of high catalytic activity, low energy consumption, high repeated utilization rate and the like.
3. The preparation method provided by the invention is simple to operate and convenient to control, and the adopted temperature programming mode enables the crystal form of the loaded oxide to show a better electrocatalytic effect.
4. The finally prepared particle electrode can be widely applied to the fields of sewage treatment, papermaking, coal mining, textile and the like.
Drawings
FIG. 1 three-dimensional reactor schematic
1 is an aeration device, 2 is a flow meter, 3 is a regulating valve, 4 is a microporous aeration head, 5 is a microporous aeration plate, 6 is a direct current power supply, 7 is a graphite plate, and 8 is a titanium plate
FIG. 2 Process for producing particle electrode
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
In the following examples, the reaction is carried out at room temperature, the room temperature is generally 5 to 30 ℃ and the various reagents used are of analytical purity.
Example 1:
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 4; 60g of gamma-Al are weighed2O3Pouring the particles into 200ml of prepared etching solution,shaking at 30 deg.C for 100min, and washing the particles with distilled water; and soaking and rinsing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (the volume ratio of the ethyl alcohol to the glacial acetic acid is 1:1) into 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a temperature programming muffle furnace, and roasting and activating for 3h at 200 ℃ at a temperature rising speed of 10 ℃/min; repeating the steps for 2 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating for 3h at 200 ℃ at a heating rate of 10 ℃/min; repeating the steps for 2 times to obtain the required gamma-Al loaded with the Ag/W metal oxide2O3-a Ti- (Ag/W) three-dimensional particle electrode. Through compression detection, the compression strength of the electrode is as high as 234MPa, compared with other particle electrodes: (<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting the distance between the electrode plates to be 6cm, and connecting an external power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor is continuously operated for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 680mg/L, 2700mg/L and 450mg/L, and the removal rates of the three-dimensional microporous aeration reactor respectively reach 44.4%, 40% and 39.3%.
Example 2:
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 5; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid is 1:1) into a 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel 60g of pretreatment was weighedPost gamma-Al2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ for 3h at a heating rate of 10 ℃/min; repeating the steps for 2 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ at a heating rate of 10 ℃/min for 3 h; repeating the steps for 2 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 239MPa, compared with other particle electrodes: (<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 6cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 620mg/L, 2400mg/L and 330mg/L, and the removal rates respectively reach 49.3%, 46.7% and 55.5%.
Example 3:
Gamma-Al2O3-Ti-(The preparation method of the Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 5; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and soaking and rinsing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to a volume ratio of 2:1, and adjusting the pH value to 2 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (the volume ratio of the ethyl alcohol to the glacial acetic acid is 1:1) into 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating for 3h at the temperature rising speed of 25 ℃/min and the temperature of 500 ℃; repeating the steps for 2 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, placing in an oven, and drying at 80 deg.CDrying for later use for 12 hours; respectively putting the dried particles into a muffle furnace, and roasting and activating for 3h at the temperature rising speed of 25 ℃/min and the temperature of 500 ℃; repeating the steps for 2 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 225MPa, compared with other particle electrodes (b)<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 7cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 700mg/L, 2560mg/L and 420mg/L, and the removal rates respectively reach 42.8%, 43.1% and 43.3%.
Example 4
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 6; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, anhydrous ethanol and glacial acetic acid (ethyl acetate)Alcohol: glacial acetic acid ═ 1:1) mixing to obtain 0.5mol/L butyl titanate mixed solution, and uniformly stirring to obtain solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ for 3h at the heating rate of 20 ℃/min; repeating the steps for 4 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ at a heating rate of 25 ℃/min for 3 h; repeating the steps for 4 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 237MPa, compared with other particle electrodes (<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 7cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 600mg/L, 2000mg/L and 320mg/L, and the removal rates respectively reach 50.9%, 55.6% and 56.8%.
Example 5
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 6; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid is 1:1) into a 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating for 3h at 700 ℃ at the heating rate of 20 ℃/min; repeating the steps for 4 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (II)The mixing volume ratio of the components is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating for 3h at 700 ℃ at a heating rate of 20 ℃/min; repeating the steps for 4 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 225MPa, compared with other particle electrodes (b)<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 8cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 750mg/L, 2740mg/L and 430mg/L, and the removal rates of the three-dimensional microporous aeration reactor respectively reach 38.7%, 39.1% and 42.0%.
Example 6
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 7; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; putting the pretreated particles into a baking ovenOven-drying at 105 deg.C for 12 hr.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid is 1:1) into a 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating for 3h at 200 ℃ at a heating rate of 10 ℃/min; repeating the steps for 2 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.1mol/L AgNO3+0.1mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating for 3h at 200 ℃ at a heating rate of 10 ℃/min; repeating the steps for 2 times to obtain the required Ag/W loaded metal oxide particle electrode. The compression strength of the electrode is up to 217MPa through compression detection, compared with other particle electrodes (b)<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 8cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 760mg/L, 2760mg/L and 435mg/L, and the removal rates of the three-dimensional microporous aeration reactor respectively reach 37.9%, 38.7% and 41.3%.
Example 7
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 7; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid is 1:1) into a 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating for 3h at 200 ℃ at a heating rate of 10 ℃/min; heavy loadRepeating the step for 2 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.5mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating for 3h at 200 ℃ at a heating rate of 10 ℃/min; repeating the steps for 2 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 206MPa, compared with other particle electrodes (b)<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 8cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 1 hour, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 780mg/L and 3000mg/L, the content of ammonia nitrogen is 610mg/L, and the removal rates of the three-dimensional microporous aeration reactor respectively reach 36.2%, 33.3% and 17.7%.
Example 8
Gamma-Al2O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 8; 60g of gamma-Al are weighed2O3Particles are poured into 200ml of prepared etching solution, and the temperature of a shaking table is set to be 30 DEG CShaking for 100min, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid is 1:1) into a 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ for 3h at the heating rate of 20 ℃/min; repeating the steps for 4 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ at a heating rate of 20 ℃/min for 3 h; repeating the steps for 4 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 238MPa, compared with other particle electrodes (b)<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 8cm, and externally connecting a power supply; placing 60g of particle electrodes between the cathode plate and the anode plate, and taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 550mg/L, 1500mg/L and 400mg/L, and the removal rates respectively reach 50.0%, 66.7% and 46%.
Example 9
Gamma-Al2O3The novel method for preparing the Ti- (Ag/W) three-dimensional particle electrode and degrading the coal chemical industry wastewater mainly comprises the following steps:
the first step is as follows: 40ml/L of HF and 2g/L of NH are weighed out respectively4F is prepared into an oxide etching solution (BOE) according to the volume ratio of 1: 8; 60g of gamma-Al are weighed2O3Pouring the particles into prepared 200ml of etching solution, shaking for 100min at the temperature of 30 ℃ of a shaking table, and washing the particles with distilled water after shaking is finished; and washing the particles by using an acetone solution, so that organic matters on the surfaces of the particles are removed. Repeatedly washing the particle electrode with distilled water after cleaning until the particle electrode is neutral; and (3) putting the pretreated particles into an oven, and baking for 12 hours at 105 ℃ for later use.
The second step is that: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 2:1, and adjusting the pH value of the mixture to 2-3 by using HCl solution to prepare solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid (ethyl alcohol: glacial acetic acid is 1:1) into a 0.5mol/L tetrabutyl titanate mixed solution, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature after the mixing is finished, and standing for 1h to finish TiO2Preparation of gel, 60g of pretreated gamma-Al is weighed2O3Soaking the particles in the prepared 200ml TiO2In the gel, and fully reacting on a shaking table; impregnating the well-impregnated Ti metal salt solution with gamma-Al2O3Taking out the particles, putting the particles in an oven, and drying the particles at the temperature of 105 ℃ for 12 hours for later use; putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ for 3h at the heating rate of 20 ℃/min; repeating the steps for 4 times to obtain the needed Ti-loaded metal oxide particle electrode.
The third step: a preparation method of an electrode loaded with Ag/W metal oxide particles. Preparing 0.5mol/L AgNO3+0.05mol/L H2WO4Ethanol solution (the mixing volume ratio of the ethanol solution and the ethanol solution is 1: 1); weighing 60g of the pretreated particles, putting the particles into the impregnation liquid, and fully reacting for 4 hours on a shaking table; impregnating the gamma-Al of the well-impregnated Ag/W metal salt solution2O3Taking out the particles, putting the particles in an oven, drying the particles for more than 12 hours at the temperature of 80 ℃, and drying the particles for later use; respectively putting the dried particles into a muffle furnace, and roasting and activating at 300 ℃ at a heating rate of 20 ℃/min for 3 h; repeating the steps for 4 times to obtain the required Ag/W loaded metal oxide particle electrode. Through compression detection, the compression strength of the electrode is up to 236MPa, compared with other particle electrodes (<200MPa) exhibit great advantages.
Firstly, placing a positive electrode plate and a negative electrode plate in a clamping groove of a three-dimensional reactor, setting a certain distance between the electrode plates to be 8cm, and externally connecting a power supply; 60g of particle electrodes which had been recycled 20 times (and likewise degraded 3h each time) were placed between the cathode and anode plates. The mechanical strength of the particle electrode at this time was 233 MPa. Taking 500ml of coal chemical wastewater in a three-dimensional reactor; opening an aeration device and a power supply, adjusting the aeration quantity to be 15ml/min and the current intensity to be 0.1A, and starting degradation research; sampling is carried out once every 30min, and indexes such as total phenol, COD, ammonia nitrogen concentration and the like are respectively analyzed.
After the three-dimensional microporous aeration reactor continuously operates for 3 hours, a better wastewater degradation effect is obtained, wherein the contents of total phenol, COD and ammonia nitrogen are respectively reduced from 1223mg/L, 4500mg/L and 741mg/L to 620mg/L, 2030mg/L and 430mg/L, and the removal rates respectively reach 49.3%, 54.9% and 42%. Therefore, the ion electrode manufactured by the invention has excellent stability.
Finally, the following description is provided: the above embodiments are only for illustrating the technical solutions of the present invention, and the detailed description of the embodiments is made with reference to the best experimental conditions of the present invention, and meanwhile, when a person skilled in the art makes modifications or approximate substitutions on the technical solutions of the present invention and does not depart from the scope of the technical solutions of the present invention, it should be covered in the claims of the present invention.
Claims (12)
1. Gamma-Al2O3-a method for preparing a Ti- (Ag/W) three-dimensional particle electrode, characterized by comprising the steps of:
first, the carrier particles are treated with gamma-Al2O3Pre-treating, weighing quantitative carrier particles, and putting the carrier particles into an etching solution for rinsing; then, treating the particles by using an acetone solution, and repeatedly washing the particle electrodes by using distilled water after washing until the particles are neutral; finally, placing the pretreated particles into an oven for drying for later use;
secondly, mixing absolute ethyl alcohol and deionized water, and adjusting the pH value to 2-3 by using an HCl solution to prepare a solution A; mixing tetrabutyl titanate, absolute ethyl alcohol and glacial acetic acid, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B with the same volume, and stirring while dropwise adding; continuously stirring at room temperature for 5min after mixing, and standing to obtain TiO2Preparing gel; subsequently soaking the support particles in the prepared TiO2Fully reacting in the gel for 1-4 h on a shaking table; taking out the carrier particles impregnated with the Ti metal salt solution and drying the carrier particles in an oven; respectively putting the dried particles into a muffle furnace, and roasting and activating for 1-4 h at 100-800 ℃; repeating the steps for 2-5 times to prepare the needed Ti-loaded metal oxide particles;
thirdly, preparing AgNO with certain concentration3+H2WO4Ethanol solution; putting the Ti-loaded metal oxide particles prepared in the second step into an immersion liquid AgNO3+H2WO4Fully reacting in an ethanol solution on a shaking table for a period of time; then taking out the Ti-loaded metal oxide particles soaked in the Ag/W metal salt solution, putting the particles into an oven, and drying the particles at the temperature of 80 ℃ to exceedDrying for later use for 12 hours; then, respectively putting the dried particles into muffle furnaces, and roasting and activating for 1-4 h at 100-800 ℃; repeating the steps for 2-5 times to obtain the gamma-Al2O3-a Ti- (Ag/W) three-dimensional particle electrode.
2. The gamma-Al of claim 12O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode is characterized in that the etching solution in the first step is 40ml/L HF and 2g/L NH4F, according to a volume ratio of 1: 4-8 of mixed solution.
3. The gamma-Al of claim 12O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode is characterized in that the volume ratio of absolute ethyl alcohol to deionized water in the second step is 1-3: 1.
4. The gamma-Al of claim 32O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode is characterized in that the volume ratio of the absolute ethyl alcohol to the deionized water in the second step is 2: 1.
5. The gamma-Al of claim 12O3-a preparation method of a Ti- (Ag/W) three-dimensional particle electrode, which is characterized in that the volume ratio of absolute ethyl alcohol to glacial acetic acid in the second step is 1: 1-2; the concentration of tetrabutyl titanate in the solution of absolute ethyl alcohol and glacial acetic acid is 0.5-10.5 mol/L.
6. The gamma-Al of claim 12O3-Ti- (Ag/W) three-dimensional particle electrode, characterized in that the second step of the preparation of the support particles is carried out with TiO2The mass-to-volume ratio of the gel is 1g (2-5) mL.
7. The gamma-Al of claim 62O3-Ti- (Ag/W) three-dimensional particle electrode, characterized in that the second step of carrier particles is carried out with TiO2The mass-to-volume ratio of the gel was 1g:3 mL.
8. The gamma-Al of claim 12O3-Ti- (Ag/W) three-dimensional particle electrode preparation method, characterized in that, the third step AgNO3The concentration of the ethanol solution is 0.5mol/L, H2WO4The concentration of the ethanol solution is 0.05 mol/L; AgNO3Ethanol solution and H2WO4The volume ratio of the ethanol solution is 1: 1.
9. The gamma-Al of claim 12O3The preparation method of the-Ti- (Ag/W) three-dimensional particle electrode is characterized in that in the second step and the third step, the temperature is raised to 100-800 ℃ at the speed of 10-25 ℃/min in a manner of temperature programming in a muffle furnace.
10. Gamma-Al produced by the production method according to any one of claims 1 to 92O3-a Ti- (Ag/W) three-dimensional particle electrode.
11. The gamma-Al of claim 102O3Application of the-Ti- (Ag/W) three-dimensional particle electrode in degrading coal chemical industry wastewater.
12. The application of claim 11, wherein the cathode and anode plates are firstly placed in the neck of the three-dimensional reactor, the distance between the plates is set to be 5cm, and the external power supply is connected; placing a quantity of gamma-Al as recited in claim 10 between the cathode and anode plates2O3-Ti- (Ag/W) three-dimensional particle electrode, taking coal chemical wastewater in a three-dimensional reactor; and opening the aeration device and the power supply, and regulating the aeration quantity and the current intensity to degrade the wastewater.
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| CN201810916122.3A CN109052575B (en) | 2018-09-25 | 2018-09-25 | Gamma-Al2O3Preparation method and application of (E) -Ti- (Ag/W) three-dimensional particle electrode |
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