CN214031842U - Nano graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device - Google Patents
Nano graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device Download PDFInfo
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- CN214031842U CN214031842U CN202023099600.8U CN202023099600U CN214031842U CN 214031842 U CN214031842 U CN 214031842U CN 202023099600 U CN202023099600 U CN 202023099600U CN 214031842 U CN214031842 U CN 214031842U
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Abstract
An electrocatalytic oxidation reaction device with a nano graphite doped ruthenium oxide electrode. The utility model particularly relates to a nanometer graphite doping ruthenium oxide electrode electrocatalytic oxidation reaction unit for degrading phenol in sewage. The utility model aims to solve the problem of low efficiency of the prior anode direct catalytic oxidation degradation of organic pollutants. It consists of a reaction tank, an anode plate, a cathode plate and a gas distribution pipe. The method comprises the following steps: and introducing the phenol-containing sewage into the water distribution pipe from the water inlet pipeline, injecting water into the reaction tank, closing the water inlet valve when the water level is over the upper ends of the anode plate and the cathode plate, switching on the power supply to electrify the anode plate and the cathode plate, simultaneously introducing air into the air distribution pipe through the air inlet pipeline, and opening the drain valve to discharge qualified effluent when the phenol-containing sewage is degraded to a water outlet index. The utility model is used for phenol in the degradation sewage.
Description
Technical Field
The utility model particularly relates to a nanometer graphite doping ruthenium oxide electrode electrocatalytic oxidation reaction unit for degrading phenol in sewage.
Background
Due to the rapid industrialization process and the increasing water consumption of human beings, human beings face a serious problem of water resource shortage. However, the problem of water pollution is becoming more and more serious. In the sources of wastewater in China, industrial wastewater accounts for a great proportion, wherein phenol-containing organic pollutants represented by phenol are one of the most harmful and most various organic pollutants. Phenol attacks the central nerve, causing bone marrow stimulation, harming human health, reducing crop yield and quality, affecting fishery production, causing destruction and degeneration of the ecological environment. The phenol-containing wastewater mainly comes from coking, oil refining, coal gas, pharmaceutical industry, phenolic resin production plants and the like, and a large amount of fecal sewage discharged in cities is also an important source of phenol pollutants in water bodies. Phenol is a biologically hardly degradable organic substance and has a strong inhibitory effect on biological treatment. In addition, because of large discharge amount, high concentration and strong toxicity of the industrial wastewater containing phenol, the conventional treatment means such as physical adsorption method, extraction method, membrane separation technology, ozone oxidation method, photocatalytic oxidation method and the like have poor treatment effect and high cost on the wastewater, or have secondary pollution and difficult subsequent treatment, and the traditional treatment process has no obvious effect. In the treatment of sewage and wastewater, electrocatalytic oxidation is one of the current researches. The method has the main advantages of stable catalytic efficiency, high oxidant utilization rate of over 95 percent, long service life of the catalytic electrode, simple process, convenient operation, low engineering investment, low operating cost and the like. The electrocatalytic oxidation technology is a treatment means with simple experimental device, controllable and convenient operation and no secondary pollution.
The research on the direct catalytic oxidation process of the anode is relatively mature, so that the synergy of the cathode and the anode is achievedCatalytic degradation of organic pollutants has been the focus of recent research. At present, inert materials are mainly used as cathode materials, and the inert cathode materials can generate hydrogen evolution side reaction (2H +2e- → H)2×) and the generation of the side reaction of cathodic hydrogen evolution inhibits the generation of hydrogen peroxide by the oxygen reduction reaction, so the oxygen reduction reaction is slow. In addition, the hydrogen precipitation reaction on the electrode is accompanied by larger overpotential, and the purpose of synergistic degradation with the anode is not achieved, so that the degradation effect of organic pollutants is greatly reduced.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the problem of low efficiency of the prior anode direct catalytic oxidation degradation of organic pollutants, and provides a nano graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device for degrading phenol in sewage.
The utility model discloses a nanometer graphite doping ruthenium oxide electrode electricity catalytic oxidation reaction unit for degrading phenol in sewage comprises reaction tank, anode plate, negative plate and gas distribution pipe, and the reaction tank is connected with water inlet pipe and outlet pipe way, installs water intaking valve and drain valve on water inlet pipe and the outlet pipe way respectively, and anode plate and negative plate set up in the reaction tank relatively and link to each other with outside DC power supply; the upper part of the inner cavity of the reaction tank is also provided with a water distribution pipe; the air distribution pipe is arranged at the bottom of the reaction tank and is connected with an external air inlet pipeline, and a plurality of aeration heads are uniformly distributed on the air distribution pipe.
The utility model has the advantages that:
the utility model discloses need not additionally add chemical reagent, utilize the transfer electron between two electrodes as the reactant, oxygen can play aeration reoxygenation effect on the one hand, combines micro-nano bubble technique, for catalytic oxidation provides sufficient oxygen, oxygen does not need additionally to add chemical reagent as the main raw materials of reductant, utilizes the strong oxidant that electrode reaction catalytic oxygen reduction generated hydroxyl radical to carry out the ring-opening degradation to the organic matter. On the other hand, the water body disturbance can be increased, and the electrochemical treatment effect is enhanced. The device has low requirement on equipment, the raw materials are cheap and easy to obtain, large-scale application in actual production is facilitated, and the device has high practical value.
Drawings
FIG. 1 is a schematic structural diagram of a nano-graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device for degrading phenol in sewage;
FIG. 2 is a schematic structural diagram of an aeration head;
FIG. 3 is a schematic view of a second cutting blade;
fig. 4 is a schematic structural view of the first cutting saw.
Detailed Description
The technical solution of the present invention is not limited to the following embodiments, and includes any combination of the following embodiments, and the following embodiments are described with reference to fig. 1 to 4.
The first embodiment is as follows: the nano-graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device for degrading phenol in sewage in the embodiment comprises a reaction tank 1, an anode plate 2, a cathode plate 3 and a gas distribution pipe 5, wherein the reaction tank 1 is connected with a water inlet pipeline 1-1 and a water outlet pipeline 1-2, the water inlet pipeline 1-1 and the water outlet pipeline 1-2 are respectively provided with a water inlet valve and a water discharge valve, and the anode plate 2 and the cathode plate 3 are oppositely arranged in the reaction tank 1 and are connected with an external direct current power supply; the upper part of the inner cavity of the reaction tank 1 is also provided with water distribution pipes 1-4; the air distribution pipe 5 is arranged at the bottom of the reaction tank 1 and is connected with an external air inlet pipeline 1-3, and a plurality of aeration heads 5-1 are uniformly distributed on the air distribution pipe 5.
The current is applied to the cathode and the anode, and meanwhile, a large amount of micro-nano bubbles are introduced into the sewage to be treated between the cathode and the anode, so that the sewage to be treated is subjected to combined treatment. The gas flow is 2-20 m3The particle size of the micro-nano bubbles is 100 nm-20 mu m.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the water distribution pipes 1-4 are provided with through holes inclined at 45 degrees. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the section of the aeration head 5-1 is trapezoidal, the first cutting saw teeth 5-2 and the second cutting saw teeth 5-3 are arranged in the aeration head 5-1, the first cutting saw teeth 5-2 are arranged above the second cutting saw teeth 5-3, and the first cutting saw teeth 5-2 and the second cutting saw teeth 5-3 are oppositely arranged on the horizontal plane and are staggered in tooth form. The others are the same as in the first or second embodiment.
The embodiment can play a role in flow equalization.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the tooth ends of the first cutting tooth 5-2 and the second cutting tooth 5-3 are flush on a vertical plane. The rest is the same as one of the first to third embodiments.
This embodiment sets up first cutting sawtooth and second cutting sawtooth in aeration head's inside, and the bubble is cut into less bubble through second cutting sawtooth and continues to rise, then touches first cutting sawtooth again and makes the bubble diminish once more, very big improvement dissolved oxygen efficiency and micro-nano bubble's production efficiency.
This embodiment is trapezoidal with the cross-section processing of aeration head, and the area along with the cross section of export constantly diminishes, has increased bubble dwell time and with the area of contact of sewage, makes the bubble schizolysis more easily, produces a large amount of micro-nano bubbles, has improved gas utilization.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the slope angle of the aeration head 5-1 is 60 degrees. The rest is the same as one of the first to fourth embodiments.
The embodiment can better realize the cutting of the bubbles.
The sixth specific implementation mode: the method for degrading the nano graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device for degrading phenol in sewage comprises the following steps:
introducing the phenol-containing sewage into the water distribution pipes 1-4 from the water inlet pipeline 1-1, injecting water into the reaction tank 1, closing the water inlet valve when the water level is over the upper ends of the anode plate 2 and the cathode plate 3, then switching on the power supply to electrify the anode plate 2 and the cathode plate 3, simultaneously introducing air into the air distribution pipe 5 through the air inlet pipeline 1-3, and opening the drain valve to discharge qualified effluent when the phenol-containing sewage is degraded to the effluent index.
The nano graphite/ruthenium/polyethylene glycol/polyvinylpyrrolidone polymer material of the embodiment is advantageous to the migration of electrolyte ions because a large number of porous structures are distributed on the surface and inside of the nano graphite/ruthenium/polyethylene glycol/polyvinylpyrrolidone polymer material and are lapped into a net structure. Typical polymers such as polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) are often used in the synthesis of composites. The two polymers of polyethylene glycol and polyvinylpyrrolidone can play roles of a protective agent, a surfactant, a dispersant, a forming agent and the like in the preparation process. The addition of PEG can effectively reduce the particle size and enlarge the active surface area. The application of PEG in electrochemistry has the advantages of mainly controlling the nucleation and growth of products. The PEG can effectively prolong the service life of the electrode and improve the stability of the electrode.
The ruthenium oxide particles can be aggregated in a small amount in the preparation process, so that the electrochemical performance of the ruthenium oxide particles is reduced, and the polyvinylpyrrolidone (PVP) has a good dispersing effect, so that the aggregation of the ruthenium oxide can be effectively prevented, and the nano graphite/ruthenium oxide composite catalyst has good electrochemical performance. The PVP can not only prevent the ruthenium oxide particles from agglomerating and enable the composite catalyst to be uniformly dispersed, but also can effectively prevent the ruthenium metal particles from becoming large and enable the ruthenium ions to exist in the form of ruthenium oxide.
Without the addition of PVP, excess hydroxide on the nanographite would form a single phenolate ion, thus forming ruthenium metal. After the addition of PVP, it prevents the nanographite from coming into direct contact with trivalent ruthenium so that ruthenium metal is not formed but exists in the form of ruthenium oxide. PVP can therefore also be considered as a protectant to prevent trivalent ruthenium from becoming ruthenium metal. The PEG protects the nano graphite/ruthenium oxide nano particles and the PVP protects the nano graphite/ruthenium oxide nano particles to play a synergistic role.
According to the embodiment, the cathode material is changed to generate active species with strong oxidizing property such as OH through indirect oxygen reduction reaction, so that the effect of cooperatively degrading organic pollutants by the anode and the cathode can be achieved, the current efficiency and the organic matter degradation effect are improved, meanwhile, the micro-nano bubble technology is combined to provide sufficient oxygen for catalytic oxidation, on the other hand, the water disturbance can be increased, and the electrochemical treatment effect is enhanced. The cathode has low speed of degrading organic pollutants, and not only is caused by the side reaction of hydrogen evolution, but also is probably caused by the fact that oxygen is reduced into water by 4 electrons at the cathode, and hydrogen peroxide and free radicals are not generated. Since hydrogen peroxide generated by the reduction of oxygen at the cathode can further indirectly generate active substances with strong oxidizing property such as active hydroxyl radicals, electrocatalysis is a process for generating a large amount of active hydroxyl radicals at the cathode. In order to improve the oxidation efficiency, a catalyst may be added to the electrode material to increase the rate of generation of active oxidizing radicals on the electrode surface.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: sodium sulfate is also added into the reaction tank 1. The rest is the same as the sixth embodiment.
The sodium sulfate plays a role in mass transfer.
The specific implementation mode is eight: the sixth or seventh embodiment is different from the sixth or seventh embodiment in that: the anode plate 2 is Ti/IrO2/RuO2And the width of the electrode is 4.5 cm. The rest is the same as the sixth or seventh embodiment.
The specific implementation method nine: this embodiment differs from one of the sixth to eighth embodiments in that: the cathode plate 3 is a stainless steel net attached with a nano graphite/ruthenium/polyethylene glycol/polyvinyl pyrrolidone composite material. The rest is the same as in one of the sixth to eighth embodiments.
In the embodiment, the nano graphite is compounded with the noble metal or the polymer to obtain the nano graphite/metal oxide or nano graphite/polymer composite material, so that the catalytic performance of the nano graphite/metal oxide or nano graphite/polymer composite material is improved, and the cathode is promoted to generate 2-electron oxygen reduction to generate hydrogen peroxide by changing the cathode material. Therefore, the use of only nano-graphite is not sufficient to fully achieve the intended effect, and a catalyst is incorporated into the nano-graphite.
The ruthenium oxide has better conductivity and higher oxygen adsorption capacity on the surface of the ruthenium oxide serving as an electrode material, and the metal ruthenium oxide has certain catalytic H2Activity and stability of O to OH & lt + & gt. And the electrode can generate OH & lt + & gt at a low potential. The reaction formula is as follows:RuOx+H2O+e﹣＝RuOx-1·OH+·OH；
loading the ruthenium oxide material onto the carbon base material having a large specific surface area can reduce the amount of ruthenium used in the ruthenium oxide catalyst. Graphite materials represented by nano-graphite also have a high electrochemical capacity per se and carbon materials are much cheaper. RuO in ruthenium oxide2Is a semiconductor type oxide and has metallic conductivity. RuO2Has better capability of catalyzing the generation of hydrogen peroxide. The electronic structure of Ru atom is 4d75s1, which is the element with the most oxidation state and can form RuO2、RuO3、Ru2O3And the like. The generation rate of the hydrogen peroxide is controlled by O on the surface of the catalyst2-And (4) determining the concentration. The ruthenium atom with high positive charge can easily adsorb oxygen molecules, and ruthenium is an electron-rich atom, so that the oxygen molecules can be effectively promoted to obtain electrons to perform reduction reaction.
The detailed implementation mode is ten: the present embodiment differs from one of the sixth to ninth embodiments in that: the preparation method of the nano graphite/ruthenium/polyethylene glycol/polyvinylpyrrolidone composite material comprises the following steps:
one, RuO2Preparation of nano graphite-s: weighing 0.2g of ruthenium chloride, dissolving the ruthenium chloride in 10mL of 1% polyethylene glycol, uniformly mixing, and slowly adding 0.0068g of polyvinylpyrrolidone under the condition of continuous stirring to obtain a ruthenium solution; dispersing 1.5g of nano-graphite in 10ml of polyethylene glycol, and uniformly mixing to obtain a nano-graphite solution; putting the prepared ruthenium solution into a separating funnel, putting the nano-graphite solution into a beaker, and putting the beaker on a magnetic stirrer; dropping the ruthenium solution in the separating funnel into a beaker at the speed of 1 drop/0.5 s to obtain a mixed solution; putting the mixed solution into a 40KHZ ultrasonic instrument for 60min, taking out, and aging at room temperature for 4-5 h; then drying in an oven at 120 ℃ and transferring to a muffle furnace at 300 ℃ for calcining for 3h to obtain RuO2Nano graphite-s;
secondly, preparing a cathode: mixing RuO2Nano graphite-s and nano graphite of 200 meshes are respectively connected withMixing Polytetrafluoroethylene (PTFE) according to a ratio of 3:1, placing the mixture into a beaker of a constant-temperature water bath at 65 ℃, dropwise adding a proper amount of absolute ethyl alcohol serving as a dispersing agent, and continuously stirring the mixture clockwise by using a glass rod until pasty paste is prepared;
and thirdly, wrapping the paste with tinfoil, then placing the paste in a roller press for rolling to prepare an electrode with the thickness of 1-2 mm, placing the electrode in distilled water, heating and boiling for 20min, and drying in an oven at 80 ℃ for 2h for later use. The others are the same as in one of the sixth to ninth embodiments.
The embodiment adopts a sol-gel method to prepare the nano graphite/ruthenium/polyethylene glycol/polyvinylpyrrolidone composite material.
The paste preparation process of the embodiment is to mix the nano-graphite and the PTFE emulsion into the condensed paste by using absolute ethyl alcohol.
The concrete implementation mode eleven: this embodiment differs from one of the sixth to tenth embodiments in that: the preparation method of the nano graphite/ruthenium/polyethylene glycol/polyvinylpyrrolidone composite material comprises the following steps:
weighing 0.2g of solid ruthenium chloride in a 25mL volumetric flask, and carrying out constant volume to obtain a ruthenium chloride solution; taking 9.2mL of concentrated ammonia water, and fixing the volume to 100mL to obtain a concentrated ammonia water solution; weighing 1.5g of nano-graphite, dissolving in 50mL of distilled water, and uniformly stirring by using a stirrer to obtain a nano-graphite solution; putting the nano graphite solution into a beaker, putting the beaker on a stirrer, and heating the beaker at 60 ℃; and mixing the ruthenium chloride solution with the concentrated ammonia water solution, placing the mixture in a separating funnel, slowly dropping the mixture into the nano-graphite solution, and simultaneously dropping 40mL of 1mol/L ammonia water into the nano-graphite. Stirring the mixed solution and continuously heating for half an hour; standing, aging, and oven drying at 100 deg.C; calcining at 350 ℃ in a muffle furnace for 3 h. The others are the same as in one of the sixth to tenth embodiments.
Precipitation is the more common method. The catalyst prepared by the method has higher active ingredients and uniform distribution, and can effectively adjust the size and the aperture of the material. The ruthenium-doped nano graphite catalyst is prepared by taking ruthenium chloride as a metal source and adopting a precipitation method. To ensure good stability of the electrode during electrolysis.
Example (b): verify through following embodiment the utility model discloses a beneficial effect:
electrocatalytic performance study:
RuO is prepared by adopting a sol-gel method2Nano graphite-s, and preparation of RuO by precipitation method2The/nano graphite-d is used for analyzing the apparent morphology and the structural composition of the composite material by methods such as SEM, TEM, AFM, XRD, Raman spectrum, XPS and the like. The results show that in RuO2In the nano graphite-s, Ru exists in the form of oxide, has a valence of +4 and is a tetragonal crystal, RuO2Uniformly dispersed on the surface of the nano graphite, the thickness of the nano graphite sheet is 2-3 nm, RuO2The thickness of the nano graphite-s is 5 nm; in RuO2In nano-graphite-d, RuO2In a hydrated amorphous state, RuO2Uniformly dispersing the particles on the surface of the nano graphite with the thickness of 2-3 nm and RuO2The thickness of the/nano graphite-d is 3-4 nm.
In diaphragm cells, RuO is added2Nano graphite-s and RuO2The nano graphite-d electrode is used as a cathode, and under the condition of continuous aeration, the current density is 38mA/cm2The electrolyte concentration is 0.1mol/L, the electrode spacing is 3cm, the initial concentration of phenol is 100mg/L, the room temperature is adopted, the electrolysis time is 120min, and the degradation rates of the composite cathode prepared by the two different preparation methods to phenol respectively reach 97.8 percent and 96.2 percent. RuO prepared by two methods2Nano graphite-s and RuO2The nano graphite-d has higher catalytic activity.
After the composite cathode is repeatedly used for many times, the degradation effect of phenol in the cathode chamber is not obviously reduced. This is mainly due to the good stability of the composite cathode. However, it is inevitable during use that a small amount of the ruthenium metal catalyst is lost during the cleaning sonication after each use. So that the degradation rate of phenol is slightly reduced in the final use stage. In the aspect of electrode appearance, the electrode is still good in stability after being used for many times, and the phenomena of electrode material falling, bubbling, damage and the like of the traditional stainless steel mesh carrier composite electrode are avoided. The reusability and stability of the composite electrode make it
In the electrochemical oxidation process, phenol is gradually degraded into small molecular acid due to the nonselective oxidation of hydroxyl radicals, and finally converted into harmless CO2And H2O2. Has better practical value and environmental protection and energy saving effects in the actual organic sewage treatment system.
Claims (6)
1. The nano-graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device is characterized by comprising a reaction tank (1), an anode plate (2), a cathode plate (3) and a gas distribution pipe (5), wherein the reaction tank (1) is connected with a water inlet pipeline (1-1) and a water outlet pipeline (1-2), the water inlet pipeline (1-1) and the water outlet pipeline (1-2) are respectively provided with a water inlet valve and a water discharge valve, and the anode plate (2) and the cathode plate (3) are oppositely arranged in the reaction tank (1) and are connected with an external direct-current power supply; the upper part of the inner cavity of the reaction tank (1) is also provided with a water distribution pipe (1-4); the air distribution pipe (5) is arranged at the bottom of the reaction tank (1) and is connected with an external air inlet pipeline (1-3), and a plurality of aeration heads (5-1) are uniformly distributed on the air distribution pipe (5).
2. The electrocatalytic oxidation reaction device with the nanographite-doped ruthenium oxide electrode as recited in claim 1, wherein the water distribution pipes (1-4) are perforated with 45-degree inclined holes.
3. The nano-graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device according to claim 1, wherein the cross section of the aeration head (5-1) is trapezoidal, the aeration head (5-1) is internally provided with a first cutting saw tooth (5-2) and a second cutting saw tooth (5-3), the first cutting saw tooth (5-2) is arranged above the second cutting saw tooth (5-3), and the first cutting saw tooth (5-2) and the second cutting saw tooth (5-3) are oppositely arranged on a horizontal plane and have staggered tooth shapes.
4. The nanographite-doped ruthenium oxide electrode electrocatalytic oxidation reaction device according to claim 3, wherein the tooth ends of the first cutting serration (5-2) and the second cutting serration (5-3) are flush on a vertical plane.
5. The nano-graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device according to claim 3, wherein the slope angle of the aeration head (5-1) is 60 °.
6. The nano graphite doped ruthenium oxide electrode electrocatalytic oxidation reaction device according to claim 1, wherein the anode plate (2) is Ti/IrO2/RuO2And the width of the electrode is 4.5 cm.
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