CN110885113B - Method for manufacturing electrode by using natural graphite ore - Google Patents
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Abstract
The invention relates to a method for manufacturing an electrode by utilizing natural graphite ore, which comprises the following steps: s1, selecting an electrode material; s2, preparing an electrode material; s3, preparing an electrode substrate; s4, cutting; s5, coarse grinding; s6, grinding waste materials; s7, pressing; s8, curing and forming; and S9, finishing. According to the preparation method, the waste materials after cutting the natural graphite are ground and then are pressed with the electrode substrate into a whole, so that waste utilization is realized, and the cost is reduced. The graphite electrode prepared by the method has the characteristics of high crystallinity, high strength and high density of natural graphite, and also has the characteristics of good conductivity and low resistivity of artificial graphite.
Description
Technical Field
The invention relates to the field of application and preparation of electrochemical materials, in particular to a method for manufacturing an electrode by utilizing natural graphite ore.
Background
The ammonia nitrogen is one of important common pollutants in water, and the ammonia nitrogen in natural water mainly comes from wastewater discharged from chemical engineering, metallurgy, meat processing, cultivation and the like, agricultural irrigation, animal excrement, garbage leachate and the like. The most predominant form of nitrogen in water is the ammonia nitrogen state (NH)4 +-N), the presence of excess ammonia nitrogen in aqueous environments can cause a number of deleterious effects. Due to NH4 +N oxidation causes the reduction of dissolved oxygen in water, and black and odorous water is formed, so that the water quality is reduced. And NH4 +N is oxidized to form nitrate Nitrogen (NO)3- -N) and nitrous Nitrogen (NO)2- -N) which has a great harmful effect on humans and aquatic organisms, and long-term consumption of NO3Water with N content over 10mg/L, methemoglobinemia, NO in water2The action of- -N and an amine produces nitrosamines, which are "triproduct" substances. Too much nitrogen in water can cause eutrophication of water body, which leads to the rapid increase of the quantity of photosynthetic microorganisms (most of algae) and the reduction of water quality. In recent years, the discharge of ammonia nitrogen-containing wastewater into water bodies causes difficulties in drinking water for people and livestock and even poisoning accidents, so the treatment of ammonia nitrogen in water bodies becomes one of the hotspots of environmental research.
At present, methods for treating ammonia nitrogen in water are mainly divided into an air stripping method, a breakpoint chlorination method, a biological denitrification method, an electrochemical oxidation method and the like.
The biological denitrification technology is the most effective and economic method for removing ammonia nitrogen in raw water, but under the low-temperature condition in winter, the biological action is seriously inhibited, and the denitrification efficiency is seriously reduced; the air stripping method needs to add a large amount of alkali, causes secondary pollution to the environment and cannot remove organic matters in water; the pointing chlorination method needs to increase the chlorine dosage under the low temperature condition, and increases the risk of environmental pollution.
The electrochemical oxidation method has the advantages of strong controllability, direct reaction with pollutants in water, no secondary pollution, mild reaction conditions, simple operation, environmental friendliness, small reagent consumption, small equipment volume, automatic control and the like, is one of the most probably industrially applied advanced oxidation technologies, and has extremely high application prospect in the aspect of green water treatment.
The electrode is a key factor for realizing the electrochemical reaction and improving the catalytic reaction rate and the current efficiency in the electrochemical oxidation reaction, and an ideal electrode material has high electrochemical activity, good stability, good conductivity, wide source, low price, environmental protection and no secondary pollution. The current electrodes for treating wastewater by electrooxidation include platinum electrodes, graphite electrodes and various oxide electrodes.
The selection of anode materials is the focus of research at the present stage, and a high-oxygen ultra-DSA anode (a titanium-based coating oxide anode with higher oxygen evolution overpotential) has the characteristics of high current efficiency, strong stability and the like under laboratory conditions, but the cost is too high, and the anode is obviously unrealistic in practical production application.
Compared with other electrodes, the graphite electrode has the characteristics of wide source, low price, environmental protection and no secondary pollution, but the current of the existing graphite is not uniformly distributed, the passing current density is small, the resistance volume is large, and the effect of treating the mineral processing wastewater by using the graphite electrode as an electrooxidation anode is not ideal.
Disclosure of Invention
The invention aims to provide a low-price natural mineral which is used as an electrode and can achieve the effect of treating ammonia nitrogen in a water body within a certain time. Therefore, the defects that the existing electrochemical oxidation technology has high cost and cannot be applied to production in a large area are overcome, and a new method is provided for treating ammonia nitrogen in water bodies in North China.
The technical scheme of the invention is as follows: a method for manufacturing an electrode by using natural graphite ore comprises the following steps:
s1, selecting electrode materials: selecting natural graphite ore as an electrode raw material;
s2, preparing an electrode material: cutting the selected graphite ore into plate-shaped electrode materials of 50mm by 40mm by 10mm, and recovering graphite waste materials cut from the graphite ore;
s3, preparing an electrode substrate: laminating and bonding 4 plate-shaped electrode materials in the step S2 by a carbon resin bonding agent to form a rectangular block-shaped electrode base body, and heating, curing and molding;
s4, cutting: equally cutting the electrode substrate into 4 graphite laminated structures along the direction vertical to the plane of the plate-shaped electrode material;
s5, coarse grinding: carrying out coarse grinding on the surface of each graphite laminated structure to obtain an electrode substrate rough blank;
s6, grinding waste materials: grinding the graphite waste in the step S2 into graphite powder, adding modified asphalt powder, adding ferric oxide serving as an air bulking inhibitor, and stirring and heating for 2-5 hours to obtain a pasty mixed material;
s7, pressing: placing the electrode substrate rough blank in the step S5 into a pressing mold, wherein the pressing mold is of a cylindrical cavity structure, the height of the pressing mold is 50mm, the diameter of the pressing mold is 45mm, adding the pasty mixed material in the step S6 into the outermost layer of the pressing mold, and pressing the mixed material on the outermost layer and the electrode substrate rough blank positioned in the center of the pressing mold together according to a method of pre-pressing and pressurizing to obtain an electrode fine blank;
s8, curing and forming: cooling the electrode fine blank, and solidifying and forming;
s9, finished product: and (3) loading the cooled electrode fine blank into a high-temperature furnace for roasting, then impregnating, sending into a graphitization furnace, carbonizing, then heating for graphitization, cooling, and then machining to obtain an electrode finished product.
Further, the cutting in steps S2 and S4 is laser cutting or linear cutting.
Furthermore, during laser cutting, laser with the wavelength ranging from 251nm to 1058nm is adopted, and the average power range of the laser beam is 0.5W to 25W.
Further, during linear cutting, the electrode wire is one of molybdenum wire, copper wire or galvanized electrode wire with the diameter of 0.04-0.2 mm, the linear speed is 350-750 m/min, and the linear cutting speed is 15-75 mm2/min。
Further, the carbon resin binder in step S3 is formed by combining one or more of modified liquid pitch, furan resin and phenolic resin, and has a viscosity of 0.2 to 16pa.s and a residual carbon content of 40 to 50%.
Further, the natural graphite ore is of an aphanitic structure, and the fixed carbon content is 65-85%; the weight ratio of the graphite powder to the modified asphalt powder and the ferric oxide in the step S6 is 3.5:1: 0.1.
Further, the mixing temperature in the step S6 is 200-300 ℃; the pre-pressing pressure in the step S7 is 150MPa, the pre-pressing time is 5min, and the pressurizing pressure is 200 MPa.
Further, in the step S8, the electrode fine blank in the step S7 is left at room temperature for 24 hours or more, and then heated to 200 ℃ at a heating rate of 2 to 5 ℃/h, and then is cured by keeping the temperature for 48 hours or more.
Further, the roasting is to use metallurgical coke powder or quartz sand as a protective medium in a roasting furnace to indirectly heat at a heating rate of 2-5 ℃/h under the condition of air isolation, and the highest temperature is 1300 ℃; the temperature-rising roasting time is 220-240 hours; and the impregnation is to impregnate the electrode fine blank by adopting high-quality asphalt.
Further, the carbonization is carried out under the protection of nitrogen at the temperature of 700-1200 ℃; the graphitization is heat treatment carried out at the temperature of more than 2500 ℃ under the action of protective gas.
The invention has the following beneficial effects:
1) the electrode substrate adopted in the invention is a natural graphite electrode, the preparation process is simple to operate, and the cost is greatly reduced in the practical production application; the difference of the electrolysis effect of the pure graphite electrode is very small, so that the natural graphite electrode is proved to be a feasible scheme;
2) the waste materials after cutting the natural graphite are ground and then are pressed with the electrode substrate into a whole, so that the waste utilization is realized, and the cost is reduced. The graphite electrode prepared by the method has the characteristics of high crystallinity, high strength and high density of natural graphite, and also has the characteristics of good conductivity and low resistivity of artificial graphite;
3) the addition of the iron oxide powder can promote the graphitization of the binding agent carbon, reduce the resistivity and improve the conductivity and oxidation resistance of the graphite electrode;
4) by adopting isostatic pressing, the problems of the graphite electrode quality and the large-diameter graphite electrode can be solved;
5) the oxidation-resistant coating can greatly improve the oxidation resistance of the graphite electrode; the service life is prolonged by more than 20 percent; namely, the quality of the graphite electrode is obviously improved.
The method adopts the natural graphite ore as the electrode, greatly lowers the cost of reducing ammonia nitrogen in the water body by an electrochemical method, and further can be widely applied to actual production.
Drawings
FIG. 1 is a schematic diagram of the manufacturing process of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1: a method for manufacturing an electrode by using natural graphite ore comprises the following steps:
s1, selecting electrode materials: selecting natural graphite ore as an electrode raw material; the natural graphite ore is used as an electrode raw material, and has the advantages of good conductivity, high and low temperature resistance (the volume of graphite does not change greatly and cracks are not easy to generate during temperature shock), stable chemical properties, no toxicity, low cost and the like.
S2, preparing an electrode material: cutting selected graphite ore into plate-shaped electrode materials with the thickness of 50mm x 40mm x 10mm (the specification can be adjusted according to actual conditions), and recovering graphite waste materials cut from the graphite ore; the selected graphite ore has an aphanitic structure and high grade, and the content of the fixed carbon is 60-85% generally. And a few as high as 90% or more. The electrode has compact block, soil, lamellar and leaf structures, and the like, and is cut in the direction perpendicular to the lamellar or leaf direction so as to ensure the stability of the electrode.
S3, preparing an electrode substrate: laminating and bonding 4 plate-shaped electrode materials in the step S2 by a carbon resin bonding agent to form a rectangular block-shaped electrode base body, and heating, curing and molding;
s4, cutting: equally cutting the electrode substrate into 4 graphite laminated structures along the direction vertical to the plane of the plate-shaped electrode material; so as to realize the rapid conduction of heat in the vertical direction in the electrolytic process;
s5, coarse grinding: carrying out coarse grinding on the surface of each graphite laminated structure to obtain an electrode substrate rough blank; the step is to increase the surface roughness of the graphite laminated structure so that graphite powder can be better attached to the graphite laminated structure in the next step;
s6, grinding waste materials: grinding the graphite waste in the step S2 into graphite powder with the granularity of 200 meshes, adding modified asphalt powder, adding ferric oxide with the granularity of 1000 meshes as an air bulking inhibitor, adding water, stirring and heating for 2-5 hours to obtain a pasty mixed material;
s7, pressing: placing the electrode substrate rough blank in the step S5 into a pressing mold, wherein the pressing mold is of a cylindrical cavity structure, the height of the pressing mold is 50mm, the diameter of the pressing mold is 45mm, adding the pasty mixed material in the step S6 into the outermost layer of the pressing mold, and pressing the mixed material on the outermost layer and the electrode substrate rough blank positioned in the center of the pressing mold together according to a method of pre-pressing and pressurizing to obtain an electrode fine blank;
s8, curing and forming: cooling the electrode fine blank, and solidifying and forming;
s9, finished product: and (3) loading the cooled electrode fine blank into a high-temperature furnace for roasting, then impregnating, sending into a graphitization furnace, carbonizing, then heating for graphitization, cooling, and then machining to obtain an electrode finished product.
Further, the cutting in steps S2 and S4 is laser cutting or linear cutting.
Furthermore, during laser cutting, laser with the wavelength ranging from 251nm to 1058nm is adopted, and the average power range of the laser beam is 0.5W to 25W.
Further, during linear cutting, the electrode wire is one of molybdenum wire, copper wire or galvanized electrode wire with the diameter of 0.04-0.2 mm, the linear speed is 350-750 m/min, and the linear cutting speed isIs 15 to 75mm2/min。
Further, the carbon resin binder in step S3 is formed by combining one or more of modified liquid pitch, furan resin and phenolic resin, and has a viscosity of 0.2 to 16pa.s and a residual carbon content of 40 to 50%.
Further, the natural graphite ore is of an aphanitic structure, and the fixed carbon content is 80%; the weight ratio of the graphite powder to the modified asphalt powder and the ferric oxide in the step S6 is 3.5:1: 0.1.
Further, the mixing temperature in the step S6 is 200-300 ℃; the pre-pressing pressure in the step S7 is 150MPa, the pre-pressing time is 5min, the pressurizing pressure is 200MPa, and the molding pressure maintaining time is 10 min; the pressure was released at a pressure release rate of 20 MPa/min.
Further, in the step S8, the electrode fine blank in the step S7 is left at room temperature for 24 hours or more, and then heated to 200 ℃ at a heating rate of 2 to 5 ℃/h, and then is cured by keeping the temperature for 48 hours or more.
Further, the roasting is to use metallurgical coke powder or quartz sand as a protective medium in a roasting furnace to indirectly heat at a heating rate of 2-5 ℃/h under the condition of air isolation, and the highest temperature is 1300 ℃; the temperature-rising roasting time is 220-240 hours; and the impregnation is to impregnate the electrode fine blank by adopting high-quality asphalt.
Further, the carbonization is carried out under the protection of nitrogen at the temperature of 700-1200 ℃; the graphitization is heat treatment carried out at the temperature of more than 2500 ℃ under the action of protective gas. Finally obtaining the mixed natural graphite anode.
After the graphite anode is manufactured, the difference between the electrolysis effect of the graphite anode and the electrolysis effect of the pure graphite electrode is verified through experiments:
(1) collecting a water sample: a natural water sample is adopted and stored in a polyethylene bottle, and the ammonia nitrogen content in the water is determined as soon as possible or electrochemical treatment is carried out.
(2) And (3) treating ammonia nitrogen in water: connecting two polar plates in an electrolytic cell by a direct current power supply, applying a voltage of 10V, and generating the voltage under the action of an external electric fieldHydroxyl free radical capable of reacting ammonia Nitrogen (NH) in water4 +-N) oxidation to N2Thereby achieving the effect of treating the ammonia nitrogen in the water body. Setting continuous treatment time gradients as 0h, 1h, 2h, 4h, 6h, 8h and 12h, respectively measuring the ammonia nitrogen concentration in the water at each time point, and comparing with the treatment effect of a pure graphite electrode under the same conditions.
(3) The ammonia nitrogen determination method comprises the following steps: the measurement is carried out by using a national standard method (HJ 536-2009) salicylic acid spectrophotometry.
(4) And (4) analyzing results: the electrolysis effect of the natural graphite electrode is very small in difference with the effect of the pure graphite electrode, so that the purpose of the experiment can be achieved, and the natural graphite electrode can be used.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for manufacturing an electrode by using natural graphite ore is characterized by comprising the following steps:
s1, selecting electrode materials: selecting natural graphite ore as an electrode raw material;
s2, preparing an electrode material: cutting the selected graphite ore into plate-shaped electrode materials of 50mm by 40mm by 10mm, and recovering graphite waste materials cut from the graphite ore;
s3, preparing an electrode substrate: laminating and bonding 4 plate-shaped electrode materials in the step S2 by a carbon resin bonding agent to form a rectangular block-shaped electrode base body, and heating, curing and molding;
s4, cutting: equally cutting the electrode substrate into 4 graphite laminated structures along the direction vertical to the plane of the plate-shaped electrode material;
s5, coarse grinding: carrying out coarse grinding on the surface of each graphite laminated structure to obtain an electrode substrate rough blank;
s6, grinding waste materials: grinding the graphite waste in the step S2 into graphite powder, adding modified asphalt powder, adding ferric oxide serving as an air bulking inhibitor, and stirring and heating for 2-5 hours to obtain a pasty mixed material;
s7, pressing: placing the electrode substrate rough blank in the step S5 into a pressing mold, wherein the pressing mold is of a cylindrical cavity structure, the height of the pressing mold is 50mm, the diameter of the pressing mold is 45mm, adding the pasty mixed material in the step S6 into the outermost layer of the pressing mold, and pressing the mixed material on the outermost layer and the electrode substrate rough blank positioned in the center of the pressing mold together according to a method of pre-pressing and pressurizing to obtain an electrode fine blank;
s8, curing and forming: cooling the electrode fine blank, and solidifying and forming;
s9, finished product: and (3) loading the cooled electrode fine blank into a high-temperature furnace for roasting, then impregnating, sending into a graphitization furnace, carbonizing, then heating for graphitization, cooling, and then machining to obtain an electrode finished product.
2. The method for manufacturing an electrode using natural graphite ore according to claim 1, wherein: the cutting in the steps S2 and S4 is by laser cutting or wire cutting.
3. The method for manufacturing an electrode using natural graphite ore according to claim 2, wherein: during laser cutting, laser with the wavelength ranging from 251nm to 1058nm is adopted, and the average power range of the laser beam is 0.5W to 25W.
4. The method for manufacturing an electrode using natural graphite ore according to claim 2, wherein: during linear cutting, the electrode wire is one of molybdenum wire, copper wire or zinc-plated electrode wire with the diameter of 0.04-0.2 mm, the linear speed is 350-750 m/min, and the linear cutting speed is 15-75 mm2/min。
5. The method for manufacturing an electrode using natural graphite ore according to claim 3 or 4, wherein: the carbon resin binder in the step S3 is formed by combining one or more than two of modified liquid asphalt, furan resin and phenolic resin, the viscosity of the binder is 0.2-16 Pa.S, and the residual carbon content is 40-50%.
6. The method for manufacturing an electrode using natural graphite ore according to claim 5, wherein: the natural graphite ore is of an aphanitic structure, and the fixed carbon content is 65-85%; the weight ratio of the graphite powder to the modified asphalt powder and the ferric oxide in the step S6 is 3.5:1: 0.1.
7. The method for manufacturing an electrode using natural graphite ore according to claim 6, wherein: the mixing temperature in the step S6 is 200-300 ℃; the pre-pressing pressure in the step S7 is 150MPa, the pre-pressing time is 5min, and the pressurizing pressure is 200 MPa.
8. The method for manufacturing an electrode using natural graphite ore according to claim 7, wherein: in the step S8, the electrode fine blank in the step S7 is placed at room temperature for more than 24 hours, then is heated to 200 ℃ at a heating rate of 2-5 ℃/h, and is then kept warm for more than 48 hours for solidification.
9. The method for manufacturing an electrode using natural graphite ore according to claim 8, wherein: the roasting is to use metallurgical coke powder or quartz sand as a protective medium in a roasting furnace to indirectly heat at a heating rate of 2-5 ℃/h under the condition of air isolation, and the highest temperature is 1300 ℃; the temperature-rising roasting time is 220-240 hours; and the impregnation is to impregnate the electrode fine blank by adopting high-quality asphalt.
10. The method for manufacturing an electrode using natural graphite ore according to claim 9, wherein: the carbonization is carried out under the protection of nitrogen at the temperature of 700-1200 ℃; the graphitization is heat treatment carried out at the temperature of more than 2500 ℃ under the action of protective gas.
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