Treatment methods for xanthate beneficiation wastewater using natural minerals

Abstract

This invention provides a method for treating xanthate-based mineral processing wastewater using natural minerals, belonging to the field of water treatment technology. The method includes: adding pyrite powder to the xanthate-based mineral processing wastewater for activation treatment, converting xanthate groups into dixanthate groups, resulting in activated mineral processing wastewater; passing the activated wastewater through a galvanic cell filter layer while aeration is introduced, obtaining a first solution; and passing the first solution sequentially through a metal purification filter layer and a control filter layer to obtain mineral processing return water. The galvanic cell filter layer comprises pyrite, pyrolusite, and graphite. Through the coupling effect of pyrite and pyrolusite, oxygen in the air is activated into reactive oxygen free radicals and / or ozone, which oxidize and degrade the xanthate-based organic matter in the mineral processing wastewater.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, specifically to the field of water treatment technology in the mining process, and particularly to a method for treating xanthate beneficiation wastewater using natural minerals. Background Technology

[0002] Mineral resource development is the foundation of industrial development. During mineral resource development, many ores require beneficiation to obtain concentrates for smelting. Flotation is one of the main beneficiation methods. In the flotation process of ores, especially in the flotation of non-ferrous metal sulfide ores, xanthate reagents are widely used as collectors for the target minerals. Xanthates, also known as xanthates, are characterized by relatively high levels of xanthate-based organic matter, high heavy metal content, and strong aeration in the beneficiation wastewater after the flotation of non-ferrous metal sulfide ores.

[0003] In xanthate-based mineral processing wastewater, the presence of xanthate organic matter causes excessive chemical oxygen demand (COD). Xanthate organic matter readily forms water-insoluble chelates with metal ions, leading to heavy metal accumulation and water pollution. Xanthate organic matter has a foul odor; even small amounts can easily cause foul-smelling water and disrupt the ecological balance of aquatic bodies.

[0004] Currently, common methods for treating mineral processing wastewater include chemical precipitation, oxidation, combined precipitation-oxidation, acidification, and ion exchange adsorption. However, these methods have drawbacks in practical applications, such as high treatment costs, long treatment times, potential for secondary pollution, and complex processing procedures. Summary of the Invention

[0005] In view of this, in order to at least partially solve at least one of the aforementioned technical problems, the present invention provides a method for treating xanthate beneficiation wastewater using natural minerals.

[0006] According to one embodiment of the present invention, a method for treating xanthate-based mineral processing wastewater using natural ore is provided, comprising: adding pyrite powder to the xanthate-based mineral processing wastewater for activation treatment, thereby converting xanthate groups into dixanthate groups to obtain activated mineral processing wastewater; passing the activated mineral processing wastewater through a galvanic cell filter layer while introducing air to obtain a first solution; and passing the first solution sequentially through a metal purification filter layer and a control filter layer to obtain mineral processing return water; wherein the galvanic cell filter layer comprises pyrite, pyrolusite, and graphite, and through the coupling effect of pyrite and pyrolusite, activating oxygen in the air into reactive oxygen free radicals and / or ozone, thereby causing the reactive oxygen free radicals and / or ozone to oxidize and degrade the xanthate-based organic matter in the mineral processing wastewater.

[0007] According to an embodiment of the present invention, the filter material layer of the galvanic cell is prepared by the following process: pyrite, pyrolusite and graphite are mixed evenly and filled into a cylindrical pipe with a diaphragm at the bottom; the particle size range of pyrite, pyrolusite and graphite includes 3~5 mm respectively.

[0008] According to an embodiment of the present invention, the mass ratio of pyrite, pyrolusite, and graphite is (2~4):(2~5):1; the height of the galvanic cell filter layer is 50~70mm.

[0009] According to an embodiment of the present invention, passing the activated mineral processing wastewater through a galvanic cell filter layer to obtain a treated first solution includes: passing the activated mineral processing wastewater through the galvanic cell filter layer at a rate of 15-30 mL / min at 20-50°C; and introducing air at a rate of 3-5 L / min.

[0010] According to an embodiment of the present invention, passing a first solution sequentially through a metal purification filter layer and a control filter layer to obtain mineral processing return water includes: passing the first solution through the metal purification filter layer with air introduced to obtain a second solution; passing the second solution through the control filter layer with air introduced to obtain mineral processing return water; wherein the metal purification filter layer includes pyrite and calcite, and the metal ions in the first solution are removed by precipitation through interfacial catalysis of pyrite.

[0011] According to an embodiment of the present invention, the mass ratio of pyrite to calcite is (1~2):2; the height of the metal purification filter layer is 40~70mm.

[0012] According to an embodiment of the present invention, the filter media layer comprises pyrolusite and calcite; the mass ratio of pyrolusite to calcite is 2:(1~2); and the height of the filter media layer is controlled to be 40~70mm.

[0013] According to an embodiment of the present invention, pyrite powder is added to xanthate-based mineral processing wastewater for activation treatment, so that the xanthate groups are converted into bixanthate groups. The activated mineral processing wastewater is obtained by: adding pyrite powder with a particle size of 0.001-0.074 mm to xanthate-based mineral processing wastewater at 20-50°C and stirring for 5-10 min, followed by standing for 10-20 min, to obtain an upper layer of activated mineral processing wastewater and a lower layer of a first mixture; the amount of pyrite powder added is 1-2% of the weight of xanthate-based mineral processing wastewater, and the stirring is solution stirring or air-filled stirring. The first mixture includes pyrite particles and a mixed slurry, and the sulfur content of the pyrite powder is greater than 45% by mass.

[0014] According to an embodiment of the present invention, after oxidizing the first mixture by introducing air, 0.1% by mass of pyrite particles of the first mixture are added to obtain a second mixture; the second mixture is added to xanthate beneficiation wastewater for recycling; wherein the recycling is performed 1 to 10 times.

[0015] According to an embodiment of the present invention, the concentration of xanthate organic matter in xanthate beneficiation wastewater is 10~150 mg / L.

[0016] According to an embodiment of the present invention, pyrite powder is added to xanthate beneficiation wastewater. Pyrite can interact with oxygen in the air, generating a relatively large number of free radicals in situ. These free radicals have strong oxidizing properties, transforming xanthate groups into more easily oxidized and degraded bixanthate groups, thereby promoting the formation of bixanthate groups and facilitating their degradation and removal in subsequent treatment steps. By assembling pyrite and pyrolusite into a galvanic cell filter layer of natural ore, wherein pyrite has redox properties, pyrolusite has oxidizing properties, and graphite serves as a conductive medium, under air-conditioning conditions, oxygen in the air participates in the reaction of the galvanic cell filter layer. Pyrite is oxidized and releases electrons, which are transferred to pyrolusite through the graphite conductive medium. This allows oxygen to accept electrons and be activated into reactive oxygen free radicals and / or ozone. Furthermore, the reactive oxygen free radicals and / or ozone act on xanthate organic matter, oxidizing and degrading it. The first solution is then passed through a metal purification filter layer and a control filter layer to remove metal ions and other impurities from the first solution, resulting in mineral processing wastewater, thus realizing the reuse of mineral processing wastewater.

[0017] The processing method of this invention is simple and easy to implement. Because it uses natural ore, the cost is low and the efficiency is high. The ore beneficiation water obtained by this method can be 100% reused, which is conducive to its promotion in the field of non-ferrous metal beneficiation. Attached Figure Description

[0018] Figure 1 A flowchart illustrating a method for treating xanthate beneficiation wastewater using natural ore according to an embodiment of the present invention is shown;

[0019] Figure 2 A process flow diagram of a method for treating xanthate beneficiation wastewater using natural ore according to an embodiment of the present invention is shown.

[0020] Figure 3 The X-ray diffraction pattern of pyrite used in the filter layer of Embodiment 1 of the present invention is shown;

[0021] Figure 4a The following are electron micrographs and distribution maps of pyrite in the filter layer of the galvanic cell of Embodiment 1 of the present invention before use:

[0022] Figure 4bThe following are electron micrographs and distribution maps of pyrite in the filter layer of the galvanic cell of Embodiment 1 of the present invention after use: surface scanning electron microscope image and total distribution spectrum.

[0023] Figure 5 The bar charts showing the removal effects of xanthate-like organic matter in Examples 1-3 of the present invention are illustrated; and

[0024] Figure 6 The bar chart shows the gold ore recovery effect of using untreated wastewater, tap water, and liquid 1 and liquid 2 obtained after treatment in Example 3 of the present invention, respectively. Detailed Implementation

[0025] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the invention. In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the embodiments of the invention for ease of explanation. However, it will be apparent that one or more embodiments may be practiced without these specific details. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0026] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "comprising" as used herein indicates the presence of features, steps, or operations, but does not exclude the presence or addition of one or more other features.

[0027] When using expressions such as "at least one of A, B, and C," the expression should generally be interpreted in accordance with the meaning commonly understood by a person skilled in the art (e.g., "a system having at least one of A, B, and C" should include, but is not limited to, systems having A alone, having B alone, having C alone, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.). When using expressions such as "at least one of A, B, or C," the expression should generally be interpreted in accordance with the meaning commonly understood by a person skilled in the art (e.g., "a system having at least one of A, B, or C" should include, but is not limited to, systems having A alone, having B alone, having C alone, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.).

[0028] In this invention, "xanthate organic compounds" can be understood as alkyl xanthates, such as sodium ethyl xanthate, potassium ethyl xanthate, sodium butyl xanthate, potassium butyl xanthate, etc.

[0029] In the flotation process of ores, especially in the flotation of non-ferrous metal sulfide ores, xanthate-based organic compounds are widely used as collectors for the target minerals. This results in the flotation wastewater from non-ferrous metal sulfide ores being characterized by large volume, high heavy metal content, and high xanthate-based organic compound content. One related technology is to use activated carbon adsorption to treat the wastewater, but this method is costly, and even after activated carbon adsorption, the wastewater is still difficult to meet discharge standards.

[0030] In realizing the concept of this invention, it was discovered that by utilizing the reaction between pyrite and xanthate groups to convert them into dixanthate groups, the subsequent oxidative degradation is enhanced. By assembling a galvanic cell filter layer using pyrite, pyrolusite, and graphite, the redox properties of pyrite can be used as an anode, and the oxidizing properties of pyrolusite can be used as a cathode. When beneficiation wastewater flows through the galvanic cell filter layer, an electrochemical system is constructed with the introduction of air. This system activates oxygen in the air into reactive oxygen free radicals and / or ozone, which oxidize and degrade xanthate-like organic matter in the beneficiation wastewater.

[0031] Specifically, according to one embodiment of the present invention, a method for treating xanthate beneficiation wastewater using natural minerals is provided. Figure 1 A flowchart illustrating a method for treating xanthate beneficiation wastewater using natural minerals according to an embodiment of the present invention is shown. Figure 2 A process flow diagram of a method for treating xanthate beneficiation wastewater using natural ore, according to an embodiment of the present invention, is shown. Please refer to... Figure 1 and Figure 2 As shown, this includes operations S101 to S103.

[0032] In operation S101, pyrite powder is added to xanthate beneficiation wastewater for activation treatment, so that the xanthate groups are converted into bixanthate groups, and the activated beneficiation wastewater is obtained.

[0033] In related technologies, the pH is typically adjusted to below 4 by adding acid, and hydrogen peroxide is added to oxidize and degrade xanthate-based organic matter. This invention adds pyrite powder (FeS2) to xanthate-based mineral processing wastewater. The pyrite powder interacts with the xanthate-based organic matter, converting xanthate groups into more easily degradable dixanthate groups, and simultaneously converting sulfide ions in pyrite into sulfate ions. The addition of pyrite powder helps adjust the pH of the xanthate-based mineral processing wastewater to around 5, making it easier for xanthate groups to react with pyrite to form dixanthate groups, thus facilitating the oxidative degradation of xanthate-based organic matter.

[0034] In operation S102, with air introduced, the activated mineral processing wastewater is passed through the galvanic cell filter layer to obtain the first solution.

[0035] According to embodiments of the present invention, natural ores possess environmental properties such as mineral surface effects, mineral redox effects, and mineral porosity effects, and natural ores have environmental purification functions, but there are many types. This invention utilizes the redox properties of pyrite, the oxidizing and catalytic properties of pyrite, and the conductivity of graphite to construct an electrochemical process when air is introduced. In this electrochemical process, pyrite is oxidized, releasing electrons, which are then reduced to reactive oxygen species (e.g., hydroxyl radicals ·OH) and / or ozone. These reactive oxygen species and / or ozone have strong oxidizing properties and high reactivity, enabling them to oxidize and degrade xanthate-like organic matter in mineral processing wastewater.

[0036] In operation S103, the first solution passes sequentially through the metal purification filter layer and the control filter layer to obtain mineral processing return water.

[0037] According to an embodiment of the present invention, the first solution passes through a metal purification filter layer to remove heavy metals from the first solution. Then, by controlling the filter layer, it is helpful to remove reducing impurities, etc., so that the resulting mineral processing recycled water meets the water quality standards for reuse.

[0038] According to embodiments of the present invention, through the coupling effect of pyrite and pyrolusite, oxygen in the air is activated into reactive oxygen free radicals and / or ozone, which then oxidize and degrade xanthate-like organic matter in mineral processing wastewater. This invention utilizes the redox properties of pyrite, the oxidative catalytic properties of pyrolusite, and the conductivity and adsorption properties of graphite to form a galvanic cell chemical reaction at the interface region between the three materials. This allows pyrite, oxygen in the air, and water to combine, and under the oxidative catalytic action of pyrolusite, oxygen is activated into reactive oxygen free radicals and / or ozone, achieving the oxidative degradation of xanthate-like organic matter in xanthate-like mineral processing wastewater. The resulting first solution, after passing through a metal purification filter layer and a control filter layer, can be 100% used as recycled water for non-ferrous metal sulfide mineral processing. Because natural ore is used as the raw material for the filter layer, it achieves both low cost and high treatment efficiency, facilitating industrial-scale application in the mineral processing field.

[0039] According to an embodiment of the present invention, operation S101 includes sub-operations S1011 to S1012.

[0040] In sub-operation S1011, at 20~50℃, pyrite powder with a particle size of 0.001~0.074mm is added to xanthate beneficiation wastewater.

[0041] In sub-operation S1012, stir for 5-10 minutes, then let stand for 10-20 minutes to obtain the upper layer of activated mineral processing wastewater and the lower layer of the first mixture.

[0042] According to embodiments of the present invention, pyrite powder has a strong adsorption capacity and can adsorb organic pollutants in xanthate beneficiation wastewater. Adjusting the particle size of the pyrite powder to between 0.001 and 0.074 mm helps increase the contact area with the xanthate beneficiation wastewater, improving reaction efficiency. Within the aforementioned temperature range of 20–50°C, for example, 20°C, 30°C, 40°C, or 50°C, the chemical reactivity between pyrite powder and xanthate organic matter is higher, which is more conducive to the reaction. Stirring helps to accelerate the full contact and mixing between pyrite powder and xanthate beneficiation wastewater, and helps to promote the conversion of xanthate groups to dixanthate groups. Stirring can be performed, for example, by solution stirring or air-filled stirring. Adjusting the stirring within the aforementioned range allows for sufficient mixing between the pyrite powder and xanthate organic matter without prolonged mixing that could lead to side reactions. Letting the mixture stand for 10–20 minutes helps unreacted pyrite powder and pyrite particles adsorbed with organic pollutants settle to the bottom of the container, forming a first mixture. The first mixture comprises pyrite particles and a mixed slurry. The upper layer of the container contains activated mineral processing wastewater, the quality of which has been improved to some extent. The amount of pyrite powder added is 1-2% by weight of the xanthate-based mineral processing wastewater, for example, 1%, 1.5%, or 2%. Pyrite powder within this range facilitates sufficient contact and reaction with xanthate-based organic matter, while providing ample adsorption sites, thereby improving the treatment efficiency of xanthate-based organic matter. The sulfur content of the pyrite powder is greater than 45% by mass. The sulfur content within the above range helps to provide sufficient sulfur ions to interact with xanthate-based organic matter, further improving the removal effect of xanthate-based organic matter.

[0043] According to an embodiment of the present invention, the filter layer of the galvanic cell is prepared by the following process:

[0044] Pyrite, pyrolusite, and graphite are mixed evenly and filled into a cylindrical pipe with a diaphragm at the bottom. The inner diameter of the cylindrical pipe is 30-34 mm, for example, 30 mm, 32 mm, or 34 mm, preferably 32 mm. The cylindrical pipe is made of plastic. The diaphragm can be, for example, filter cloth. An air passage can be provided 5 mm from the bottom of the diaphragm in the cylindrical pipe as needed. The particle size range of pyrite, pyrolusite, and graphite is 3-5 mm. Setting the particle size of the three materials within the above range and adjusting the cylindrical pipe as described above helps to ensure sufficient contact with the mineral processing wastewater while allowing the wastewater to pass smoothly through the galvanic cell filter layer.

[0045] According to an embodiment of the present invention, the mass ratio of pyrite, pyrolusite, and graphite is (2~4):(2~5):1, for example, it can be 2:2:1, 2:3:1, 3:2:1, 3:3:1, 3:4:1, 2:4:1, 2:5:1, 3:5:1, 4:5:1, etc. Adjusting the mass ratio of the three components to the above range helps to regulate the galvanic cell reaction system and optimize the oxidative degradation effect of xanthate-based organic compounds. The height of the galvanic cell filter layer is 50~70mm, for example, it can be 50mm, 60mm, or 70mm. Setting the height of the galvanic cell filter layer to the above range further assists in improving the oxidative degradation effect of xanthate-based organic compounds.

[0046] According to an embodiment of the present invention, operation S102 includes sub-operation S1021.

[0047] In sub-operation S1021, at a temperature of 20~50℃ (e.g., 20℃, 30℃, 40℃, or 50℃), the activated mineral processing wastewater is passed through the galvanic cell filter layer at a rate of 15~30 mL / min (e.g., 15 mL / min, 18 mL / min, 22 mL / min, 25 mL / min, or 30 mL / min), with an air flow rate of 3~5 L / min (e.g., 3 L / min, 4 L / min, or 5 L / min). Adjusting the parameters of the galvanic cell filter layer to the above range helps to ensure sufficient contact between the mineral processing wastewater and the materials and air in the galvanic cell filter layer, further promoting the full oxidative degradation of xanthate-based organic matter by reactive oxygen free radicals and / or ozone.

[0048] According to an embodiment of the present invention, operation S103 includes sub-operations S1031 to S1032.

[0049] In sub-operation S1031, with air introduced, the first solution is passed through a metal purification filter layer to obtain the second solution.

[0050] In sub-operation S1032, with air introduced, the second solution is passed through a controlled filter bed to obtain mineral processing return water.

[0051] According to an embodiment of the present invention, the metal purification filter layer includes pyrite and calcite. The interfacial catalysis of pyrite promotes the removal of metal ions from the first solution by precipitation. After passing through the galvanic cell filter layer, the first solution is in a slightly acidic state (pH around 5) due to the activation of oxygen into reactive oxygen free radicals. Under these acidic conditions, metal ions such as iron and copper ions are dispersed in a colloidal state in the first solution. The interfacial catalysis of pyrite helps to promote the precipitation of metal ions, especially iron ions, in the form of goethite. Goethite has an adsorption effect, which helps to adsorb other metal ions in the first solution. Calcite, also known as calcium carbonate, is alkaline. Adding calcite helps to adjust the pH of the first solution, which helps to promote the precipitation process of heavy metals, such as the formation of goethite. Through the interfacial catalysis of pyrite and the alkaline environment provided by calcite, metal ions in the first solution can be effectively removed from the solution in the form of precipitation, resulting in a relatively pure second solution.

[0052] Furthermore, passing the second solution through a controlled filter layer helps to purify the second solution, which in turn helps to remove any residual metal ions, reducing substances, or other suspended solids.

[0053] Please continue to refer to this. Figure 2 The inner diameter and material of the cylindrical channels in the metal purification filter layer and the control filter layer can be the same as those in the galvanic cell filter layer, as needed. The diaphragm arrangement can also be the same as in the galvanic cell filter layer. The air inlet channels in the metal purification filter layer and the control filter layer can be positioned similarly to those in the galvanic cell filter layer. This ensures sufficient contact between oxygen in the air and the natural ore, improving the treatment efficiency of mineral processing wastewater.

[0054] According to an embodiment of the present invention, the mass ratio of pyrite to calcite is (1~2):2, for example, it can be 1:2, 1.5:2 or 1:1. After mixing, the pyrite occupies between 1 / 3 and 1 / 2 of the entire metal purification filter layer. Adjusting the mass ratio of the two within the above range helps to synergistically promote the full precipitation of iron ions in the form of goethite. The height of the metal purification filter layer is 40~70mm, for example, it can be 40mm, 50mm, 60mm or 70mm. Setting the height of the metal purification filter layer within the above range further assists in improving the precipitation and removal effect of metal ions (especially iron ions).

[0055] According to an embodiment of the present invention, the controlled filter media layer comprises pyrolusite and calcite. Pyrolusite has good oxidation catalytic ability, which helps to remove residual metal ions and reducing substances in the second solution, further improving the purification effect of the second solution. Calcite helps to adjust the pH of the passed second solution to neutral, obtaining reusable mineral processing return water. Simultaneously, calcite can assist in improving the removal effect of metal ions and reducing substances. The mass ratio of pyrolusite to calcite is 2:(1~2), for example, it can be 1:1, 2:1.5, or 2:1. Adjusting the mass ratio within the above range helps to synergistically promote the sufficient removal of metal ions and reducing substances. The height of the controlled filter media layer is 40~60mm, for example, it can be 40mm, 50mm, or 60mm. Setting the height of the controlled filter media layer within the above range further assists in improving the removal effect of metal ions and reducing substances, so that the outflowing solution can be directly used 100% for mineral processing return water.

[0056] The particle size range of pyrite, calcite, and pyrolusite in the metal purification filter layer and the control filter layer includes 3~5mm, and the particle size of the above raw materials can be the same or different.

[0057] According to an embodiment of the present invention, the processing method further includes: oxidizing the first mixture by introducing air, and then adding 0.1% by mass of pyrite particles of the first mixture to obtain a second mixture;

[0058] The second mixture is added to the xanthate beneficiation wastewater for recycling; the recycling frequency is 1-10 times. By introducing air, the reduced metal ions and organic matter in the first mixture are oxidized. Adding 0.1% pyrite particles helps provide more active sites. Through multiple recycling cycles, the removal efficiency of various harmful substances from the xanthate beneficiation wastewater is improved. Recycling the second mixture reduces the consumption of pyrite particles and lowers treatment costs.

[0059] It should be noted that the pyrite in the galvanic cell filter layer, metal purification filter layer, and control filter layer contains more than 30% sulfur by mass, the pyrolusite contains more than 20% manganese by mass (to ensure good oxidizing properties), the graphite contains more than 60% fixed carbon by mass, and the calcite contains more than 80% calcium carbonate by mass. The particle size range of pyrite, calcite, and pyrolusite in the metal purification filter layer and control filter layer is 3~5mm, and the particle sizes of the above raw materials can be the same or different.

[0060] According to embodiments of the present invention, the concentration of xanthate organic matter in the xanthate beneficiation wastewater is 10-150 mg / L, for example, it can be 10 mg / L, 30 mg / L, 50 mg / L, 70 mg / L, 90 mg / L, 110 mg / L, 130 mg / L, or 150 mg / L. When the concentration of xanthate organic matter is within the above range, the above-mentioned galvanic cell filter layer, metal purification filter layer, and control filter layer have a good removal effect on xanthate organic matter, and xanthate organic matter can be degraded by 95-99.5%.

[0061] According to an embodiment of the present invention, the mineral processing wastewater activated by pyrite powder can pass slowly once or quickly multiple times through the galvanic cell filter layer of the natural ore as needed, and then through the metal purification filter layer and the control filter layer.

[0062] In one specific embodiment:

[0063] The xanthate beneficiation wastewater from the ore dressing plant is mixed with pyrite particles of 0-0.074 mm in a stirring device and then allowed to stand to obtain activated ore dressing wastewater.

[0064] The mineral processing wastewater activated by pyrite is passed through a pre-constructed mineral galvanic cell filter layer. During the process of the wastewater passing through the galvanic cell filter layer, air is introduced to help obtain the first solution after treatment by the galvanic cell filter material.

[0065] By passing the first solution through a metal purification filter layer constructed of pyrite and calcite, and then introducing air, a second solution treated with pyrite and calcite can be obtained.

[0066] By passing the second solution, after being treated with pyrite and calcite, through a controlled filter layer constructed of pyrolusite and calcite, and introducing air, well-treated return water for mineral processing can be obtained.

[0067] The treated recycled water from mineral processing was used to determine the xanthate components in the aqueous solution and was reused in the mineral processing process.

[0068] The first mixture of pyrite particles after static treatment and liquid slurry is activated by air injection, and after adding 0.1% new pyrite particles, it is mixed with xanthate beneficiation wastewater to achieve the reuse of pyrite.

[0069] The present invention will be further illustrated below through embodiments and related test experiments and results. In the following detailed description, numerous specific details are set forth for ease of explanation to provide a comprehensive understanding of the embodiments of the present invention. However, it will be apparent that one or more embodiments may be practiced without these specific details. Moreover, the details in the following embodiments can be arbitrarily combined to form other feasible embodiments without conflict.

[0070] It should be noted that the specific embodiments described below are merely illustrative examples, and the scope of protection of the present invention is not limited thereto. The chemicals and raw materials used in the following embodiments are all commercially available or prepared using recognized processing methods.

[0071] Example 1:

[0072] The process of constructing the galvanic cell filter layer: Prepare 40g of pyrite particles with a sulfur content exceeding 45% by mass and a diameter of 3-5mm; prepare 40g of pyrolusite with a manganese content of 25% by mass and a diameter of 3-5mm; prepare 10g of high-purity graphite in flake form with a diameter of 3-5mm. Mix the prepared materials together using a cone mixing method to obtain a mixed galvanic cell filter layer raw material. Add 10g of the mixed material to a 32mm diameter plastic pipe each time to act as a filter layer (the bottom of the filter layer is separated by a filter cloth). While adding the mixed mineral materials, vibrate appropriately. Add 90g of the mixed mineral materials in 9 portions to obtain a filter layer A1 of approximately 62mm.

[0073] Figure 3 The X-ray diffraction pattern of pyrite used in the filter layer of Embodiment 1 of the present invention is shown. Figure 3 The image shows that the pyrite contains relatively pure FeS2.

[0074] Construction process of pyrite and calcite filter media layer: Prepare 25g of pyrite particles with a sulfur content exceeding 45% by mass and a diameter of 3-5mm; prepare 45g of calcite particles with a calcium carbonate content exceeding 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone pile 5 times, add 10g of the mixed ore mixture into a 32mm diameter plastic pipe each time to act as a filter layer (the bottom of the filter layer is separated by a filter cloth). While adding the mixed ore, vibrate appropriately. Add 70g of the mixed mineral material in 7 portions to obtain a filter media layer B1 of approximately 48mm.

[0075] Construction process of pyrolusite and calcite filter media: Prepare 45g of pyrolusite with a manganese content of 25% by mass and a diameter of 3-5mm; prepare 25g of calcite with a calcium carbonate content of over 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone pile 5 times, add 10g of the mixed ore mixture into a 32mm diameter plastic pipe each time to act as a filter layer (the bottom of the filter layer is separated by a filter cloth). While adding the mixed ore, vibrate appropriately. Add 70g of the mixed mineral material in 7 portions to obtain a filter media layer C1 of approximately 50mm.

[0076] Prepare 600 mL of a solution containing 100 mg / L sodium ethyl xanthate (hereinafter referred to as ethyl xanthate). At 20–25 °C, add 6 g of pyrite particles with a sulfur content exceeding 45% and a diameter of 0–0.074 mm to the solution and stir for 10 min, then let it stand for 10 min. Maintaining the above temperature, pass the activated supernatant through the galvanic cell filter layer A1 at a rate of 20 mL / min, while simultaneously introducing air at a rate of approximately 3.6 L / min, to obtain the galvanic cell-treated solution. Figure 4a The electron microscope image and distribution map of pyrite in the filter layer of the galvanic cell of Embodiment 1 of the present invention are shown before use. Figure 4b The image shows a surface scanning electron microscope (SEM) image and a distribution map (total spectral density) of pyrite in the galvanic cell filter layer of Embodiment 1 of the present invention after use. (See also:) Figures 4a-4b As shown, the surface structure of pyrite exhibits significant changes, indicating the adsorption of some impurities from the mineral processing wastewater. Comparison of the distribution spectrum reveals a higher oxygen content on the pyrite surface, suggesting that pyrite not only adjusts the pH of the wastewater but also assists in the formation of reactive oxygen species and / or ozone, promoting the oxidative degradation of xanthate-like organic compounds.

[0077] The solution treated by the galvanic cell was passed through a pyrite and calcite filter layer B1 at a rate of 22 mL / min, while air was introduced at a rate of approximately 3 L / min, to obtain a solution treated with pyrite and calcite. This pyrite and calcite solution was then passed through a pyrolusite and calcite filter layer C1 at a rate of 18 mL / min, while air was introduced at a rate of approximately 3 L / min, to obtain a treated mineral processing liquid for reuse. Measurement of the xanthate content in the solution showed that the ethyl xanthate content had been degraded by 95.17%.

[0078] Example 2:

[0079] The process of constructing the galvanic cell filter layer: Prepare 30g of pyrite particles (3-5mm) with a sulfur content exceeding 45% by mass; prepare 50g of pyrolusite (3-5mm) with a manganese content of 25% by mass; and prepare 10g of high-purity graphite (3-5mm) in flake form. Mix the prepared ores using a cone mixing method five times to obtain the mixed galvanic cell filter layer raw material. Add 10g of the mixed material to a 32mm diameter plastic pipe to act as the filter layer (the bottom of the filter layer is separated by a filter cloth). While adding the mixed mineral material, vibrate appropriately. Add 90g of the mixed mineral material in 10 portions to obtain a filter layer A2 of approximately 65mm.

[0080] Construction process of pyrite and calcite filter media layer: Prepare 40g of pyrite particles with a sulfur content exceeding 30% by mass and a diameter of 3-5mm; prepare 40g of calcite particles with a calcium carbonate content exceeding 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone pile 5 times, add 10g of the mixture into a 32mm diameter plastic pipe each time to serve as the filter layer (the bottom of the filter layer is separated by filter cloth). While adding the mixed ore, vibrate appropriately. Add 80g of the mixed ore in 8 portions to obtain a filter media layer B2 of approximately 59mm.

[0081] Conditions for constructing the pyrolusite and calcite filter media layer: Prepare 50g of pyrolusite with a manganese content of 22% by mass and a diameter of 3-5mm; prepare 30g of calcite with a calcium carbonate content of over 80% and a diameter of 3-5mm. After mixing the two ores in a cone pile 5 times, add 10g of the mixture into a 32mm diameter plastic pipe each time to serve as the filter layer (the bottom of the filter layer is separated by a filter cloth). While adding the mixed ore, vibrate appropriately. Add 80g of the mixed ore in 8 portions to obtain a filter media layer C2 of approximately 58mm.

[0082] After grinding pyrite with a sulfur content exceeding 30%, the grinding fineness is controlled at 78.12%, and the flotation pulp concentration is approximately 35%. 300 g / t of water glass modifier is added. Flotation is carried out using an open-circuit flotation process: one coarse flotation stage (20 g / t of sodium ethyl xanthate + 80 g / t of sodium butyl xanthate + 15 g / t of No. 2 oil) + one scavenging stage ((10 g / t of sodium ethyl xanthate + 40 g / t of sodium butyl xanthate + 10 g / t of No. 2 oil)) + one cleaner flotation stage. The flotation concentrate, middlings, and tailings are filtered to obtain xanthate-containing wastewater, which, upon measurement, contains a xanthate content of approximately 72.27 mg / L.

[0083] At 20-25℃, 600 mL of a xanthate solution with a content of approximately 72.27 mg / L was mixed with 12 g of pyrite particles (0-0.074 mm) containing more than 45% sulfur and stirred for 10 min, then allowed to stand for 10 min. Maintaining the above temperature, the activated supernatant solution was passed through a galvanic cell filter layer A2 at a rate of 20 mL / min, with an air flow rate of approximately 4 L / min to obtain the galvanic cell-treated solution. The galvanic cell-treated solution was then passed through a pyrite and calcite filter layer B2 at a rate of 20 mL / min, with an air flow rate of approximately 3.6 L / min to obtain the pyrite and calcite-treated solution. The pyrite and calcite-treated solution was then passed through a pyrolusite and calcite filter layer C2 at a rate of 18 mL / min, with an air flow rate of approximately 3 L / min to obtain the treated mineral processing liquid. Measurement of the xanthate content in the solution showed that the xanthate-related organic matter content had been degraded by 97.24%.

[0084] Example 3:

[0085] The process of constructing the galvanic cell filter layer: Prepare 30g of pyrite particles (3-5mm) with a sulfur content exceeding 45% by mass; prepare 60g of pyrolusite (3-5mm) with a manganese content of 25% by mass; and prepare 15g of high-purity graphite (3-5mm) in flake form. Mix the prepared ores using a cone mixing method five times, weighing 90g of the mixture to obtain the mixed galvanic cell filter layer raw material. Add 10g of the mixture to a 32mm diameter plastic pipe to act as the filter layer (the bottom of the filter layer is separated by a filter cloth). Vibrate appropriately while adding the mixed mineral material. Add the 90g mixed mineral material in nine batches to obtain a filter layer A3 of approximately 68mm.

[0086] Construction process of pyrite and calcite filter media layer: Prepare 30g of pyrite particles with a sulfur content exceeding 45% by mass and a diameter of 3-5mm; prepare 50g of calcite particles with a calcium carbonate content exceeding 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone pile 5 times, add 10g of the mixture into a 32mm diameter plastic pipe each time to serve as the filter layer (the bottom of the filter layer is separated by filter cloth). While adding the mixed ore, vibrate appropriately. Add 80g of the mixed ore in 8 portions to obtain a filter media layer B3 of approximately 63mm.

[0087] Construction process of pyrolusite and calcite filter media: Prepare 40g of pyrolusite with a manganese content of 25% by mass and a diameter of 3-5mm; prepare 40g of calcite with a calcium carbonate content of over 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone pile 5 times, add 10g of the mixture into a 32mm diameter plastic pipe each time to act as a filter layer (the bottom of the filter layer is separated by a filter cloth). While adding the mixed ore, vibrate appropriately. Add 80g of the mixed ore in 8 portions to obtain a filter media layer C3 of approximately 52mm.

[0088] The waste liquor from the beneficiation of gold-bearing pyrite (under normal operating conditions) was measured to contain 38.7 mg / L xanthate. 2000 ml of this waste liquor was mixed with 20 g of pyrite at 20-25°C for 15 min and allowed to stand for 10 min. Maintaining the above temperature, the activated supernatant solution was passed through a galvanic cell filter layer A3 at a rate of 15 mL / min, with an air flow rate of approximately 3 L / min, to obtain the galvanic cell-treated solution. The galvanic cell-treated solution was then passed through a pyrite and calcite filter layer B3 at a rate of 20 mL / min, with an air flow rate of approximately 4 L / min, to obtain a pyrite and calcite-treated solution. Finally, the pyrite and calcite-treated solution was passed through a pyrolusite and calcite filter layer C3 at a rate of 16 mL / min, with an air flow rate of approximately 3 L / min, to obtain approximately 1928 ml of treated liquid. The content of xanthate in the solution was measured, and it was found that 99.27% ​​of the xanthate had been degraded.

[0089] Figure 5 The bar charts showing the removal effects of xanthate-based organic matter in Examples 1-3 of the present invention are illustrated. Figure 5 As shown, the filter layer constructed by this invention can achieve sufficient degradation of xanthate.

[0090] The treated liquid from Example 3 was divided into 900mL portions of Liquid 1 and 900mL portions of Liquid 2 for parallel experiments. Liquid 1 and Liquid 2 had no difference in composition, but were distinguished by different names for ease of subsequent experiments. Untreated wastewater, tap water, Liquid 1, and Liquid 2 were added to the grinding and flotation processes of the gold mine as recycled water for mineral processing (specific process parameters are as follows: grinding concentration 65%, grinding fineness 72.6%, flotation process involving one roughing and one scavenging followed by a mixed concentrate followed by a final cleaning, xanthate dosage 60+25g / t, No. 2 oil dosage 20g / t). Figure 6 The bar charts shown illustrate the gold ore recovery effects of Example 3 of the present invention using untreated wastewater, tap water, and liquid 1 and liquid 2 obtained after treatment in Example 3, respectively. Figure 6 As shown, the gold recovery rates in the ore reached 92.24%, 91.96%, and 92.27%, indicating that the liquid treated by the multiple filter layers of this invention can be reused as mineral processing wastewater, thereby avoiding the waste of water resources.

[0091] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for treating xanthate beneficiation wastewater using natural ore, comprising: Pyrite powder is added to the xanthate-based mineral processing wastewater for activation treatment, so that the xanthate groups are converted into bixanthate groups, and the activated mineral processing wastewater is obtained. With air introduced, the activated mineral processing wastewater is passed through the galvanic cell filter layer to obtain the first solution; The first solution is passed sequentially through a metal purification filter layer and a control filter layer to obtain mineral processing return water; The filter layer of the galvanic cell includes pyrite, pyrolusite and graphite. Through the coupling effect of pyrite and pyrolusite, pyrite is used as the anode and pyrolusite as the cathode. The electrochemical process is constructed by utilizing the conductivity of graphite to activate oxygen in the air into reactive oxygen free radicals and / or ozone, so that the reactive oxygen free radicals and / or ozone oxidize and degrade xanthate organic matter in the mineral processing wastewater. The galvanic cell filter layer is prepared through the following process: Mix pyrite, pyrolusite and graphite evenly and fill them into a cylindrical pipe with a diaphragm at the bottom. The particle size range of pyrite, pyrolusite, and graphite is 3-5 mm. The mass ratio of pyrite, pyrolusite, and graphite is (2~4):(2~5):1; the process of passing the activated mineral processing wastewater through the galvanic cell filter layer to obtain the treated first solution includes: passing the activated mineral processing wastewater through the galvanic cell filter layer at a rate of 15~30 mL / min at 20~50℃; the air flow rate is 3~5 L / min.

2. The processing method according to claim 1, wherein, The height of the filter material layer of the galvanic cell is 50~70mm.

3. The processing method according to claim 1, wherein, The first solution is passed sequentially through a metal purification filter layer and a control filter layer to obtain mineral processing return water, comprising: With air introduced, the first solution is passed through a metal purification filter layer to obtain the second solution; With air introduced, the second solution is passed through the controlled filter media layer to obtain mineral processing return water; The metal purification filter layer includes pyrite and calcite, and the metal ions in the first solution are removed by precipitation through interfacial catalysis of pyrite.

4. The processing method according to claim 3, wherein, The mass ratio of pyrite to calcite is (1~2):2; The height of the metal purification filter layer is 40~70mm.

5. The processing method according to claim 3, wherein, The controlled filter media layer includes pyrolusite and calcite; The mass ratio of pyrolusite to calcite is 2:(1~2); the height of the filter media layer is 40~60mm.

6. The processing method according to claim 1, wherein, The step of adding pyrite powder to the xanthate-based mineral processing wastewater for activation treatment, thereby converting the xanthate groups into bixanthate groups, yields activated mineral processing wastewater comprising: At 20~50℃, pyrite powder with a particle size of 0.001~0.074mm is added to the xanthate beneficiation wastewater and stirred for 5~10min, then allowed to stand for 10~20min to obtain the upper layer of activated beneficiation wastewater and the lower layer of the first mixture. The amount of pyrite powder added is 1-2% of the weight of xanthate beneficiation wastewater, the stirring is air-filled stirring, the first mixture includes pyrite particles and mixed slurry, and the sulfur content of the pyrite powder is greater than 45% by mass.

7. The processing method according to claim 6, wherein, After oxidizing the first mixture by introducing air, 0.1% by mass of pyrite particles of the first mixture are added to obtain the second mixture; The second mixture is added to the xanthate beneficiation wastewater for recycling. The number of times the cycle is used is 1 to 10.

8. The method according to claim 1, wherein, The concentration of xanthate organic matter in the xanthate beneficiation wastewater is 10~150 mg / L.

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