Method for treating xanthate beneficiation wastewater by using natural ore

Abstract

The invention provides a method for treating xanthate beneficiation wastewater by using natural ore, and belongs to the technical field of water treatment. The treatment method comprises the following steps: adding pyrite powder into xanthate beneficiation wastewater for activating treatment, so that xanthate groups are converted into dixanthate groups, and activated beneficiation wastewater is obtained; under the condition that air is introduced, enabling the activated beneficiation wastewater to pass through a primary battery filter material layer to obtain a first solution; the first solution sequentially passes through a metal purification filter material layer and a control filter material layer, and backwater for mineral separation is obtained; wherein the primary battery filter material layer comprises pyrite, pyrolusite and graphite, and oxygen in the air is activated into active oxygen free radicals and / or ozone through the coupling effect of the pyrite and the pyrolusite, so that the active oxygen free radicals and / or the ozone oxidize and degrade xanthate organic matters in the beneficiation wastewater.

Description

Technical Field

[0001] The invention relates to the technical field of water treatment, in particular to the technical field of water treatment in the process of mine development, and in particular to a method for treating xanthate ore dressing wastewater by using natural ore. Background Art

[0002] Mining resource development is the foundation of industrial development. In the process of mining resource development, many ores need to be processed to obtain concentrate products for smelting. Flotation is one of the main methods of mineral processing. In the flotation process of ore, especially the flotation process of non-ferrous metal sulfide ores, xanthate reagents are widely used as collectors for target minerals in mineral processing. Xanthate is also called xanthate. The mineral processing wastewater after flotation of non-ferrous metal sulfide ores has the characteristics of a large amount of xanthate organic matter, high heavy metal content, and strong bubble properties.

[0003] In xanthate-type ore dressing wastewater, the presence of xanthate-type organic matter causes the chemical oxygen demand (COD) to exceed the standard. Xanthate-type organic matter easily forms water-insoluble chelates with metal ions, causing heavy metals to accumulate and cause water pollution. Xanthate-type organic matter has a foul odor. Even if the amount is small, it can easily cause the water to stink and affect the ecological balance of the water body.

[0004] At present, the commonly used treatment methods for mineral processing wastewater are chemical precipitation, oxidation, precipitation-oxidation combined method, acidification, and ion exchange adsorption. However, in practical applications, the above methods have the disadvantages of high treatment cost, long treatment time, easy to cause secondary pollution to the environment, and complex treatment process. Summary of the invention

[0005] In view of this, in order to at least partially solve at least one of the above-mentioned technical problems, the present invention provides a method for treating xanthate ore dressing wastewater using natural ore.

[0006] According to an embodiment of one aspect of the present invention, there is provided a method for treating xanthate-based mineral processing wastewater using natural ore, comprising: adding pyrite powder to the xanthate-based mineral processing wastewater for activation treatment, so that the xanthate group is converted into a dixanthate group, and activated mineral processing wastewater is obtained; in the case of introducing air, the activated mineral processing wastewater is passed through a galvanic filter layer to obtain a first solution; the first solution is sequentially passed through a metal purification filter layer and a control filter layer to obtain return water for mineral processing; wherein the galvanic filter layer comprises pyrite, pyrolusite and graphite, and oxygen in the air is activated into active oxygen free radicals and / or ozone through the coupling effect of pyrite and pyrolusite, so that the active oxygen free radicals and / or ozone oxidatively degrade the xanthate-based organic matter in the mineral processing wastewater.

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

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

[0009] According to an embodiment of the present invention, the activated mineral processing wastewater is passed through the galvanic cell filter layer to obtain the treated first solution, which 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 the air intake is 3-5 L / min.

[0010] According to an embodiment of the present invention, the first solution is passed through a metal purification filter layer and a control filter layer in sequence to obtain return water for mineral processing, including: under the condition of passing air, the first solution is passed through the metal purification filter layer to obtain a second solution; under the condition of passing air, the second solution is passed through the control filter layer to obtain return water for mineral processing; wherein the metal purification filter layer includes pyrite and calcite, and the metal ions in the first solution are removed by precipitation through the interface catalysis of pyrite.

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

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

[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 group is converted into a dixanthate group, and the activated mineral processing wastewater is obtained, including: at 20-50°C, pyrite powder with a particle size of 0.001-0.074 mm is added to the xanthate-based mineral processing wastewater and stirred for 5-10 minutes, and then allowed to stand for 10-20 minutes to obtain an upper layer of activated mineral processing wastewater and a first mixture of a lower layer; the amount of pyrite powder added is 1-2% of the weight of the xanthate-based mineral processing wastewater, 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%.

[0014] According to an embodiment of the present invention, after the first mixture is filled with air for oxidation, 0.1% of the mass of pyrite particles of the first mixture are added to obtain a second mixture; the second mixture is added to xanthate-based mineral processing wastewater for recycling; wherein the number of recycling times is 1 to 10 times.

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

[0016] According to an embodiment of the present invention, pyrite powder is added to xanthate-type ore dressing wastewater, pyrite can interact with oxygen in the air, generate a relatively large number of free radicals in situ, and the free radicals have strong oxidizing properties, converting the xanthate group into a dixanthate group that is more easily oxidized and degraded, thereby promoting the formation of the dixanthate group, which is convenient for degradation and removal in subsequent processing steps. By assembling pyrite and pyrolusite into a primary battery filter material layer of natural ore, wherein pyrite has redox properties, pyrolusite has oxidizing properties, and graphite is used as a conductive medium, under the condition of air passing, oxygen in the air participates in the reaction of the primary battery filter material layer, pyrite is oxidized to release electrons, which are transferred to pyrolusite through the graphite conductive medium, so that oxygen receives electrons and is activated to become active oxygen free radicals and / or ozone, and further, active oxygen free radicals and / or ozone act on xanthate-type organic matter to oxidize and degrade it. Then the first solution is passed through a metal purification filter layer and a control filter layer to remove metal ions and other impurities in the first solution to obtain mineral processing return water, thereby realizing the reuse of mineral processing wastewater.

[0017] The treatment method of the present invention is simple and easy to implement. Due to the use of natural ore, the cost is low and the efficiency is high. The return water for mineral processing obtained by the treatment method can be 100% recycled, which is helpful for promotion in the field of non-ferrous metal mineral processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 A flow chart showing a method for treating xanthate-based ore dressing wastewater using natural ore according to an embodiment of the present invention is shown;

[0019] Figure 2 The process flow chart of the method for treating xanthate-type ore dressing wastewater using natural ore according to an embodiment of the present invention is shown;

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

[0021] Figure 4a The electron microscope image and the total number spectrum of the distribution map of the pyrite of the original battery filter material layer of Example 1 of the present invention before use are shown;

[0022] Figure 4bThe electron microscope image and the total number spectrum of the distribution map of the pyrite of the original battery filter material layer of Example 1 of the present invention after use are shown;

[0023] Figure 5 A bar chart showing the removal effect of xanthate organic matter in Examples 1 to 3 of the present invention respectively; and

[0024] Figure 6 A bar chart showing the gold recovery effect 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. DETAILED DESCRIPTION

[0025] Below, 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 present invention. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of embodiments of the present invention. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion of concepts of the present invention.

[0026] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The term "comprising" used herein indicates the existence of features, steps, operations, but does not exclude the existence or addition of one or more other features.

[0027] In the case of using expressions such as "at least one of A, B, and C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, or C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0028] In the present invention, "xanthate organic matter" can be understood as alkyl xanthate, for example, sodium ethyl xanthate, potassium ethyl xanthate, sodium butyl xanthate, potassium butyl xanthate, and the like.

[0029] In the flotation process of ore, especially the flotation process of non-ferrous metal sulfide ore, xanthate organic matter is widely used as a collector of the target mineral in the ore dressing, so that the ore dressing wastewater after the flotation of non-ferrous metal sulfide ore has a large amount, high heavy metal content and high xanthate organic matter content. One method in the related technology is to use activated carbon adsorption to treat the ore dressing wastewater, but the treatment cost is high, and the wastewater after activated carbon adsorption is still difficult to meet the discharge standard.

[0030] In the process of realizing the concept of the present invention, it is found that by utilizing pyrite to react with xanthate groups, it is converted into dixanthate groups, thereby enhancing the subsequent oxidative degradation. By using pyrite, pyrolusite and graphite to assemble a primary battery filter material layer, the redox property of pyrite can be used as an anode, and the oxidizing property of pyrolusite can be used as a cathode, when the ore dressing wastewater flows through the primary battery filter material layer, an electrochemical system is constructed under the condition of air being introduced, and the oxygen in the air is activated into active oxygen free radicals and / or ozone, and the active oxygen free radicals and / or ozone oxidatively degrade the xanthate organic matter in the ore dressing wastewater.

[0031] Specifically, according to an embodiment of one aspect of the present invention, a method for treating xanthate-based ore dressing wastewater using natural ore is provided. Figure 1 The flowchart of the method for treating xanthate ore dressing wastewater using natural ore according to the embodiment of the present invention is shown. Figure 2 The process flow chart of the method for treating xanthate-type ore dressing wastewater using natural ore according to the embodiment of the present invention is shown. Figure 1 and Figure 2 As shown, operations S101 to S103 are included.

[0032] In operation S101, pyrite powder is added to xanthate-based ore dressing wastewater for activation treatment, so that the xanthate groups are converted into dixanthate groups, thereby obtaining activated ore dressing wastewater.

[0033] In the related art, the pH is usually adjusted to below 4 by adding acid, and hydrogen peroxide is added to oxidatively degrade xanthate organic matter. In the present invention, pyrite powder (FeS2) is added to the xanthate ore dressing wastewater. The pyrite powder interacts with the xanthate organic matter to convert the xanthate group into a dixanthate group that is more easily degraded, and at the same time, the sulfide ions in the pyrite are converted into sulfate ions. The addition of pyrite powder helps to adjust the pH of the xanthate ore dressing wastewater to about 5, making it easier for the xanthate group to react with pyrite to form a dixanthate group, and thus the xanthate organic matter is more easily oxidized and degraded.

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

[0035] According to an embodiment of the present invention, natural ores have environmental properties such as mineral surface effect, mineral redox effect, and mineral channel effect. Natural ores have the function of environmental purification, but there are many types. The present invention uses pyrite, pyrolusite and graphite to form a primary battery filter layer, utilizes the redox property of pyrite, the oxidizability and catalyticity of pyrolusite and the conductivity of graphite, and constructs an electrochemical process when air is introduced. In the constructed electrochemical process, pyrite is oxidized to release electrons, and oxygen accepts these electrons and is reduced to active oxygen free radicals (for example, hydroxyl free radicals OH) and / or ozone. Active oxygen free radicals and / or ozone have strong oxidizability and high reactivity, and can oxidize and degrade xanthate organic matter in mineral processing wastewater.

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

[0037] According to an embodiment of the present invention, the first solution passes through a metal purification filter layer to remove heavy metals in the first solution, and then the filter layer is controlled to help remove reducing impurities, etc., so that the obtained mineral processing return water meets the water quality standards for reuse.

[0038] According to an embodiment of the present invention, oxygen in the air is activated into active oxygen free radicals and / or ozone through the coupling effect of pyrite and pyrolusite, so that the active oxygen free radicals and / or ozone can oxidize and degrade xanthate organic matter in the ore dressing wastewater. The present invention utilizes the redox characteristics of pyrite, the oxidation catalytic characteristics of pyrolusite, the conductivity and adsorption of graphite, and forms a primary battery chemical reaction in the interface area between the three materials, so that pyrite, oxygen in the air, and water are combined, and under the oxidation catalytic effect of pyrolusite, oxygen is activated into active oxygen free radicals and / or ozone, thereby achieving oxidation and degradation of xanthate organic matter in xanthate ore dressing wastewater. The first solution obtained can be used as 100% as non-ferrous metal sulfide ore dressing return water after passing through the metal purification filter layer and the control filter layer in turn. Since natural ore is used as the raw material of the filter layer, the cost is low and the processing efficiency is high, which is conducive to industrial promotion in the field of ore dressing.

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

[0040] In sub-operation S1011, pyrite powder with a particle size of 0.001-0.074 mm is added to the xanthate ore dressing wastewater at 20-50°C.

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

[0042] According to an embodiment of the present invention, pyrite powder has a strong adsorption capacity and can adsorb organic pollutants in xanthate-type ore dressing wastewater. The particle size of pyrite powder is adjusted between 0.001 and 0.074 mm, which helps to increase the contact area with xanthate-type ore dressing wastewater and improve the reaction efficiency. In the above-mentioned temperature range of 20 to 50 ° C, for example, it can be 20 ° C, 30 ° C, 40 ° C or 50 ° C, the chemical reaction activity between pyrite powder and xanthate-type 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-type ore dressing wastewater, which helps to promote the conversion of xanthate groups to dixanthate groups. Stirring can be performed, for example, by solution stirring or air stirring. Stirring is adjusted within the above range so that pyrite powder can be fully mixed with xanthate-type organic matter, and the side reaction will not occur for too long. Standing for 10 to 20 minutes helps to settle the unreacted pyrite powder and the pyrite particles adsorbed with organic pollutants to the bottom of the container to form a first mixture. The first mixture includes pyrite particles and mixed slurry, and the upper layer of the container is activated mineral processing wastewater, and the water quality of the mineral processing wastewater has been improved to a certain extent. The amount of pyrite powder added is 1-2% of the weight of the xanthate mineral processing wastewater, for example, it can be 1%, 1.5% or 2%. The pyrite powder in the above range helps to fully contact and react with xanthate organic matter, and at the same time provides sufficient adsorption sites to improve the treatment efficiency of xanthate organic matter. The sulfur content of the pyrite powder is greater than 45%. The sulfur content within the above range helps to provide sufficient sulfur ions to interact with xanthate organic matter, further improving the removal effect of xanthate organic matter.

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

[0044] Pyrite, pyrolusite and graphite are mixed evenly and filled into a cylindrical pipe with a diaphragm wrapped at the bottom. The inner diameter of the cylindrical channel is 30-34 mm, for example, 30 mm, 32 mm or 34 mm, preferably 32 mm. The material of the cylindrical channel includes plastic. The diaphragm can be, for example, a filter cloth. A channel for introducing air can be set as needed at 5 mm from the bottom diaphragm of the cylindrical pipe. The particle size ranges of pyrite, pyrolusite and graphite include 3-5 mm respectively. Setting the particle size of the three materials in the above range and adjusting the cylindrical channel as described above helps to fully contact the mineral processing wastewater while allowing the mineral processing wastewater to pass smoothly through the primary battery filter material 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 to the above range helps to regulate the three to construct a primary battery reaction system and optimize the oxidation degradation effect of xanthate organic matter. The height of the primary battery filter layer is 50-70 mm, for example, it can be 50 mm, 60 mm or 70 mm. Setting the height of the primary battery filter layer to the above range further helps to improve the oxidation degradation effect of xanthate organic matter.

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

[0047] In sub-operation S1021, at 20-50°C, for example, 20°C, 30°C, 40°C or 50°C, the activated mineral processing wastewater is passed through the galvanic filter material layer at a rate of 15-30mL / min, for example, 15mL / min, 18mL / min, 22mL / min, 25mL / min or 30mL / min, and the air intake is 3-5L / min, for example, 3L / min, 4L / min or 5L / min. Adjusting the parameters of the galvanic filter material layer to the above range helps to promote the mineral processing wastewater to fully contact with the materials and air in the galvanic filter material layer, and further promotes the active oxygen free radicals and / or ozone to fully oxidize and degrade xanthate organic matter.

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

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

[0050] In sub-operation S1032, the second solution is passed through a control filter material layer while air is introduced to obtain return water for mineral processing.

[0051] According to an embodiment of the present invention, the metal purification filter layer includes pyrite and calcite, and the metal ions in the first solution are removed by precipitation through the interfacial catalysis of pyrite. The first solution that passes through the primary battery filter layer is in a slightly acidic condition (pH of about 5) because oxygen is activated into active oxygen free radicals. Under such acidic conditions, metal ions such as iron ions and copper ions are dispersed in the first solution in a colloidal state, and the interfacial catalysis of pyrite helps to promote the metal ions in the first solution, especially the iron ions, to precipitate in the form of goethite. Goethite has an adsorption effect and helps to adsorb other metal ions in the first solution. Calcite, that is, calcium carbonate, is alkaline, and the addition of calcite helps to assist in adjusting the pH value of the first solution and helps to promote the process of heavy metal precipitation, such as the generation of goethite. Through the interfacial catalysis of pyrite and the alkaline environment provided by calcite, the metal ions in the first solution can be effectively removed from the solution in the form of precipitation. A relatively pure second solution is obtained.

[0052] Furthermore, the second solution is passed through the control filter layer to purify the second solution, which helps to remove metal ions, reducing substances or other suspended matter that may remain therein.

[0053] Please refer to Figure 2 The inner diameter range and material of the cylindrical channel of the metal purification filter layer and the control filter layer can be the same as those of the original battery filter layer as required, and the setting of the diaphragm can also be the same as that of the original battery filter layer. The position of the air inlet channel set in the metal purification filter layer and the control filter layer can be the same as that of the original battery filter layer. This allows the oxygen in the air to fully contact the natural ore, thereby improving the treatment efficiency of the 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, 1:2, 1.5:2 or 1:1. After the two are mixed, pyrite occupies between 1 / 3 and 1 / 2 of the entire metal purification filter material 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 material layer is 40-70 mm, for example, 40 mm, 50 mm, 60 mm or 70 mm. Setting the height of the metal purification filter material layer to the above range further helps to improve the precipitation of metal ions (especially iron ions) and the removal effect.

[0055] According to an embodiment of the present invention, the control filter layer includes pyrolusite and calcite. Pyrolusite has good oxidation catalytic ability, which helps to remove the 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 second solution to neutrality, and obtains the reused mineral processing return water. At the same time, calcite can help improve the removal effect of metal ions and reducing substances; the mass ratio of pyrolusite and calcite is 2: (1~2), for example, it can be 1: 1, 2: 1.5 or 2: 1, and adjusting the mass ratio of the two within the above range helps to synergistically promote the full removal of metal ions and reducing substances. The height of the control filter layer is 40~60mm, for example, it can be 40mm, 50mm or 60mm. The height of the control filter layer is set to the above range, which further helps to improve the removal effect of metal ions and reducing substances, so that the outflowing solution can be directly used for mineral processing return water 100%.

[0056] The particle sizes of pyrite, calcite and pyrolusite in the metal purification filter material layer and the control filter material layer respectively range from 3 to 5 mm, and the particle sizes of the above raw materials can be the same or different.

[0057] According to an embodiment of the present invention, the treatment method further comprises: after charging air into the first mixture for oxidation, adding pyrite particles of 0.1% of the mass of the first mixture to obtain a second mixture;

[0058] The second mixture is added to the xanthate ore dressing wastewater for recycling; the number of recycling times is 1 to 10 times. By filling with air, the reduced metal ions, organic matter, etc. in the first mixture are oxidized, and then 0.1% of pyrite particles are added, which helps to provide more active sites. Through multiple recycling, it helps to improve the removal effect of various harmful substances in the xanthate ore dressing wastewater. By recycling the second mixture, the consumption of pyrite particles is reduced and the processing cost is reduced.

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

[0060] According to an embodiment of the present invention, the concentration of xanthate organic matter in xanthate ore dressing 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, etc. When the concentration of xanthate organic matter is within the above range, the above-mentioned primary battery filter material layer, metal purification filter material layer and control filter material layer have a good removal effect on xanthate organic matter, and the xanthate organic matter can be degraded by 95-99.5%.

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

[0062] In one specific embodiment:

[0063] The xanthate 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 for treatment to obtain activated ore dressing wastewater.

[0064] The pyrite-activated ore dressing wastewater is passed through a constructed mineral galvanic cell filter layer. In the process of the ore dressing wastewater passing through the galvanic cell filter layer, air is added to assist in obtaining a first solution treated with the galvanic cell filter material.

[0065] The first solution is passed through a metal purification filter layer constructed of pyrite and calcite, and air is introduced to obtain a second solution treated with pyrite and calcite.

[0066] The second solution after the treatment of pyrite and calcite is passed through a control filter layer constructed of pyrolusite and calcite, and air is introduced to obtain treated return water for mineral processing.

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

[0068] The first mixture of the pyrite particles after static treatment and the liquid mixed slurry is filled with air for activation, and after adding 0.1% of new pyrite particles, it is mixed with xanthate mineral processing wastewater to achieve the reuse of pyrite.

[0069] The present invention is further described below by embodiments and related test experiments and results thereof. In the detailed description below, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present invention. However, it is obvious that one or more embodiments may also be implemented without these specific details. And, in the absence of conflict, the details in the following embodiments may be combined into other feasible embodiments at will.

[0070] It should be noted that the following specific examples are only for illustration, and the protection scope of the present invention is not limited thereto. The chemicals and raw materials used in the following examples are all commercially available or homemade by recognized processing methods.

[0071] Embodiment 1:

[0072] The process of building the original battery filter layer: prepare 40g of pyrite particles with a sulfur content of more than 45% and a size of 3-5mm; prepare 40g of pyrolusite with a manganese content of 25% and a size of 3-5mm; prepare 10g of high-purity graphite with a flaky shape and a size of 3-5mm. Mix the prepared materials and mix them 5 times using the ore cone mixing method to obtain a mixed raw material for the original battery filter layer. Put 10g of the raw material for the original battery filter layer into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed mineral material, and add 90g of the mixed mineral material in 9 times to obtain a filter layer A1 of about 62mm.

[0073] Figure 3 FIG. 1 shows an X-ray diffraction spectrum of pyrite used in the filter material layer of Example 1 of the present invention. Figure 3 As shown, it can be seen that the pyrite contains relatively pure FeS2.

[0074] The process of building the pyrite and calcite filter layer: prepare 25g of pyrite particles with a sulfur content of more than 45% and a size of 3-5mm; prepare 45g of calcite with a calcium carbonate content of more than 80% and a size of 3-5mm. After mixing the two ores in a cone for 5 times, add 10g of the mixed ore each time into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed ore, and add 70g of the mixed mineral material in 7 times to obtain a filter layer B1 of about 48mm.

[0075] The process of building the pyrolusite and calcite filter layer: 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 more than 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone for 5 times, add 10g of the mixed ore each time into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed ore, and add 70g of the mixed mineral material in 7 times to obtain a filter layer C1 of about 50mm.

[0076] Prepare 600mL of a solution containing 100mg / L of sodium ethyl xanthate (abbreviated as ethyl xanthate), add 6g of pyrite particles with a sulfur content of more than 45% and a size of 0-0.074mm to the solution at 20-25°C, stir for 10min, and let stand for 10min. Maintain the above temperature, pass the activated supernatant through the original battery filter layer A1 at a rate of 20mL / min, and at the same time, the air intake is about 3.6L / min, to obtain a solution after the original battery treatment. Figure 4a The surface scanning electron microscope image and the total distribution spectrum of the pyrite of the original battery filter material layer of Example 1 of the present invention before use are shown. Figure 4b The electron microscope image and the total number spectrum of the distribution map of the pyrite in the original battery filter material layer of Example 1 of the present invention after use are shown. Figure 4a~Figure 4b As shown, it can be seen that the structure of the pyrite surface has changed greatly, and some impurities in the ore dressing wastewater have been adsorbed. Comparing the distribution spectrum, it can be seen that the oxygen content on the pyrite surface has increased, indicating that pyrite can not only adjust the pH of the ore dressing wastewater, but also assist oxygen in forming active oxygen free radicals and / or ozone, promoting the oxidative degradation of xanthate organic matter.

[0077] The solution treated with the primary battery was passed through the pyrite and calcite filter material layer B1 at a rate of 22 mL / min, and the air flow rate was about 3 L / min, to obtain the solution treated with pyrite and calcite. The solution treated with pyrite and calcite was passed through the pyrolusite and calcite filter material layer C1 at a rate of 18 mL / min, and the air flow rate was about 3 L / min, to obtain the treated mineral processing recycling liquid. By measuring the content of xanthate in the solution, the content of ethyl yellow has been degraded by 95.17%.

[0078] Embodiment 2:

[0079] The construction process of the original battery filter layer: prepare 30g of pyrite particles with a sulfur content of more than 45% and a size of 3-5mm; prepare 50g of pyrolusite with a manganese content of 25% and a size of 3-5mm; prepare 10g of high-purity graphite with a scaly shape and a size of 3-5mm. Mix the various prepared ores, and mix them 5 times using the ore cone mixing method to obtain a mixed raw material for the original battery filter layer. Put 10g of the raw material for the original battery filter layer into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed mineral material, and add 90g of the mixed mineral material in 10 times to obtain a filter layer A2 of about 65mm.

[0080] The process of building the pyrite and calcite filter layer: prepare 40g of pyrite particles with a sulfur content of more than 30% and a size of 3-5mm; prepare 40g of calcite with a calcium carbonate content of more than 80% and a size of 3-5mm. After mixing the two ores in a cone for 5 times, add 10g of the mixed ore each time into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed ore, and add 80g of the mixed ore in 8 times to obtain a filter layer B2 of about 59mm.

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

[0082] After grinding pyrite with sulfur content exceeding 30%, the grinding fineness is controlled at 78.12%, the flotation pulp concentration is about 35%, 300g / t of water glass adjuster is added, and flotation is carried out by adopting a flotation open circuit process of one coarse (20g / t of sodium ethyl xanthate + 80g / t of sodium butyl xanthate + 15g / t of No. 2 oil) + one sweep (10g / t of sodium ethyl xanthate + 40g / t of sodium butyl xanthate + 10g / t of No. 2 oil) + one fine. The flotation concentrate, middlings and tailings are filtered to obtain the xanthate-containing wastewater, and the xanthate content in the solution is determined to be about 72.27mg / L.

[0083] At 20-25°C, 600 mL of a solution with a xanthate content of about 72.27 mg / L was mixed with 12 g of pyrite particles with a sulfur content of more than 45% and a size of 0-0.074 mm, stirred for 10 minutes, and allowed to stand for 10 minutes. Maintaining the above temperature, the activated supernatant solution was passed through the original battery filter material layer A2 at a rate of 20 mL / min, and the air intake was about 4 L / min to obtain the solution after the original battery treatment. The solution after the original battery treatment was passed through the pyrite and calcite filter material layer B2 at a rate of 20 mL / min, and the air intake was about 3.6 L / min, to obtain the solution after the pyrite and calcite treatment. The solution after the pyrite and calcite treatment was passed through the pyrolusite and calcite filter material layer C2 at 18 mL / min, and the air intake was about 3 L / min, to obtain the treated mineral processing recycling liquid. By measuring the xanthate content in the solution, the content of xanthate organic matter has been degraded by 97.24%.

[0084] Embodiment 3:

[0085] The construction process of the original battery filter layer: prepare 30g of pyrite particles with a sulfur content of more than 45% and a size of 3-5mm; prepare 60g of pyrolusite with a manganese content of 25% and a size of 3-5mm; prepare 15g of high-purity graphite with a scaly shape and a size of 3-5mm. Mix the various prepared ores, mix them 5 times using the ore cone mixing method, weigh 90g of them, and obtain the mixed raw materials for the original battery filter layer. Put 10g of the raw materials for the original battery filter layer into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed mineral materials, add 90g of the mixed mineral materials in 9 times, and obtain a filter layer A3 of about 68mm.

[0086] The process of building the pyrite and calcite filter layer: prepare 30g of pyrite particles with a sulfur content of more than 45% and a size of 3-5mm; prepare 50g of calcite with a calcium carbonate content of more than 80% and a size of 3-5mm. After mixing the two ores in a cone for 5 times, add 10g of the mixed ore each time into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed ore, and add 80g of the mixed ore in 8 times to obtain a filter layer B3 of about 63mm.

[0087] The process of building the pyrolusite and calcite filter layer: 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 more than 80% by mass and a diameter of 3-5mm. After mixing the two ores in a cone for 5 times, add 10g of the mixed ore each time into a plastic pipe with a diameter of 32mm as a filter layer (the bottom of the filter layer is separated by a filter cloth), vibrate appropriately while adding the mixed ore, and add 80g of the mixed ore in 8 times to obtain a filter layer C3 of about 52mm.

[0088] The waste liquid from the beneficiation of a gold-containing pyrite (the beneficiation waste liquid in the working condition) was measured to contain 38.7 mg / L of xanthate. 2000 ml of the beneficiation waste liquid was stirred and mixed with 20 g of pyrite at 20-25 ° C for 15 minutes and allowed to stand for 10 minutes. Maintaining the above temperature, the activated supernatant solution was passed through the original battery filter material layer A3 at a rate of 15 mL / min, and the air intake was about 3 L / min to obtain the solution after the original battery treatment. The solution after the original battery treatment was passed through the pyrite and calcite filter material layer B3 at a rate of 20 mL / min, and the air intake was about 4 L / min, to obtain the solution after the pyrite and calcite treatment. The solution after the pyrite and calcite treatment was passed through the pyrolusite and calcite filter material layer C3 at 16 mL / min, and the air intake was about 3 L / min, and about 1928 ml of the treated liquid was obtained. By measuring the xanthate content in the solution, it was found that the xanthate content had been degraded by 99.27%.

[0089] Figure 5 The figure shows the removal effect of xanthate organic matter in Examples 1 to 3 of the present invention respectively. Figure 5 As shown, it can be seen that the filter material layer constructed by the present invention can achieve sufficient degradation of xanthate.

[0090] The treated liquid in Example 3 was divided into 900 mL of liquid 1 and 900 mL of liquid 2 for parallel experiments. There was no difference in the composition of liquid 1 and liquid 2. For the convenience of subsequent experiments, different names were used to distinguish them. Untreated wastewater, tap water, liquid 1 and liquid 2 were added into the grinding and flotation process of the gold mine respectively as return water for beneficiation (specific process parameters are as follows: grinding concentration 65%, grinding fineness 72.6%, one roughing and one scavenging, and then mixed concentrate for beneficiation flotation process, the amount of xanthate used was 60+25 g / t, and the amount of No. 2 oil used was 20 g / t). Figure 6 The bar chart shows the gold recovery effect of untreated wastewater, tap water, liquid 1 and liquid 2 obtained after treatment in Example 3 of the present invention. Figure 6 As shown, it can be seen that the recovery rates in the gold ore reach 92.24%, 91.96% and 92.27%, indicating that the liquid treated by the multiple filter material layers of the present invention can be reused as return water for mineral processing, thereby avoiding the waste of water resources.

[0091] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is 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 in the scope of protection of the present invention.

Claims

1. A method for treating xanthate ore dressing wastewater using natural ore, comprising: Adding pyrite powder to the xanthate-based ore dressing wastewater for activation treatment, so that the xanthate group is converted into a dixanthate group, and the activated ore dressing wastewater is obtained; Under the condition of introducing air, the activated mineral processing wastewater is passed through the galvanic cell filter material layer to obtain a first solution; The first solution is sequentially passed through a metal purification filter material layer and a control filter material layer to obtain return water for mineral processing; Wherein, the primary battery filter material layer includes pyrite, pyrolusite and graphite, and the oxygen in the air is activated into active oxygen free radicals and / or ozone through the coupling effect of pyrite and pyrolusite, so that the active oxygen free radicals and / or ozone oxidatively degrade the xanthate organic matter in the mineral processing wastewater.

2. The processing method according to claim 1, wherein: The original battery filter material layer is prepared by the following process: Mix pyrite, pyrolusite and graphite evenly and fill them into a cylindrical pipe with a diaphragm wrapped at the bottom; The particle sizes of pyrite, pyrolusite and graphite range from 3 to 5 mm respectively.

3. The processing method according to claim 2, wherein: The mass ratio of pyrite, pyrolusite and graphite is (2~4):(2~5):1; The height of the original battery filter material layer is 50-70 mm.

4. The processing method according to claim 1, wherein: The activated mineral processing wastewater is passed through the galvanic cell filter layer to obtain a treated first solution, which comprises: At 20-50° C., the activated mineral processing wastewater is passed through the galvanic cell filter material layer at a rate of 15-30 mL / min; The air intake is 3~5L / min.

5. The processing method according to claim 1, wherein: The first solution is sequentially passed through a metal purification filter material layer and a control filter material layer to obtain return water for mineral processing, comprising: Passing the first solution through a metal purification filter material layer while introducing air to obtain a second solution; Under the condition of introducing air, passing the second solution through the control filter material layer to obtain return water for mineral processing; Wherein, the metal purification filter material layer includes pyrite and calcite, and the metal ions in the first solution are removed in a precipitation manner through the interface catalysis of pyrite.

6. The processing method according to claim 5, wherein: The mass ratio of pyrite to calcite is (1~2):2; The height of the metal purification filter material layer is 40-70 mm.

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

8. The processing method according to claim 1, wherein: The step of adding pyrite powder to the xanthate-based ore dressing wastewater for activation treatment so that the xanthate group is converted into a dixanthate group to obtain the activated ore dressing wastewater comprises: At 20-50° C., adding pyrite powder with a particle size of 0.001-0.074 mm to the xanthate-based ore dressing wastewater and stirring for 5-10 minutes, and then standing for 10-20 minutes to obtain an upper layer of activated ore dressing wastewater and a first mixture of a lower layer; The amount of the pyrite powder added is 1-2% of the weight of the xanthate-type mineral processing wastewater, the stirring is solution stirring or air-filled stirring, the first mixture includes pyrite particles and mixed slurry, and the sulfur content of the pyrite powder is greater than 45%.

9. The processing method according to claim 8, wherein: After the first mixture is charged with air for oxidation, 0.1% of the mass of the first mixture of pyrite particles is added to obtain a second mixture; adding the second mixture to the xanthate-based ore dressing wastewater for recycling; The number of cycles is 1 to 10.

10. The method according to claim 1, wherein: The concentration of xanthate organic matter in the xanthate ore dressing wastewater is 10-150 mg / L.

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