A method for comprehensive recovery and selective separation of copper and molybdenum from copper-molybdenum ore

Abstract

The application provides a copper-molybdenum comprehensive recovery and selective separation method of copper-molybdenum ore, relates to the recovery and separation field of copper-molybdenum ore, and solves the problem of the further separation and recovery of copper-molybdenum by using ordinary flocculants. The method comprises the following steps: mixing a mineral sample containing molybdenite and chalcopyrite with water and stirring to obtain a mineral slurry; adding an adjusting agent to adjust the pH of the mineral slurry to pH < 6; then adding a dispersing agent and continuing to stir; adding a pH-sensitive flocculant containing a hydrophobic group and a pH-sensitive group and continuing to stir to obtain a mixed mineral slurry; performing flotation on the mixed mineral slurry to obtain a copper-molybdenum mixed concentrate product; placing the copper-molybdenum mixed concentrate product into a stirring tank and stirring to mix uniformly; adding an adjusting agent to adjust the pH to pH >= 6 and stirring to obtain a copper-molybdenum mixed concentrate after deflocculation; adding an inhibitor to the copper-molybdenum mixed concentrate after deflocculation and stirring; then sequentially adding a collector and a foaming agent and stirring to perform aeration flotation to obtain a copper concentrate and a molybdenum concentrate. The application can realize the selective separation of copper and molybdenum.

Description

Technical Field

[0001] This invention belongs to the field of copper-molybdenum ore recovery and separation technology, specifically relating to a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore. Background Technology

[0002] Molybdenite and chalcopyrite are important mineral resources in industrial production, possessing excellent properties and widely used in chemical, aerospace, and steel industries. Molybdenite and chalcopyrite typically occur together in sulfide deposits. With the depletion of rich ore resources, the efficient beneficiation and utilization of low-grade and tailings deposits are receiving increasing attention.

[0003] The main characteristics of low-grade, complex copper-molybdenum sulfide ores are "poor, fine, and complex." During beneficiation, they require thorough grinding into fine particles. Conventional flotation methods typically face two technical challenges in recovering these minerals. First, there's the challenge of fine-particle flotation: fine grinding increases the facet ratio of the copper-molybdenum sulfide ores, enhancing their hydrophilicity and leading to severe non-selective adsorption. Simultaneously, the small mass and low momentum of fine particles reduce their probability of collision and adhesion with air bubbles, easily causing fine particle mixing. Second, there's the technical challenge of copper-molybdenum separation: associated chalcopyrite and molybdenite have similar floatability, often requiring mixed copper-molybdenum flotation followed by separation. Conventional flocculation flotation can improve the difficulty of flotating fine particles, but the mixed copper-molybdenum flocs formed using ordinary flocculants increase the difficulty of copper-molybdenum separation, hindering further separation and recovery. Summary of the Invention

[0004] Based on the above analysis, the present invention aims to provide a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore, which solves the problem that the mixed flocs of copper and molybdenum formed by using ordinary flocculants increase the difficulty of copper-molybdenum separation and are not conducive to further separation and recovery of copper and molybdenum.

[0005] The objective of this invention is mainly achieved through the following technical solutions:

[0006] This invention provides a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore, comprising:

[0007] Step 1: Mix the ore sample containing molybdenite and chalcopyrite with water and stir to obtain a slurry; add an adjuster to adjust the pH of the slurry to pH < 6; then add a dispersant and continue stirring; add a pH-sensitive flocculant including hydrophobic groups and pH-sensitive groups and continue stirring to obtain a mixed slurry;

[0008] Step 2: The mixed slurry is floated using a flotation machine. First, a collector is added and stirred, then a frother is added and stirred, and then aerated flotation is performed to obtain a copper-molybdenum mixed concentrate product.

[0009] Step 3: Place the copper-molybdenum mixed concentrate product into a mixing tank and stir to mix evenly; add an adjuster to adjust the pH to pH≥6, stir, and obtain the deflocculated copper-molybdenum mixed concentrate;

[0010] Step 4: Add inhibitor to the deflocculated copper-molybdenum mixed concentrate and stir; then add collector and stir, then add frother and stir, and aerate for flotation for 3-6 minutes to obtain copper concentrate and molybdenum concentrate.

[0011] Furthermore, in step 1, the mass concentration of the slurry is controlled to be 5% to 30%.

[0012] Furthermore, in step 1, the dispersant is sodium hexametaphosphate or water glass, and the amount of dispersant added is 0.8–2 kg / t. 矿样 .

[0013] Furthermore, in step 1, the amount of flocculant added is 0.04–0.4 kg / t. 矿样 .

[0014] Furthermore, in step 2, the collector is one or more of kerosene or ethyl thiocyanate, and the amount of collector added is 0.05–0.25 kg / t. 矿样 .

[0015] Furthermore, in step 2, the foaming agent is methyl isobutyl methanol or pine oil, and the amount of foaming agent added is 0.03–0.2 kg / t. 矿样 .

[0016] Furthermore, in step 1, the pH-sensitive flocculant is a polyacrylamide copolymer, which includes a first structural unit and a second structural unit. The first structural unit is:

[0017]

[0018] The second structural unit is:

[0019]

[0020] R1 and R5 are each independently selected from hydrogen and methyl; R2 is selected from alkylene containing 1 to 3 carbon atoms, such as methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2(CH3)CH-); R3 and R4 are each independently selected from methyl and ethyl; R6 is an alkyl group containing 8 to 14 carbon atoms.

[0021] Furthermore, the weight-average molecular weight of the polyacrylamide copolymer is 70,000 to 100,000; and / or, the molar ratio of the first structural unit to the second structural unit is 1.9:1 to 5.7:1; and / or,

[0022] The intrinsic viscosity of polyacrylamide copolymers is 380–580 mL / g.

[0023] Furthermore, in step 4, the inhibitor is sodium thioglycolate or sodium sulfide, and the amount of inhibitor added is 2–10 kg / t. 矿样 .

[0024] Furthermore, in step 4, the foaming agent is methyl isobutyl methanol or pine oil, and the amount of foaming agent added is 0.05–0.2 kg / t. 矿样 .

[0025] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0026] a) The copper-molybdenum ore comprehensive recovery and selective separation method of the present invention utilizes a pH-sensitive flocculant. This flocculant has the function of hydrophilicity / hydrophobicity and charge conversion with pH, ​​which can achieve selective flocculation and deflocculation of fine-particle ore samples containing molybdenite and chalcopyrite under different acidity / alkalinity. First, utilizing the positive charge and strong hydrophobicity of the pH-sensitive flocculant near the acidic pH, the hydrophobic chalcopyrite and molybdenite in the ore sample are selectively flocculated to form agglomerated flocs. Then, a mixed flotation method is used to comprehensively recover molybdenite and chalcopyrite to obtain a copper-molybdenum mixed concentrate product. Subsequently, utilizing the hydrophilicity and electronegativity of the pH-sensitive flocculant in weakly acidic and alkaline environments, the pH of the copper-molybdenum mixed concentrate product is appropriately adjusted to achieve dissociation between the mixed flocs of molybdenite and chalcopyrite and the flocculant, weakening the flocculation effect, enhancing the dissociation degree of fine-particle molybdenite and chalcopyrite, and significantly reducing the difficulty of copper-molybdenum separation. Finally, copper and molybdenum were separated by a flotation method that suppresses copper and floats molybdenum to obtain molybdenum concentrate and copper concentrate.

[0027] b) The method of the present invention can be divided into three parts: selective flocculation flotation, deflocculation, and copper-molybdenum separation. The method of the present invention is of great significance for the comprehensive utilization and copper-molybdenum separation process of low-grade complex sulfide copper-molybdenum ore.

[0028] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures particularly pointed out in the written description. Attached Figure Description

[0029] The accompanying drawings are only used to further understand the technical solutions of the present invention and constitute a part of the specification. They are used together with the embodiments of the present invention to explain the technical solutions of the present invention and do not constitute a limitation on the technical solutions of the present invention.

[0030] Figure 1 This is a process flow diagram of Embodiment 4 of the present invention;

[0031] Figure 2 These are images of selective flocculation after embodiment 3 of the present invention;

[0032] Figure 3 This is an image of the copper-molybdenum mixed concentrate after deflocculation in Example 3 of the present invention. Detailed Implementation

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention. Unless otherwise specified, the numerical values, fractions or ratios involved are all mass values, mass fractions or mass ratios.

[0034] This invention provides a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore, comprising the following steps:

[0035] Step 1: Mix the ore sample containing molybdenite and chalcopyrite with water and stir to obtain a slurry; add an adjuster to adjust the pH of the slurry to pH < 6; then add a dispersant and continue stirring; add a pH-sensitive flocculant including hydrophobic groups and pH-sensitive groups and continue stirring to obtain a mixed slurry;

[0036] Step 2: The above mixed slurry is floated using a flotation machine. First, a collector is added and stirred, then a frother is added and stirred, and then aerated flotation is performed to obtain a copper-molybdenum mixed concentrate product.

[0037] Step 3: Place the copper-molybdenum mixed concentrate product into a mixing tank and mix for 2-5 minutes; add an adjuster to adjust the pH to pH ≥ 6 (e.g., 6-10.0), and mix for 2-5 minutes to obtain the deflocculated copper-molybdenum mixed concentrate;

[0038] Step 4: Add inhibitor to the deflocculated copper-molybdenum mixed concentrate and stir for 5-10 minutes; then add collector and stir for 2-3 minutes; then add frother and stir for 2-3 minutes; and finally aerate and float for 3-6 minutes to obtain copper concentrate and molybdenum concentrate.

[0039] Specifically, in step 1 above, the ore sample containing molybdenite and chalcopyrite contains fine-grained materials, with the particle size of the fine-grained materials being more than 65% of -600 mesh and more than 95% of -400 mesh.

[0040] Specifically, in step 1 above, the mineral sample containing molybdenite and chalcopyrite can be a natural low-quality copper-molybdenum sulfide ore or an artificially mixed mineral.

[0041] Specifically, in step 1 above, if the slurry concentration is too high, the slurry and bubbles cannot flow freely, the aeration conditions are disrupted, and the concentrate quality and recovery rate decrease. If the slurry concentration is too low, reagent and energy consumption is high, the flotation machine's production capacity decreases, the froth layer thickness decreases, and the froth removal effect and concentrate product recovery rate are affected. Therefore, the slurry concentration should be controlled between 5% and 30%.

[0042] Specifically, in step 1 above, the modifier is a hydrochloric acid or sulfuric acid solution with a mass concentration of 5% to 20%, preferably a sulfuric acid solution with a mass concentration of 10%.

[0043] Specifically, in step 1 above, the dispersant is sodium hexametaphosphate or water glass. If the amount of dispersant added is too large, the ions obtained from hydrolysis in the dispersant will be further adsorbed on the surface of molybdenite and chalcopyrite, reducing the surface potential and hydrophobicity of molybdenite and chalcopyrite, leading to a decrease in concentrate grade and recovery rate. If the amount of dispersant added is too small, it will not achieve the desired dispersion effect on gangue minerals such as quartz, resulting in non-selective adsorption and flocculation of gangue by the flocculant, and a serious decrease in concentrate grade. Therefore, the amount of dispersant added should be controlled at 0.8–2 kg / t. 矿样 The purpose of stirring after adding the dispersant is to promote the full adsorption of the dispersant onto the gangue, reduce the agglomeration between mineral particles, and thus improve the flotation effect. Considering that excessive stirring time would lead to excessive energy consumption and equipment wear, stirring should be controlled to 2–5 minutes.

[0044] Specifically, in step 1 above, the pH-sensitive flocculant is a polyacrylamide copolymer, which includes a first structural unit and a second structural unit. The first structural unit is:

[0045]

[0046] The second structural unit is:

[0047]

[0048] R1 and R5 are each independently selected from hydrogen and methyl; R2 is selected from alkylene containing 1 to 3 carbon atoms, such as methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2(CH3)CH-); R3 and R4 are each independently selected from methyl and ethyl; R6 is an alkyl group containing 8 to 14 carbon atoms.

[0049] Specifically, the aforementioned polyacrylamide copolymers include hydrophobic groups (dodecyl glucoside groups) and pH-sensitive groups (tertiary amine groups), giving the copolymers pH sensitivity in addition to hydrophobic modification, allowing them to respond to acidity and alkalinity. Specifically, the pH-sensitive groups are reactive and can undergo protonation or deprotonation reactions in environments with different pH levels. Therefore, the polyacrylamide copolymers of this invention, as flocculants, alter the electrical properties of the flocculant itself, thereby achieving flocculation of molybdenite and chalcopyrite and dissociation between the mixed flocs and the flocculant by changing the pH value.

[0050] Specifically, R1 and R5 are each independently selected from hydrogen and methyl; R2 is ethylene; and R3 and R4 are both ethyl.

[0051] Specifically, R6 is a straight-chain alkyl group containing 8, 9, 10, 11, 12, 13, or 14 carbon atoms, such as -(CH2)8 or -(CH2). 12 -(CH2) 14 .

[0052] Specifically, the molar ratio of the first structural unit to the second structural unit of the polyacrylamide copolymer is 1.9:1 to 5.7:1, and can be further 3:1 to 5:1. For example, the molar ratio of the first structural unit to the second structural unit can be 1.92:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 5.67:1, etc.

[0053] Specifically, the weight-average molecular weight of polyacrylamide copolymers can be 70,000 to 100,000, such as 75,000, 80,000, 85,000, 90,000, 95,000, etc.

[0054] Specifically, the intrinsic viscosity of polyacrylamide copolymers is 380–580 mL / g, for example, 385 mL / g, 390 mL / g, 400 mL / g, 420 mL / g, 450 mL / g, 470 mL / g, 490 mL / g, 500 mL / g, 520 mL / g, 550 mL / g, and 570 mL / g.

[0055] Specifically, polyacrylamide copolymers can be random copolymers or block copolymers.

[0056] Specifically, the present invention also provides a method for preparing the above-mentioned polyacrylamide copolymer, wherein the polyacrylamide copolymer is obtained by cosolvent polymerization.

[0057] Specifically, the preparation method of polyacrylamide copolymers includes reacting reactants to obtain polyacrylamide copolymers; wherein, the reactants include a first polymerizing monomer (also known as a pH-sensitive monomer), a second polymerizing monomer, and an alkyl glucoside containing a hydrophobic group; the second polymerizing monomer includes acrylamide and / or methacrylamide, and the structural formulas of the first polymerizing monomer and the alkyl glucoside are as follows:

[0058] First polymer monomer: Alkyl glucoside:

[0059] Among them, R1, R2, R3, R4, and R6 are subject to the aforementioned limitations.

[0060] Specifically, the preparation method of this invention is simple. While the first and second monomers are polymerizing, dodecyl glucoside reacts with the amide group of the second monomer to obtain a polyacrylamide copolymer. That is, two reactions occur in a single process, simplifying the preparation process. Furthermore, during the initiator-induced free radical copolymerization, the amino groups on the amide group and the hydroxyl groups on the alkyl glycoside are reactive groups with very low activation energies. They graft and remove water molecules, and this reaction occurs throughout the entire polymerization process.

[0061] Specifically, dodecyl glucoside can be reacted with the second monomer first, and then copolymerized with the first monomer.

[0062] Specifically, the first polymerizing monomer includes one or more of diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, 2-(ethyl(methyl)amino)ethyl methacrylate, and 2-(ethyl(methyl)amino)ethyl acrylate.

[0063] Specifically, alkyl glucosides include one, two, or three of the following: octyl glucosides, dodecyl glucosides, and tetradecyl glucosides.

[0064] Specifically, the mass of the first polymerizing monomer is 38-57% of the total mass of the reactants, and can further be 40-50%, for example 38.8%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, and 56.1%.

[0065] Specifically, the mass of the second polymerizing monomer is 43-62% of the total mass of the reactants, and can further be 45-55%, for example 43.9%, 45%, 47%, 49%, 50%, 52%, 54%, 58%, 60%, and 61.2%.

[0066] Specifically, the mass of alkyl glucoside is 2-14% of the total mass of the reaction raw materials, more preferably 6-14%, and even more preferably 6-10%, for example 3%, 4%, 5%, 6%, 8%, 9%, and most preferably 10%. Maintaining the mass content of alkyl glucoside within the above range not only further enhances the hydrophobic association of the obtained polyacrylamide copolymer, but also gives the polyacrylamide copolymer higher solubility, which is beneficial for its use as a flocculant.

[0067] Specifically, the reaction temperature of the reactants can be 40–60°C, such as 45°C, 50°C, 55°C, etc., preferably 50°C. A water bath heating method can be used to maintain the reactants at a temperature of 40–60°C. Maintaining the reaction temperature within this range not only increases the polymerization rate but also does not reduce the intrinsic viscosity of the polymer, ensuring that the intrinsic viscosity of the resulting polymer remains within a suitable range.

[0068] Specifically, the reaction time of the reactants can be 2 to 7 hours, such as 3 hours, 4 hours, 5 hours, or 6 hours, with 5 hours being preferred. A reaction time of 2 to 7 hours not only allows the polymerization reaction to proceed fully but also prevents cross-linking of the product, which is beneficial for improving the conversion rate.

[0069] Specifically, the preparation methods of polyacrylamide copolymers include:

[0070] The reactants are dissolved in water to form a reactant solution;

[0071] A redox initiator is added to the raw material solution, and the reaction is carried out at 40–60°C for 2–7 hours to obtain a gel-like polymer; and

[0072] The gel-like polymer was washed with anhydrous ethanol, dried, and then ground into powder to obtain polyacrylamide copolymer powder.

[0073] Specifically, the mass percentage of the reactants in the reactant solution is 20-45%, for example 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, preferably 30%. Maintaining the mass concentration of the reactants within the above range not only increases the polymerization rate but also facilitates the purification and dissolution of the product.

[0074] Specifically, the mass of the redox initiator is 0.2% to 1.2% of the total mass of the reactants, for example, 0.3%, 0.5%, 0.6%, 0.8%, 1.0%, preferably 1.0%. Maintaining the mass of the redox initiator within the above range ensures that the number of reaction centers remains within an appropriate range without causing a decrease in molecular weight, which is beneficial for controlling the molecular weight of the obtained polymer.

[0075] Specifically, redox initiators include oxidants and reductants. When using them, the oxidant is added to the raw material solution first, followed by the reductant.

[0076] Specifically, the molar ratio of oxidant to reducing agent can be 1:2. For example, the oxidant can be potassium persulfate, and the reducing agent can be sodium bisulfite.

[0077] Specifically, in the preparation method of the present invention, after the redox initiator is added to the reaction system, nitrogen gas is introduced into the system to remove air, especially oxygen, to prevent oxygen from inhibiting free radical polymerization. The nitrogen introduction time can be more than 10 minutes, more preferably 10 to 20 minutes, such as 12 minutes, 15 minutes, or 18 minutes, and preferably 15 minutes. This nitrogen introduction time can maximize the removal of air from the reaction system without causing waste.

[0078] Specifically, the preparation methods of polyacrylamide copolymers include:

[0079] (1) Add deionized water to the reaction apparatus, and add the first polymer monomer, the second polymer monomer and the alkyl glucoside to the reaction apparatus and stir thoroughly to obtain the raw material solution.

[0080] (2) Add the redox initiator potassium persulfate-sodium bisulfite to the above raw material solution, stir thoroughly, introduce high-purity nitrogen into the reaction device to remove the air in the device and seal it; the order of adding the initiator is to add the oxidant potassium persulfate first, and then add the reducing agent sodium bisulfite.

[0081] (3) Place the sealed reaction device after the above treatment into a constant temperature water bath and stir to initiate the polymerization reaction. After the polymerization is completed, a milky white gel-like polymer compound is generated. Take out the reaction device and cool it to room temperature.

[0082] (4) The white gelatinous substance after repeated washing and purification with ethanol and cooling is dried at 70°C for 24 hours to become a solid. It is then taken out and ground into powder to obtain a pH-sensitive polyacrylamide copolymer.

[0083] Specifically, the stirring in step (3) above can be done by mechanical stirring, and the stirring speed can be controlled at 70 to 100 rpm, such as 75 rpm, 80 rpm, 85 rpm, 90 rpm, 95 rpm, etc.

[0084] Specifically, the washing and purification time in step (4) above can be 2 hours, so that the unreacted monomers can be completely washed away.

[0085] Specifically, the polyacrylamide copolymer flocculant of the present invention exhibits extremely low turbidity and positive charge in acidic conditions due to the positive charge of the protonated tertiary amine; under alkaline conditions, the increase in pH causes the protonation effect to disappear, and in order to make the polymer present a low-energy state distribution in water, the polymer chains will shrink and coil, and the hydrophobic parts will aggregate to form micelles, which in turn leads to an increase in solution turbidity and a negative charge. Therefore, the polyacrylamide copolymer flocculant has good pH response capability.

[0086] Specifically, in step 1 above, if the amount of flocculant added is too large, the flocculant will coat the interaction sites of molybdenite and chalcopyrite during the flocculation process, which is not conducive to the further growth and enlargement of the flocs, ultimately resulting in a low grade and recovery rate of the concentrate obtained from flotation. If the amount of flocculant added is too small, the collision probability between the flocculant and molybdenite and chalcopyrite will decrease, resulting in insufficient flocculation and a decrease in the recovery rate of molybdenite and chalcopyrite. Therefore, the amount of flocculant added should be controlled at 0.04–0.4 kg / t. 矿样 .

[0087] Specifically, in step 1 above, the purpose of stirring after adding the flocculant is to allow the flocculant to fully react with molybdenite and chalcopyrite, forming molybdenite and chalcopyrite flocs with larger apparent sizes and a denser structure. Considering that excessive stirring time would lead to excessive energy consumption and equipment wear, the stirring time is controlled to 2-5 minutes.

[0088] Specifically, in step 1 above, the mixed slurry includes flocs formed by hydrophobic fine-grained molybdenite and chalcopyrite, which are large in size and have a compact structure; the mixed slurry also includes gangue mineral quartz, which does not form obvious flocs, but has large gaps between particles and strong dispersibility.

[0089] Specifically, in step 2 above, the collector is one or more of kerosene or ethyl thiocyanate. Excessive collector addition will disrupt the selectivity of the flotation process, significantly reducing the concentrate grade and making further concentrate refining and separation difficult. Insufficient collector addition will result in insufficient adsorption on the surfaces of molybdenite and chalcopyrite, leading to inadequate mineralization of the bubbles and minerals, and consequently, a lower concentrate recovery rate. Therefore, the collector addition should be controlled at 0.05–0.25 kg / t. 矿样 The purpose of stirring after adding the collector is to promote its adsorption on the surface of molybdenite and chalcopyrite, thereby increasing their hydrophobicity, enhancing the mineralization of bubbles and minerals, and thus improving the recovery of molybdenite and chalcopyrite. Considering that excessive stirring time would lead to excessive energy consumption and equipment wear, stirring time is controlled to 2-3 minutes.

[0090] Specifically, in step 2 above, the frother is methyl isobutyl methanol or pine oil. Excessive frother will create a large amount of viscous foam, which easily causes gangue minerals to adhere to the bubbles, leading to a decrease in concentrate grade. Insufficient frother will result in a thin foam layer, making the foam brittle and prone to collapse, difficult to scrape off, and severely reducing concentrate yield. Therefore, the amount of frother added should be controlled at 0.03–0.2 kg / t. 矿样 The purpose of stirring after adding the foaming agent is to ensure that the foaming agent is evenly dispersed in the slurry, improve the stability of bubbles in the slurry, and increase the residence time of bubbles in the slurry. Considering that excessive stirring time leads to excessive energy consumption, while insufficient stirring time results in uneven dispersion of the foaming agent, stirring should be controlled at 2-3 minutes.

[0091] Specifically, in step 2 above, excessive flotation speed increases the inertial force causing mineral particles to detach from bubbles, hindering bubble mineralization and leading to excessively high turbulent flow velocity in the rising slurry, thus affecting flotation efficiency. Conversely, insufficient flotation speed prevents adequate suspension of mineral particles, reducing the probability of collisions between particles and bubbles and lowering recovery rates. Therefore, the flotation speed should be controlled at 1500–1900 rpm. Excessive aeration flotation time significantly reduces concentrate grade and economic efficiency, while insufficient time severely reduces concentrate recovery. Therefore, aeration flotation should be controlled at 3–6 minutes.

[0092] Specifically, in step 3 above, the modifier is a sodium hydroxide or sodium carbonate solution with a mass concentration of 0.5% to 5%. The purpose of stirring after adding the modifier is to ensure that it is fully and evenly dispersed in the concentrate slurry, adjust the slurry pH, reduce the hydrophobicity and surface potential of the pH-sensitive flocculant, and promote the dissociation of molybdenite and chalcopyrite flocs. Considering that excessive stirring time will increase unnecessary mechanical energy consumption, while insufficient pH adjustment and unsatisfactory floc dissociation effect are possible, stirring is controlled to 2–5 minutes.

[0093] Specifically, in step 4 above, the inhibitor is sodium thioglycolate or sodium sulfide. The inhibitor forms a hydrophilic film on the surface of chalcopyrite, inhibiting its flotation. If the inhibitor dosage is too high, molybdenite may also be inhibited, leading to a decrease in recovery rate; if the inhibitor dosage is too low, the inhibition of chalcopyrite will be insufficient, resulting in poor copper-molybdenum separation. Therefore, the inhibitor dosage should be controlled at 2–10 kg / t. 矿样 The purpose of stirring after adding the inhibitor is to ensure that the inhibitor acts fully and evenly on the surface of the chalcopyrite, preventing it from floating. Considering that excessive stirring time can lead to oxidation and inactivation of the inhibitor, while insufficient stirring time will result in inadequate interaction with the chalcopyrite, stirring should be controlled for 5–10 minutes.

[0094] Specifically, in step 4 above, the collector is kerosene. Adding too much collector will disrupt the selectivity of the flotation process, significantly reducing the grade of the molybdenum concentrate. Adding too little collector will result in insufficient adsorption on the molybdenite surface, leading to inadequate mineralization of the bubbles and minerals, and consequently, a lower concentrate recovery rate. Therefore, the collector dosage should be controlled at 0.1–0.5 kg / t. 矿样 The purpose of stirring after adding the collector is to promote its adsorption on the surface of molybdenite, thereby increasing its hydrophobicity, enhancing the mineralization of bubbles and minerals, and thus improving the recovery of molybdenite. Considering that excessive stirring time would lead to unnecessary energy consumption and equipment wear, stirring time is controlled to 2–3 minutes.

[0095] Specifically, in step 4 above, the frother is methyl isobutyl methanol or pine oil. Adding too much frother will create a large amount of viscous foam, which easily causes gangue minerals to adhere to the bubbles, leading to a decrease in concentrate grade. Adding too little frother will result in a thin foam layer, making the foam brittle and easily broken, difficult to scrape off, and severely reducing concentrate yield. Therefore, the amount of frother added should be controlled at 0.05–0.2 kg / t. 矿样 The purpose of stirring after adding the foaming agent is to ensure that the foaming agent is evenly dispersed in the slurry, improve the stability of bubbles in the slurry, and increase the residence time of bubbles in the slurry. Considering that excessive stirring time leads to excessive energy consumption, while insufficient stirring time results in uneven dispersion of the foaming agent, stirring should be controlled at 2-3 minutes.

[0096] Specifically, in step 4 above, if the aeration flotation time is too long, the concentrate grade will decrease significantly, resulting in poor economic benefits; if it is too short, the concentrate recovery rate will be severely reduced. Therefore, the aeration flotation time should be controlled to 3–6 minutes.

[0097] Specifically, in step 2 above, aerated flotation includes roughing, cleaning, and scavenging.

[0098] Specifically, in step 2 above, the selection process can be repeated multiple times.

[0099] Specifically, in step 4 above, aerated flotation includes roughing, cleaning, and scavenging; both cleaning and scavenging can be performed multiple times.

[0100] Specifically, in the method of the present invention, the recovery rate of molybdenum can reach more than 58%, and the recovery rate of copper can reach more than 74%.

[0101] Compared with existing technologies, the copper-molybdenum ore comprehensive recovery and selective separation method of the present invention utilizes a pH-sensitive flocculant. This flocculant has the function of hydrophilicity / hydrophobicity and charge conversion with pH, ​​which can achieve selective flocculation and deflocculation of fine-particle ore samples containing molybdenite and chalcopyrite under different acidity and alkalinity. First, utilizing the positive charge and strong hydrophobicity of the pH-sensitive flocculant near the acidic pH, the hydrophobic chalcopyrite and molybdenite in the ore sample are selectively flocculated to form agglomerated flocs. Then, a mixed flotation method is used to comprehensively recover molybdenite and chalcopyrite to obtain a copper-molybdenum mixed concentrate product. Subsequently, utilizing the hydrophilicity and electronegativity of the pH-sensitive flocculant in weakly acidic and alkaline environments, the pH of the copper-molybdenum mixed concentrate product is appropriately adjusted to achieve dissociation between the mixed flocs of molybdenite and chalcopyrite and the flocculant, weakening the flocculation effect, enhancing the dissociation degree of fine-particle molybdenite and chalcopyrite, and significantly reducing the difficulty of copper-molybdenum separation. Finally, copper and molybdenum were separated by a flotation method that suppresses copper and floats molybdenum to obtain molybdenum concentrate and copper concentrate.

[0102] The method of this invention can be divided into three parts: selective flocculation flotation, deflocculation, and copper-molybdenum separation. The method of this invention is of great significance for the comprehensive utilization and copper-molybdenum separation process of low-grade complex sulfide copper-molybdenum ore.

[0103] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments.

[0104] The dispersant sodium hexametaphosphate used in the embodiments of the present invention is of analytical grade.

[0105] In the embodiments of this invention, the collectors kerosene and ethyl thiocyanate are of analytical grade, and the foaming agent pine oil is of industrial grade.

[0106] In this embodiment of the invention, a 10% sulfuric acid solution and a 2% sodium hydroxide solution were used to adjust the pH. Both the sulfuric acid and sodium hydroxide were of analytical grade.

[0107] Example 1

[0108] This embodiment provides a pH-sensitive flocculant, the preparation method of which includes:

[0109] (1) Add 25 mL of deionized water to the reaction apparatus, and then add the weighed 6.05 g acrylamide, 2.41 g diethylaminoethyl methacrylate, and 2.32 g dodecyl glucoside solution (40% by mass) sequentially to the reaction apparatus. Stir until all three substances are dissolved in the deionized water to obtain a 30% solution of reaction raw materials. Simultaneously, the mass of dodecyl glucoside is 10% of the total mass of the three reaction raw materials.

[0110] (2) First, add 0.052g of potassium persulfate to the above solution, then add 0.040g of sodium bisulfite to the solution, stir thoroughly to dissolve both, and the mass of the redox initiator is 1.0% of the total mass of the reaction raw materials. Continuously purge the reaction apparatus with high-purity nitrogen for 15 minutes, and seal the apparatus after purging the air.

[0111] (3) Place the reaction apparatus in a constant temperature water bath at 50°C and mechanically stir at 75 rpm. After stirring for 5 hours, the reaction apparatus will contain a milky white gel-like substance. Remove the reaction apparatus and cool it to room temperature.

[0112] (4) The white gelatinous substance was repeatedly washed and purified with ethanol, and dried at a constant temperature of 70°C for 24 hours to obtain a solid product. The product was then ground into powder to obtain a pH-sensitive polyacrylamide copolymer (poly(acrylamide-diethylaminoethyl methacrylate-dodecyl glycoside)). Its weight-average molecular weight was measured to be 100,000 and its intrinsic viscosity was 575.88 mL / g.

[0113] Example 2

[0114] This embodiment provides a pH-sensitive flocculant, the preparation method of which includes:

[0115] (1) Add 15 mL of deionized water to the reaction apparatus, and then add 4.00 g of acrylamide, 2.00 g of dimethylaminoethyl methacrylate, and 2.45 g of tetradecyl glycoside solution (40% by mass) sequentially to the reaction apparatus. Stir until all three substances are dissolved in the deionized water to obtain a reaction raw material solution with a mass fraction of 36%. Simultaneously, the mass of tetradecyl glycoside is 14% of the total mass of the three reaction raw materials.

[0116] (2) First, add 0.090g of potassium persulfate to the above solution, then add 0.064g of sodium bisulfite to the solution, stir thoroughly to dissolve both, and the mass of the redox initiator is 2.0% of the total mass of the reaction raw materials. Continuously purge the reaction apparatus with high-purity nitrogen for 15 minutes, and seal the apparatus after purging the air.

[0117] (3) Place the reaction apparatus in a constant temperature water bath at 55°C and mechanically stir at 75 rpm. After stirring for 4 hours, the reaction apparatus will contain a milky white gel-like substance. Remove the reaction apparatus and cool it to room temperature.

[0118] (4) The white gelatinous substance was repeatedly washed and purified with ethanol, and dried at a constant temperature of 70°C for 24 hours to obtain a solid product. The product was then ground into powder to obtain a pH-sensitive polyacrylamide copolymer poly(acrylamide-dimethylaminoethyl methacrylate-tetradecyl glycoside). Its weight-average molecular weight was measured to be 89,000 and its intrinsic viscosity was 486.79 mL / g.

[0119] Example 3

[0120] This embodiment provides a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore. The ore sample containing molybdenite and chalcopyrite in this embodiment is prepared by mixing 90% quartz (-0.012mm), 90% molybdenite (-0.011mm), and 90% chalcopyrite (-0.010mm) at a mass ratio of 48:1:1, resulting in an ore sample with 96% quartz, 2% molybdenite, and 2% chalcopyrite, containing 1.04% molybdenum and 0.61% copper. All contents refer to mass percentages. The method includes the following steps:

[0121] (1) Selective flocculation

[0122] Add the mineral sample and water to the mixing tank to prepare a 5% slurry. Stir for 5 minutes to fully wet the minerals. During stirring, add 10% sulfuric acid solution dropwise to adjust the pH of the slurry to 4.0. Add sodium hexametaphosphate dispersant and stir for 3 minutes. The amount of sodium hexametaphosphate added is 1.2 kg / t. 矿样 Then add flocculant poly(acrylamide-diethylaminoethyl methacrylate-dodecyl glycoside), at a dosage of 0.04 kg / t. 矿样 The mixture was stirred for 5 minutes at a stirring speed of 900 rpm to obtain a mixed slurry. The flocculant used in this embodiment is the same as that in Example 1.

[0123] like Figure 2 As shown, after selective flocculation, the black blocky part in the figure is the flocs formed by hydrophobic fine-grained molybdenite and chalcopyrite in the mixed ore. The flocs are large in size and have a compact structure, while the gray part is the gangue mineral quartz. The quartz did not form obvious flocs, and the gaps between the particles are large, indicating strong dispersibility.

[0124] (2) Copper-molybdenum mixed flotation

[0125] The mixed slurry after the above treatment is fed into a flotation cell for flotation at a speed of 1600 rpm. Kerosene, the collector, is added and stirred for 3 minutes at a rate of 0.15 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.05 kg / t. 矿样 After 4 minutes of flotation, a copper-molybdenum mixed concentrate was obtained.

[0126] (3) Deflocculation of copper-molybdenum mixed concentrate

[0127] The pH of the copper-molybdenum mixed concentrate was adjusted to 6.0 using a 2% sodium hydroxide solution, and the mixture was stirred for 5 minutes at a speed of 500 rpm to obtain the deflocculated copper-molybdenum mixed concentrate. Figure 3As shown, after deflocculation of the copper-molybdenum mixed concentrate, the mixed flocs of molybdenite and chalcopyrite are broken up, the flocculation binding between molybdenite and chalcopyrite is weakened, and the two minerals are clearly separated, which is conducive to the deep separation of copper and molybdenum.

[0128] The copper-molybdenum mixed concentrate has a molybdenum grade of 8.54% and a molybdenum recovery rate of 85.9%, and a copper grade of 4.76% and a copper recovery rate of 82.2%.

[0129] (4) Copper-molybdenum separation

[0130] The deflocculated copper-molybdenum mixed concentrate was fed into a flotation cell for copper-molybdenum separation. The flotation speed was 1600 rpm, and sodium sulfide, an inhibitor, was added and stirred for 5 minutes at a rate of 1.0 kg / t. 矿样 Add kerosene as a collector and stir for 3 minutes. The amount of kerosene added is 0.10 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.08 kg / t. 矿样 The flotation process lasted for 5 minutes, yielding molybdenum concentrate and copper concentrate. The molybdenum concentrate had a molybdenum grade of 31.28% and a recovery rate of 80.71%, while the copper concentrate had a copper grade of 18.35% and a copper recovery rate of 75.21%.

[0131] Example 4

[0132] This embodiment provides a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore, the process flow of which is as follows: Figure 1 As shown, the ore sample containing molybdenite and chalcopyrite in this embodiment is prepared by using molybdenum concentrate tailings as the raw ore for copper-molybdenum recovery and separation; wherein, the liberated particle size of the molybdenum concentrate tailings is -600 mesh or more (over 65%) and -400 mesh or more (over 95%); the molybdenum grade in the molybdenum concentrate tailings is 0.08%, and the copper grade is 0.22%, all of which refer to mass percentages. The process includes the following steps:

[0133] (1) Selective flocculation

[0134] Add the raw ore sample and water to the flotation cell to prepare a 25% slurry. Stir for 5 minutes to fully wet the minerals. During stirring, add 10% sulfuric acid solution dropwise to adjust the pH of the slurry to 4.2. Add sodium hexametaphosphate dispersant and stir for 3 minutes. The amount of sodium hexametaphosphate added is 0.5 kg / t. 矿样 Then add flocculant poly(acrylamide-diethylaminoethyl methacrylate-dodecyl glycoside), at a dosage of 0.1 kg / t. 矿样 Stir for 3 minutes to obtain a mixed slurry. The flocculant used in this embodiment is the flocculant from Example 1.

[0135] (2) Copper-molybdenum mixed flotation

[0136] The above mixed slurry was subjected to flotation at a speed of 1800 rpm. An appropriate amount of copper sulfate activator was added, and the mixture was stirred for 3 minutes. The amount of copper sulfate added was 0.1 kg / t. 矿样 Add kerosene as a collector and stir for 1 minute. The amount of kerosene added is 0.075 kg / t. 矿样 Add the collector ethyl thiocyanate and stir for 2 minutes. The amount of ethyl thiocyanate added is 0.075 kg / t. 矿样 Add pine oil (a foaming agent) and stir for 3 minutes. The amount of pine oil added is 0.04 kg / t. 矿样 Flotation; the flotation process adopts a closed-loop process of one roughing, two cleaning, and one scavenging step.

[0137] The above-mentioned closed-circuit process of one rougher, two cleaners, and one scavenger is as follows: the tailings from the first cleaning and the concentrate from the first scavenger are returned to the feed for the rougher, and the tailings from the second cleaning are returned to the feed for the first cleaning. After the closed-circuit process experiment, a copper-molybdenum mixed concentrate is finally obtained.

[0138] (3) Deflocculation of copper-molybdenum mixed concentrate

[0139] The pH of the copper-molybdenum mixed concentrate was adjusted to 8.0 using a 2% sodium hydroxide solution, and the mixture was stirred for 5 minutes to obtain the deflocculated copper-molybdenum mixed concentrate. The copper grade in the concentrate was 13.12%, with a copper recovery rate of 89.08%, and the molybdenum grade was 2.01%, with a molybdenum recovery rate of 72.26%.

[0140] (4) Copper-molybdenum separation

[0141] After deflocculation, the copper-molybdenum mixed concentrate enters a flotation cell for copper-molybdenum separation. The flotation speed is 1800 rpm, and sodium sulfide, an inhibitor, is added and stirred for 10 minutes. The amount of sodium sulfide added is 8.0 kg / t. 矿样 Add kerosene as a collector and stir for 3 minutes. The amount of kerosene added is 0.24 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.10 kg / t. 矿样 The flotation process employs a closed-circuit process consisting of one roughing stage, four finishing stages, and two sweeping stages.

[0142] The aforementioned closed-circuit process of one rougher, four cleaners, and two scavengers involves returning the tailings from the first cleaner and the first scavenger to the rougher feed, the tailings from the second cleaner to the first cleaner feed, the concentrate from the second scavenger to the first scavenger feed, the tailings from the third cleaner to the second cleaner feed, and the tailings from the fourth cleaner to the third cleaner feed. After closed-circuit process experiments, the final separated copper and molybdenum concentrates were obtained.

[0143] The molybdenum concentrate has a molybdenum grade of 30.02% and a recovery rate of 58.27%, while the copper concentrate has a copper grade of 14.14% and a copper recovery rate of 99.99%.

[0144] Example 5

[0145] This embodiment provides a method for comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore. The ore sample containing molybdenite and chalcopyrite in this embodiment is prepared by mixing 90% quartz (-0.012mm), 90% molybdenite (-0.011mm), and 90% chalcopyrite (-0.010mm) at a mass ratio of 48:1:1, resulting in an ore sample with 96% quartz, 2% molybdenite, and 2% chalcopyrite, containing 1.04% molybdenum and 0.61% copper. All contents refer to mass percentages. The method includes the following steps:

[0146] (1) Selective flocculation

[0147] Add the mineral sample and water to the mixing tank to prepare a 5% slurry. Stir for 5 minutes to fully wet the minerals. During stirring, add 10% sulfuric acid solution dropwise to adjust the pH of the slurry to 5.0. Add sodium hexametaphosphate dispersant and stir for 3 minutes. The amount of sodium hexametaphosphate added is 1.2 kg / t. 矿样 Then add flocculant poly(acrylamide-dimethylaminoethyl methacrylate-tetradecyl glycoside), at a dosage of 0.04 kg / t. 矿样 The mixture was stirred for 5 minutes at a stirring speed of 900 rpm to obtain a mixed slurry. The flocculant used in this embodiment is the flocculant from Example 2.

[0148] (2) Copper-molybdenum mixed flotation

[0149] The mixed slurry after the above treatment is fed into a flotation cell for flotation at a speed of 1600 rpm. Kerosene, the collector, is added and stirred for 3 minutes at a rate of 0.15 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.05 kg / t. 矿样 After 4 minutes of flotation, a copper-molybdenum mixed concentrate was obtained.

[0150] (3) Deflocculation of copper-molybdenum mixed concentrate

[0151] The pH of the copper-molybdenum mixed concentrate was adjusted to 8.0 using a 2% sodium hydroxide solution, and the mixture was stirred for 5 minutes at a stirring speed of 500 rpm to obtain the deflocculated copper-molybdenum mixed concentrate.

[0152] The copper-molybdenum mixed concentrate has a molybdenum grade of 7.97% and a molybdenum recovery rate of 82.7%, a copper grade of 4.55% and a copper recovery rate of 80.9%.

[0153] (4) Copper-molybdenum separation

[0154] The deflocculated copper-molybdenum mixed concentrate was fed into a flotation cell for copper-molybdenum separation. The flotation speed was 1600 rpm, and sodium sulfide, an inhibitor, was added and stirred for 5 minutes at a rate of 1.0 kg / t. 矿样 Add kerosene as a collector and stir for 3 minutes. The amount of kerosene added is 0.10 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.08 kg / t. 矿样 The flotation process lasted for 5 minutes, yielding molybdenum concentrate and copper concentrate. The molybdenum concentrate had a molybdenum grade of 30.73% and a recovery rate of 81.56%, while the copper concentrate had a copper grade of 17.61% and a copper recovery rate of 74.22%.

[0155] The inventors conducted numerous experiments during their research, and some of the less effective solutions are listed below as comparative examples:

[0156] Comparative Example 1

[0157] This comparative example provides a method for the comprehensive recovery and separation of copper and molybdenum in copper-molybdenum ore. The ore sample containing molybdenite and chalcopyrite in this example is the same as that in Example 3, and will not be described again here. The method includes:

[0158] (1) Selective flocculation

[0159] Mineral sample and water were added to a mixing tank to prepare a 5% slurry. The mixture was stirred for 5 minutes to fully wet the minerals. During the stirring process, 10% sulfuric acid solution was added dropwise to adjust the pH of the slurry to 4.0. Sodium hexametaphosphate was added as a dispersant and stirred for 3 minutes. The amount of sodium hexametaphosphate added was 1.2 kg / t of mineral sample. Then, poly(acrylamide-diethylaminoethyl methacrylate-dodecyl glycoside) flocculant was added at a rate of 0.04 kg / t of mineral sample. The mixture was stirred for 5 minutes to obtain a mixed slurry. The flocculant used in this comparative example is the flocculant from Example 1.

[0160] (2) Copper-molybdenum mixed flotation

[0161] The mixed slurry after the above treatment is fed into a flotation cell for flotation at a speed of 1600 rpm. Kerosene, the collector, is added and stirred for 3 minutes at a rate of 0.15 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.05 kg / t. 矿样 After 4 minutes of flotation, a copper-molybdenum mixed concentrate was obtained.

[0162] The copper-molybdenum mixed concentrate has a molybdenum grade of 8.28% and a molybdenum recovery rate of 86.7%, and a copper grade of 4.82% and a copper recovery rate of 81.5%.

[0163] (3) Copper-molybdenum separation

[0164] The above-mentioned copper-molybdenum mixed concentrate was subjected to copper-molybdenum separation at a flotation speed of 1600 rpm. Sodium sulfide, an inhibitor, was added and stirred for 5 minutes at a rate of 1.0 kg / t. 矿样 Add kerosene as a collector and stir for 3 minutes. The amount of kerosene added is 0.10 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.08 kg / t. 矿样 The flotation process lasted 5 minutes, yielding molybdenum concentrate and copper concentrate. The molybdenum concentrate had a molybdenum grade of 27.49% and a recovery rate of 75.48%, while the copper concentrate had a copper grade of 12.29% and a copper recovery rate of 65.88%.

[0165] By comparing Example 3 and this comparative example, the recovery rates of copper and molybdenum in this comparative example were both lower than those in Example 3.

[0166] Comparative Example 2

[0167] This comparative example provides a method for the comprehensive recovery and separation of copper and molybdenum in copper-molybdenum ore. The ore sample containing molybdenite and chalcopyrite in this example is the same as that in Example 4, and will not be described again here. The method includes:

[0168] (1) Flocculation and flotation

[0169] Add the mineral sample and water to the flotation cell to prepare a 25% slurry. Stir for 5 minutes to fully wet the minerals. During stirring, add 10% sulfuric acid solution dropwise to adjust the pH of the slurry to 4.2. Add sodium hexametaphosphate dispersant and stir for 3 minutes. The amount of sodium hexametaphosphate added is 0.5 kg / t of mineral sample. Then add polyacrylamide flocculant at a rate of 0.1 kg / t. 矿样 Stir for 3 minutes.

[0170] The above-mentioned ore sample was subjected to flotation at a speed of 1800 rpm. An appropriate amount of copper sulfate activator was added, and the mixture was stirred for 3 minutes. The amount of copper sulfate added was 0.1 kg / t. 原矿 Add kerosene as a collector and stir for 1 minute. The amount of kerosene added is 0.075 kg / t. 矿样 Add the collector ethyl thiocyanate and stir for 2 minutes. The amount of ethyl thiocyanate added is 0.075 kg / t. 矿样 Add pine oil (a foaming agent) and stir for 3 minutes. The amount of pine oil added is 0.04 kg / t. 矿样 The flotation process employs a closed-circuit process consisting of one roughing stage, two cleaning stages, and one scaveng

[0171] The above-mentioned closed-circuit process of one rougher, two cleaners, and one scavenger is specifically as follows: the tailings from the first cleaning and the concentrate from the first scavenger are returned to the feed for the rougher, and the tailings from the second cleaning are returned to the feed for the first cleaning. After the closed-circuit process experiment, a copper-molybdenum mixed concentrate is finally obtained.

[0172] The copper-molybdenum mixed concentrate has a copper grade of 11.83% and a copper recovery rate of 85.81%, and a molybdenum grade of 2.00% and a molybdenum recovery rate of 67.99%.

[0173] (2) Copper-molybdenum separation

[0174] The copper-molybdenum mixed concentrate was subjected to copper-molybdenum separation at a flotation speed of 1800 rpm. Sodium sulfide, an inhibitor, was added and stirred for 10 minutes. The amount of sodium sulfide added was 8.0 kg / t. 矿样 Add kerosene as a collector and stir for 3 minutes. The amount of kerosene added is 0.24 kg / t. 矿样 Then add the foaming agent pine oil and stir for 3 minutes. The amount of pine oil added is 0.10 kg / t. 矿样 The flotation process employs a closed-circuit process consisting of one roughing stage, four finishing stages, and two sweeping stages.

[0175] The aforementioned closed-circuit process of one rougher, four cleaners, and two scavengers involves returning the tailings from the first cleaner and the first scavenger to the rougher feed, the tailings from the second cleaner to the first cleaner feed, the concentrate from the second scavenger to the first scavenger feed, the tailings from the third cleaner to the second cleaner feed, and the tailings from the fourth cleaner to the third cleaner feed. After closed-circuit process experiments, the final separated copper and molybdenum concentrates were obtained.

[0176] The molybdenum concentrate has a molybdenum grade of 25.30% and a recovery rate of 48.91%, while the copper concentrate has a copper grade of 11.48% and a copper recovery rate of 74.85%.

[0177] By comparing Example 4 and this comparative example, the separation effect of molybdenite and chalcopyrite in this comparative example is not as good as that in Example 4.

[0178] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. 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 comprehensive recovery and selective separation of copper and molybdenum in copper-molybdenum ore, characterized in that, include: Step 1: Mix the ore sample containing molybdenite and chalcopyrite with water and stir to obtain a slurry; Add a modifier to the slurry to adjust the pH to <6; then add a dispersant and continue stirring; add a pH-sensitive flocculant including hydrophobic groups and pH-sensitive groups, and continue stirring to obtain a mixed slurry; Step 2: The mixed slurry is floated using a flotation machine. First, a collector is added and stirred, then a frother is added and stirred, and then aerated flotation is performed to obtain a copper-molybdenum mixed concentrate product. Step 3: Place the copper-molybdenum mixed concentrate product into a mixing tank and stir to mix evenly; add an adjuster to adjust the pH to pH≥6, stir, and obtain the deflocculated copper-molybdenum mixed concentrate; Step 4: Add inhibitor to the deflocculated copper-molybdenum mixed concentrate and stir; then add collector and stir, then add frother and stir, and aerate and float for 3-6 minutes to obtain copper concentrate and molybdenum concentrate; In step 1, the pH-sensitive flocculant is a polyacrylamide copolymer, which includes a first structural unit and a second structural unit. The first structural unit is: The second structural unit is: R1 and R5 are each independently selected from hydrogen and methyl; R2 is selected from alkylene groups containing 1 to 3 carbon atoms; R3 and R4 are each independently selected from methyl and ethyl; and R6 is an alkyl group containing 8 to 14 carbon atoms.

2. The method according to claim 1, characterized in that, In step 1, the mass concentration of the slurry is controlled to be 5%~30%.

3. The method according to claim 1, characterized in that, In step 1, the dispersant is sodium hexametaphosphate or water glass, and the amount of dispersant added is 0.8~2 kg / t. 矿样 .

4. The method according to claim 1, characterized in that, In step 1, the amount of flocculant added is 0.04~0.4 kg / t. 矿样 .

5. The method according to claim 1, characterized in that, In step 2, the collector is one or more of kerosene or ethyl thiocyanate, and the amount of collector added is 0.05~0.25 kg / t. 矿样 .

6. The method according to claim 1, characterized in that, In step 2, the foaming agent is methyl isobutyl methanol or pine oil, and the amount of foaming agent added is 0.03~0.2 kg / t. 矿样 .

7. The method according to claim 1, characterized in that, R2 is selected from methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2(CH3)CH-).

8. The method according to claim 7, characterized in that, The weight-average molecular weight of the polyacrylamide copolymer is 70,000 to 100,000; and / or, The molar ratio of the first structural unit to the second structural unit is 1.9:1 to 5.7:1; and / or, The intrinsic viscosity of the polyacrylamide copolymer is 380–580 mL / g.

9. The method according to claim 1, characterized in that, In step 4, the inhibitor is sodium thioglycolate or sodium sulfide, and the amount of inhibitor added is 2~10 kg / t. 矿样 .

10. The method according to any one of claims 1-9, characterized in that, In step 4, the foaming agent is methyl isobutyl methanol or pine oil, and the amount of foaming agent added is 0.05~0.2 kg / t. 矿样 .

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