An adjusting agent for the flotation of porphyry copper-molybdenum ore and a method of using the same

Abstract

The application provides an adjusting agent for porphyry copper-molybdenum ore flotation and a use method thereof, and relates to the technical field of mineral processing and ore dressing. The adjusting agent comprises, calculated based on the total mass of raw materials of the adjusting agent as 100%, 20%-50% of inorganic alkaline compounds, 15%-45% of water-soluble copolymers, 5%-30% of surface complexing agents, 1%-10% of dispersing aids, and the balance of carriers. The adjusting agent provided by the application can provide a more stable flotation environment and reduce process fluctuations through the optimized proportioning and synergistic effect of the components. The selection of the components also considers environmental friendliness, which conforms to the development trend of green ore dressing technology.

Description

Technical Field

[0001] This application relates to the field of mineral processing and beneficiation technology, and in particular to a modifier for flotation of porphyry copper-molybdenum ore and its application method. Background Technology

[0002] Porphyry copper-molybdenum deposits, a core type of deposit in copper and molybdenum resource development, have complex ore compositions. Copper minerals such as chalcopyrite and bornite are finely intergrown and closely associated with molybdenite, along with abundant gangue minerals such as pyrite, quartz, feldspar, and kaolinite. During the grinding process, these minerals are prone to mud formation, worsening the flotation environment, significantly increasing the difficulty of flotation separation, and imposing stringent requirements on the selectivity of flotation collectors. Current industrial practices commonly employ mixed flotation-reseparation, preferential flotation, or equal-floatable processes to treat these ores. These processes rely on the synergistic effects of modifiers, collectors, and frothers to control the pH value of the pulp system, mineral surface characteristics, and frothing behavior. However, existing modifier systems have significant drawbacks: insufficient flotation foam stability, often manifesting as sticky foam, excessively thick foam layers, and poor fluidity, severely hindering concentrate scraping efficiency and reducing mineral separation accuracy; in pursuit of higher copper or molybdenum recovery rates, operators are often forced to increase concentrate yield, leading to increased gangue mineral inclusions, a significant decrease in concentrate grade, and increased circulating load, threatening production stability; the potential for improving copper and molybdenum recovery rates is limited, and process parameters fluctuate frequently; some traditional modifiers are used in excessive amounts, imposing a heavy environmental burden and failing to align with the development trend of green mineral processing. These problems highlight the inadequacy of existing modifiers in improving foam performance and balancing concentrate yield and recovery, necessitating the development of a new type of flotation modifier to optimize the flotation process.

[0003] To address the aforementioned problems, existing technologies urgently need improvement. Summary of the Invention The purpose of this application is to provide a modifier for flotation of porphyry copper-molybdenum ore and its application method to solve the above-mentioned problems.

[0004] To achieve the above objectives, this application adopts the following technical solution: This application provides a modifier for flotation of porphyry copper-molybdenum ore, which, based on the total mass of the raw materials of the modifier as 100%, comprises: 20%-50% inorganic alkaline compound, 15%-45% water-soluble copolymer, 5%-30% surface complexing agent, 1%-10% dispersing aid, and the balance being a carrier.

[0005] Optionally, the inorganic alkaline compound includes at least one of sodium hydroxide, sodium carbonate, and lime.

[0006] Optionally, the functional groups of the water-soluble copolymer include at least two of carboxyl, sulfonic acid, and amide groups.

[0007] Optionally, the method for preparing the water-soluble copolymer includes: preparing it by copolymerization and / or graft copolymerization of carboxyl-containing monomers, sulfonic acid-containing monomers and amide-containing monomers; The carboxyl-containing monomers include at least one of acrylic acid, methacrylic acid, maleic acid, and itaconic acid; the sulfonic acid-containing monomers include at least one of styrene sulfonic acid and its salts, allyl sulfonic acid and its salts, vinyl sulfonic acid and its salts, and 2-acrylamido-2-methylpropanesulfonic acid. The amide-containing monomer includes at least one of acrylamide, methacrylamide, and N,N-dimethylacrylamide.

[0008] Optionally, the number-average molecular weight of the water-soluble copolymer is 1 × 10⁻⁶. 4 -1×10 7 .

[0009] Optionally, the surface complexing agent includes at least one of carboxylate compounds, hydroxamic acid compounds, and sulfur-containing organic ligands; The carboxylate compounds include at least one of sodium citrate, sodium tartrate, and sodium oxalate. The hydroxamic acid compounds include at least one of octyl hydroxamic acid, benzyl hydroxamic acid, and dodecyl hydroxamic acid; The sulfur-containing organic ligand includes at least one of mercaptoacetic acid, diethyl dithiocarbamate, and thioacetamide. Optionally, the dispersing agent includes at least one of lignin sulfonate, sodium polyacrylate, and sodium polyacrylate derivatives.

[0010] Optionally, the modifier is applied to mixed flotation and / or copper-molybdenum separation flotation.

[0011] Optionally, the mixed flotation includes: Porphyry copper-molybdenum ore is ground and then mixed with water to obtain porphyry copper-molybdenum ore slurry; the modifier, the first collector and the first frother are added to the porphyry copper-molybdenum ore slurry, the pH value is adjusted to alkaline and copper-molybdenum separation flotation is carried out to obtain the first concentrate and the first tailings; The first collector and the first frother are added to the first tailings for flotation to obtain the second concentrate and the second tailings.

[0012] In the porphyry copper-molybdenum deposit, the copper grade is 0.20-1.0%, and the molybdenum grade is 0.01-0.1%. The pH value is 9-12.

[0013] The first collector includes at least one of xanthates, dithiophosphates, or thiocarbamates.

[0014] The first foaming agent includes at least one of pine oil, methyl isobutyl alcohol, or higher alcohols.

[0015] The fineness of the grinding process is such that at least 60% of the particles have a particle size of -74μm.

[0016] The concentration of the porphyry copper-molybdenum ore slurry is 25-45 wt%.

[0017] The amount of the modifier is 100-500 grams per ton of the slurry.

[0018] Optionally, the copper-molybdenum separation flotation includes: The modifier, inhibitor, second collector and second frother are added to the copper-molybdenum separation flotation feed slurry to be separated, and the copper-molybdenum separation flotation is carried out to obtain molybdenum crude concentrate and copper crude concentrate. The inhibitor includes at least one of sodium sulfide, sodium sulfite, and sodium bisulfite; The second collector includes at least one of xanthates, dithiophosphates, or thiocarbamates; The second foaming agent includes at least one of pine oil, methyl isobutyl alcohol, or higher alcohols; The amount of the modifier is 100-500 grams per ton of the slurry.

[0019] Compared with the prior art, the beneficial effects of this application include: This application provides a modifier for the flotation of porphyry copper-molybdenum ore. Through the synergistic effect of its components, the physicochemical environment of the pulp is optimized. The viscosity of the flotation froth is reduced, and its fluidity is enhanced, making concentrate scraping smoother and more efficient. Due to the effective suppression and good particle dispersion of gangue minerals, the concentrate yield is reduced, while the gangue inclusions are significantly decreased, thereby improving the grade of the copper-molybdenum concentrate. Furthermore, the recovery rates of copper and molybdenum are also improved, and the stability of the entire flotation process is enhanced. The problems of large fluctuations in copper-molybdenum recovery rates, unstable process parameters, and poor environmental friendliness of some traditional reagents in the prior art are improved in the modifier of this embodiment. Through the optimized ratio and synergistic effect of its components, this modifier can provide a more stable flotation environment and reduce process fluctuations. The selection of its components also considers environmental friendliness, conforming to the development trend of green mineral processing. The modifier provided in this application offers a comprehensive solution that not only improves the performance of flotation froth but also simultaneously improves the recovery rate of copper and molybdenum without sacrificing concentrate grade, and enhances process stability, demonstrating significant technological progress and engineering application value. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0021] Figure 1 A schematic diagram of the mixed flotation process provided for the embodiments; Figure 2 A schematic diagram of the closed-loop process for copper-molybdenum flotation in actual field production provided in Example 6; Figure 3 This is a schematic diagram of the flotation process in Example 7; Figure 4 This is a diagram showing the foam state during the flotation process in Example 7; Figure 5 This is a diagram showing the foam state during the flotation process of Comparative Example 7. Figure 6 This is a schematic diagram of the process flow for the copper-molybdenum separation flotation closed-circuit test provided in Example 9. Detailed Implementation

[0022] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0023] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0024] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0025] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0026] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0027] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0028] To better explain the technical solution provided in this application, the technical solution provided in this application will be described in general before the specific implementation.

[0029] In a first aspect, this application provides a modifier for flotation of porphyry copper-molybdenum ore, comprising, based on 100% of the total mass of the raw materials, 20%-50% of an inorganic alkaline compound, 15%-45% of a water-soluble copolymer, 5%-30% of a surface complexing agent, 1%-10% of a dispersing aid, with the balance being a carrier.

[0030] Optionally, based on the total mass of the raw materials of the modifier being 100%, the amount of the inorganic alkaline compound can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any value between 20% and 50%; the amount of the water-soluble copolymer can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, or any value between 15% and 45%; the amount of the surface complexing agent can be 5%, 10%, 15%, 20%, 25%, 30%, or any value between 5% and 30%; and the dispersing aid can be 1%, 3%, 5%, 7%, 9%, 10%, or any value between 1% and 10%.

[0031] Understandably, porphyry copper-molybdenum flotation is a specific beneficiation technology for porphyry copper-molybdenum ores. This process aims to effectively separate copper and molybdenum minerals by utilizing the differences in surface properties between copper minerals (such as chalcopyrite) and molybdenum minerals (such as molybdenite) and gangue minerals. Furthermore, through the synergistic effect of these components, the physicochemical environment of the pulp is optimized. The viscosity of the flotation froth decreases, and its fluidity increases, making concentrate scraping smoother and more efficient. Because gangue minerals are effectively suppressed and well dispersed, the concentrate yield is reduced, while the amount of gangue entrainment is significantly decreased, thereby improving the grade of the copper-molybdenum concentrate. In addition, the recovery rates of copper and molybdenum are also improved, and the stability of the entire flotation process is enhanced.

[0032] In an optional embodiment, the inorganic alkaline compound includes at least one of sodium hydroxide, sodium carbonate, and lime.

[0033] Inorganic alkaline compounds are chemical substances that exhibit alkalinity in water. In flotation operations, they are commonly used to adjust the pH of the pulp to an alkaline range, which has a positive effect on the selective flotation of some minerals and the inhibition of others.

[0034] In one alternative embodiment, the functional groups of the water-soluble copolymer include at least two of carboxyl, sulfonic acid, and amide groups.

[0035] It is understandable that water-soluble copolymers contain at least two or more functional groups from carboxyl, sulfonic acid and amide groups, which can synergistically regulate the surface properties of minerals, the double electric layer structure and foam behavior in the flotation pulp system, thereby improving unfavorable phenomena such as sticky foam, thick foam layer and entrainment of fine mud or gangue minerals during the flotation process.

[0036] In an optional embodiment, the method for preparing the water-soluble copolymer includes: preparing it by copolymerization and / or graft copolymerization of carboxyl-containing monomers, sulfonic acid-containing monomers and amide-containing monomers; The carboxyl-containing monomer includes at least one of acrylic acid, methacrylic acid, maleic acid, and itaconic acid; the sulfonic acid-containing monomer includes at least one of styrene sulfonic acid and its salts, allyl sulfonic acid and its salts, vinyl sulfonic acid and its salts, and 2-acrylamido-2-methylpropanesulfonic acid. The sulfonic acid-containing monomers include at least one of styrene sulfonic acid and its salts, allyl sulfonic acid and its salts, vinyl sulfonic acid and its salts, and 2-acrylamide-2-methylpropanesulfonic acid. The amide-containing monomer includes at least one of acrylamide, methacrylamide, and N,N-dimethylacrylamide.

[0037] In one optional embodiment, the number-average molecular weight of the water-soluble copolymer is 1 × 10⁻⁶. 4 -1×10 7 .

[0038] In one optional embodiment, the surface complexing agent includes at least one of carboxylate compounds, hydroxamic acid compounds, and sulfur-containing organic ligands; The carboxylate compounds include at least one of sodium citrate, sodium tartrate, and sodium oxalate. The hydroxamic acid compounds include at least one of octyl hydroxamic acid, benzyl hydroxamic acid, and dodecyl hydroxamic acid; The sulfur-containing organic ligand includes at least one of mercaptoacetic acid, diethyl dithiocarbamate, and thioacetamide.

[0039] In an optional embodiment, the dispersing agent includes at least one of lignin sulfonate, sodium polyacrylate, and sodium polyacrylate derivatives.

[0040] Secondly, this application also provides a method for using a modifier for flotation of porphyry copper-molybdenum ore, wherein the modifier is applied to mixed flotation and / or copper-molybdenum separation flotation.

[0041] In an optional implementation, the mixed flotation includes: Porphyry copper-molybdenum ore is ground and then mixed with water to obtain porphyry copper-molybdenum ore slurry; the modifier, the first collector and the first frother are added to the porphyry copper-molybdenum ore slurry, the pH value is adjusted to alkaline and copper-molybdenum separation flotation is carried out to obtain the first concentrate and the first tailings; The first collector and the first frother are added to the first tailings for flotation to obtain the second concentrate and the second tailings.

[0042] In one optional embodiment, the porphyry copper-molybdenum ore has a copper grade of 0.20-1.0% and a molybdenum grade of 0.01-0.1%.

[0043] Optionally, in porphyry copper-molybdenum deposits, the copper grade can be 0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.7%, 0.80%, 0.90%, 1.0%, or any value between 0.20% and 1.0%; the molybdenum grade can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, or any value between 0.01% and 0.1%.

[0044] In one alternative implementation, the pH value is 9-12.

[0045] Optionally, the pH value can be 9, 10, 11, 12, or any value between 9 and 12.

[0046] In an optional embodiment, the first collector includes at least one of xanthates, dithiophosphates, or thiocarbamates.

[0047] In an optional embodiment, the first foaming agent comprises at least one of pine oil, methyl isobutyl alcohol, or higher alcohols.

[0048] In an optional embodiment, the fineness of the grinding is such that at least 60% of the particles have a particle size of -74 μm.

[0049] In an optional embodiment, the concentration of the porphyry copper-molybdenum ore slurry is 25-45 wt%.

[0050] Optionally, the concentration of the porphyry copper-molybdenum ore pulp can be 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, or any value between 25-45wt%.

[0051] In one optional embodiment, the amount of the modifier is 100-500 grams per ton of the slurry.

[0052] Optionally, the dosage of the modifier can be 100 grams per ton of the slurry, 150 grams per ton of the slurry, 200 grams per ton of the slurry, 250 grams per ton of the slurry, 300 grams per ton of the slurry, 350 grams per ton of the slurry, 400 grams per ton of the slurry, 450 grams per ton of the slurry, 500 grams per ton of the slurry, or any value between 100 and 500 grams per ton of the slurry.

[0053] Optionally, the copper-molybdenum separation flotation includes: The modifier, inhibitor, second collector and second frother are added to the copper-molybdenum separation flotation feed slurry to be separated, and the copper-molybdenum separation flotation is carried out to obtain molybdenum crude concentrate and copper crude concentrate. The inhibitor includes at least one of sodium sulfide, sodium sulfite, and sodium bisulfite; The second collector includes at least one of xanthates, dithiophosphates, or thiocarbamates; The second foaming agent includes at least one of pine oil, methyl isobutyl alcohol, or higher alcohols; The amount of the modifier is 100-500 grams per ton of the slurry.

[0054] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0055] Example 1 This embodiment provides a modifier for the flotation of porphyry copper-molybdenum ore, comprising, by mass percentage: 35% sodium carbonate; 25% water-soluble copolymer, wherein the water-soluble copolymer is a copolymer of acrylic acid and acrylamide; 15% surface complexing agent, comprising 8% sodium citrate, 4% phenylhydroxyxamic acid and 3% mercaptoacetic acid; 8% dispersing agent, comprising 4% sodium lignosulfonate, 3% sodium polyacrylate and 1% low molecular weight sodium polyacrylate; the balance being a carrier, which is deionized water.

[0056] The number-average molecular weight of the water-soluble copolymer is 5 × 10⁻⁶. 5 The water-soluble copolymer is prepared by mixing acrylic acid and acrylamide in a ratio of 8:2 and dissolving them in deionized water. After adjusting the pH of the reaction system with sodium hydroxide, deionized water and a chelating agent (EDTA) are added to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen purging device. The mixture is stirred and nitrogen is purged to remove dissolved oxygen. After heating to 60°C and stabilizing, an initiator (ammonium persulfate) is added and reacted for 2 hours. The mixture is then dried and pulverized to obtain the final product.

[0057] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore, the process flow of which is as follows: Figure 1 As shown, the specific steps are as follows: This embodiment selects a porphyry copper-molybdenum ore as the test sample. The main minerals are chalcopyrite and molybdenite, and the gangue minerals are mainly quartz and silicate minerals. The ore has a high content of fine mud, and the froth tends to be sticky during the flotation process. The copper grade is 0.51%, and the molybdenum grade is 0.011%.

[0058] Porphyry copper-molybdenum ore was ground and then mixed with water to obtain porphyry copper-molybdenum ore slurry with a concentration of 34.2 wt%. A modifier, BK404 (collector) and No. 2 oil (frother) were added to the porphyry copper-molybdenum ore slurry at a ratio of 250 grams per ton of porphyry copper-molybdenum ore slurry to adjust the pH value to 12 for copper-molybdenum separation flotation to obtain the first concentrate (concentrate 1) and the first tailings. Collector and frother are added to the first tailings for flotation to obtain the second concentrate (concentrate 2) and the second tailings.

[0059] Example 2 The modifier for flotation of porphyry copper-molybdenum ore provided in this embodiment is the same as that in embodiment 1; the only difference from embodiment 1 is that the amount of modifier used in the method of using the modifier for flotation of porphyry copper-molybdenum ore is adjusted to 500 grams per ton of porphyry copper-molybdenum ore slurry.

[0060] Example 3 This embodiment provides a modifier for flotation of porphyry copper-molybdenum ore: The composition of the modifier is the same as in Example 1; This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore: This embodiment selects a porphyry copper-molybdenum deposit as the test sample. The copper mineral in this ore is mainly chalcopyrite, and the molybdenum mineral is mainly molybdenite. The ore has a fine grain size, and the fine mud content in the pulp after grinding is high. The copper grade of the raw ore is 0.78%, and the molybdenum grade is 0.0082%.

[0061] The process flow is the same as in Example 1. The difference from Example 1 is that the amount of adjuster used in this example is adjusted to 300 grams per ton of porphyry copper-molybdenum ore slurry.

[0062] Example 4 This embodiment provides a modifier for flotation of porphyry copper-molybdenum ore: The composition of the modifier is the same as in Example 1; This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore: This embodiment selects a porphyry copper-molybdenum ore as the test sample. The copper mineral in this ore is mainly chalcopyrite, and the molybdenum mineral is mainly molybdenite. The pulp after grinding has a high content of fine mud. The raw ore has a copper grade of 1.1% and a molybdenum grade of 0.09%.

[0063] The process flow is the same as in Example 1. The difference from Example 1 is that the amount of adjuster used in this example is adjusted to 300 grams per ton of porphyry copper-molybdenum ore slurry.

[0064] Example 5 This embodiment provides a modifier for flotation of porphyry copper-molybdenum ore: The composition of the modifier is the same as in Example 1; This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore: This embodiment selects a porphyry copper-molybdenum ore as the test sample. The copper mineral in this ore is mainly chalcopyrite, and the molybdenum mineral is mainly molybdenite. The pulp after grinding has a high content of fine mud. The raw ore has a copper grade of 0.2% and a molybdenum grade of 0.0072%.

[0065] The process flow is the same as in Example 1. The difference from Example 1 is that the amount of adjuster used in this example is adjusted to 300 grams per ton of porphyry copper-molybdenum ore slurry.

[0066] Example 6 This embodiment provides a modifier for flotation of porphyry copper-molybdenum ore: The composition of the modifier is the same as in Example 1.

[0067] This embodiment also provides a method for using the modifier for porphyry copper-molybdenum flotation, employing a closed-loop process for copper-molybdenum flotation based on actual on-site production. The process flow is as follows: Figure 2 As shown, the specific steps are as follows: A copper-molybdenum separation flotation feed from a certain concentrator was selected as the test sample. The flotation process employed a copper-molybdenum separation flotation technique. A belt conveyor sample from another concentrator was also selected as the test sample, with a raw ore copper grade of approximately 0.46% and a molybdenum grade of approximately 0.011%.

[0068] Add modifier, sodium sulfide, kerosene and No. 2 oil to the copper-molybdenum separation flotation feed slurry to be separated, and after copper-molybdenum separation flotation, molybdenum crude concentrate and copper crude concentrate are obtained.

[0069] The copper concentrate produced by the roughing process is subjected to three-stage cleaning. The aim is to fully recover the molybdenum entrained within it, thereby improving the overall molybdenum recovery rate. The molybdenum middlings produced by the cleaning process are returned to the roughing process.

[0070] The rough molybdenum concentrate obtained from the separation roughing process undergoes two-stage cleaning to improve the grade of the final molybdenum concentrate. Tailings from each stage are returned to the previous stage.

[0071] Example 7 This embodiment provides a modifier for flotation of porphyry copper-molybdenum ore: A copper-molybdenum separation flotation feed from a certain concentrator was selected as the test sample, and the flotation process adopted the copper-molybdenum separation flotation technology.

[0072] The composition of the modifier is the same as in Example 1.

[0073] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore, the process flow of which is as follows: Figure 3 As shown, the specific steps are as follows: The above-mentioned modifier, sodium sulfide, kerosene, and No. 2 oil are added to the copper-molybdenum separation flotation feed slurry to be separated. After the copper-molybdenum separation flotation is carried out, molybdenum crude concentrate and copper crude concentrate are obtained. The amount of modifier added is 10 grams per ton of slurry.

[0074] Example 8 This embodiment provides a modifier for flotation of porphyry copper-molybdenum ore: A copper-molybdenum separation flotation feed from a certain concentrator was selected as the test sample, and the flotation process adopted the copper-molybdenum separation flotation technology.

[0075] The composition of the modifier is the same as in Example 7.

[0076] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore, the specific steps of which are as follows: The above-mentioned modifier, sodium sulfide, kerosene, and No. 2 oil are added to the copper-molybdenum separation flotation feed slurry to be separated. After the copper-molybdenum separation flotation is carried out, molybdenum crude concentrate and copper crude concentrate are obtained. The amount of modifier added is 20 grams per ton of slurry.

[0077] Example 9 This embodiment provides a closed-circuit test of copper-molybdenum separation flotation using the modifier of this application. The same copper-molybdenum separation feed as in Example 7 was used for the roughing addition of the modifier. A schematic diagram of the flotation process is shown below. Figure 6 The concentration of the test pulp and the other flotation reagents were kept consistent, with only the type and amount of flotation conditioner being adjusted.

[0078] Comparative Example 1 The modifier composition provided in this comparative example for the flotation of porphyry copper-molybdenum ore is the same as that in Example 1.

[0079] This comparative example also provides a method for using a modifier in the flotation of porphyry copper-molybdenum ore, the specific steps of which are as follows: Porphyry copper-molybdenum ore was ground and mixed with water to obtain porphyry copper-molybdenum ore slurry with a concentration of 30 wt%. Kerosene and No. 2 oil were added, and the pH value was adjusted to 12 for copper-molybdenum separation flotation to obtain the first concentrate (concentrate 1) and the first tailings. Collector and frother are added to the first tailings for flotation to obtain the second concentrate (concentrate 2) and the second tailings.

[0080] Comparative Example 2 This comparative example provides a modifier with the same composition as in Example 1 for the flotation of porphyry copper-molybdenum ore.

[0081] The difference between the usage method and Example 1 is that the amount of the modifier used in the flotation of porphyry copper-molybdenum ore is adjusted to 750 grams per ton of porphyry copper-molybdenum ore slurry.

[0082] Comparative Example 3 This comparative example provides a modifier with the same composition as in Example 3 for the flotation of porphyry copper-molybdenum ore.

[0083] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore. The only difference from Example 3 is that no modifier is added in this comparative example.

[0084] Comparative Example 4 This comparative example provides a modifier with the same composition as in Example 4 for the flotation of porphyry copper-molybdenum ore.

[0085] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore. The only difference from Example 4 is that no modifier is added in this comparative example.

[0086] Comparative Example 5 This comparative example provides a modifier with the same composition as in Example 5 for the flotation of porphyry copper-molybdenum ore.

[0087] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore. The only difference from Example 5 is that no modifier is added in this comparative example.

[0088] Comparative Example 6 This embodiment provides a modifier with the same composition as in Example 6 for the flotation of porphyry copper-molybdenum ore.

[0089] This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore. The only difference from Example 6 is that no modifier is added in this comparative example.

[0090] Comparative Example 7 This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore. The only difference from Example 7 is that no modifier is added in this comparative example.

[0091] Comparative Example 8 This embodiment also provides a method for using the modifier for flotation of porphyry copper-molybdenum ore. The only difference from Example 7 is that the modifier in this comparative example is replaced with water glass, and the amount added is 150 grams per ton of slurry.

[0092] Comparative Example 9 This comparative example provides a closed-circuit test of copper-molybdenum separation flotation using the modifier of this application. The same copper-molybdenum separation flotation feed as the comparative example is used, along with the same copper-molybdenum separation closed-circuit process and the same flotation operating conditions and reagent system (except for the modifier, the other collectors, frothers, depressants and their dosages are kept the same). Only the modifier is replaced with water glass commonly used on site, with an addition amount of 150 g / t, added at the same location, and a closed-circuit test is conducted.

[0093] The comparative experimental results of Examples 1, 2, 1, and 2 are shown in Table 1: Table 1. Comparative experimental results of Examples 1-2 and Comparative Examples 1-2

[0094] As shown in Table 1, compared with the blank conditions, the flotation index of porphyry copper-molybdenum ore was significantly improved after adding the modifier described in this invention.

[0095] When the amount of modifier added was 250 g / t, the total copper recovery rate increased from approximately 85.74% under blank conditions to approximately 87.5%, and the total molybdenum recovery rate increased from approximately 57.65% to approximately 77.36%, showing a significant improvement in recovery rate. Simultaneously, the copper and molybdenum grades in the tailings decreased significantly, indicating a reduction in the loss of valuable minerals.

[0096] When the amount of modifier added is 500g / t, the recovery rates of copper and molybdenum remain at a high level, the flotation foam state is stable, the foam entrainment phenomenon is effectively suppressed, and the flotation process is easy to operate.

[0097] When the amount of modifier added is 750g / t, although the copper recovery rate does not change much, the flotation froth layer becomes thinner and the concentrate yield decreases, indicating that excessive modifier dosage has a certain impact on flotation selectivity.

[0098] Based on the above results, it can be seen that the modifier described in this invention, when added in the range of 150-500 g / t, can significantly improve the froth state of porphyry copper-molybdenum ore flotation, reduce entrainment while simultaneously increasing the recovery rate of copper and molybdenum, and significantly enhance the stability of the flotation process.

[0099] The comparative experimental results of Example 3 and Comparative Example 3 are shown in Table 2: Table 2 shows the comparative experimental results of Example 3 and Comparative Example 3.

[0100] As shown in Table 2, under the condition of adding 300 g / t of the modifier of the present invention, the copper grade in concentrate 1 is 8.01%, the copper recovery rate is 83.83%, and the molybdenum recovery rate is 79.23%; the copper grade and molybdenum grade in the tailings are reduced to 0.10% and 0.0010%, respectively, indicating that the loss of useful minerals is reduced and the flotation index is significantly improved.

[0101] The comparative experimental results of Example 4 and Comparative Example 4 are shown in Table 3: Table 3 Comparative experimental results of Example 4 and Comparative Example 4

[0102] Table 3 shows that, under the condition of adding 300 g / t of the modifier of this invention, the copper grade in concentrate 1 is 14.51%, the copper recovery rate is 81.65%, and the molybdenum recovery rate is 59.37%; the molybdenum grade in the tailings decreases to 0.0030%, and the molybdenum recovery rate is 35.18%. The results indicate that, under the conditions of this ore sample, the addition of the modifier of this invention significantly improves the enrichment of molybdenum in concentrate 1, effectively controls molybdenum loss in the tailings, and maintains a high copper recovery rate.

[0103] The comparative experimental results of Example 5 and Comparative Example 5 are shown in Table 4: Table 4. Comparative experimental results of Example 5 and Comparative Example 5

[0104] As shown in Table 4, with the addition of 300 g / t of the modifier of this invention, the molybdenum recovery rate in concentrate 1 was 50.20%, significantly higher than the 23.77% under the blank condition; the molybdenum recovery rate in tailings decreased from 60.32% to 30.63%, indicating a significant reduction in molybdenum loss. Meanwhile, the copper recovery rate in the concentrate remained at a reasonable level, demonstrating that the modifier of this invention can improve molybdenum recovery without adversely affecting copper flotation.

[0105] The comparative experimental results of Example 6 and Comparative Example 6 are shown in Table 5: Table 5 shows the comparative experimental results between Example 6 and Comparative Example 6.

[0106] As shown in Table 5, compared with the on-site production conditions, the total recovery rate of copper and molybdenum was improved after adding the modifier of the present invention, the loss of useful minerals in the tailings was reduced, and the stability of the flotation process was significantly enhanced, indicating that the modifier of the present invention is suitable for copper-molybdenum ore flotation under industrial conditions.

[0107] The comparative experimental results of Examples 7, 8, 7, and 8 are shown in Table 6. The foam state during the flotation process in Example 7 is as follows: Figure 4 As shown, the foam state during the flotation process of Comparative Example 7 is as follows: Figure 5 As shown: Table 6 shows the comparative experimental results of Examples 7-8 and Comparative Examples 7-8.

[0108] As shown in Table 6, the results indicate that when the modifier described in this invention is added to the copper-molybdenum separation flotation section, the separation effect can be effectively improved under the condition of a lower addition amount.

[0109] When the addition amount was adjusted to 10 g / t, the molybdenum grade in the molybdenum rough concentrate was significantly improved, the molybdenum recovery rate remained at a high level, and the molybdenum inclusions in the copper rough concentrate were low, resulting in good copper-molybdenum separation.

[0110] When the amount of modifier added is 20 g / t, the selectivity of copper-molybdenum separation is further enhanced, and the molybdenum content in copper rough concentrate is further reduced, but the molybdenum recovery rate decreases slightly, indicating that excessive amount of modifier added has a certain impact on the separation index.

[0111] Experimental results show that the modifier described in this invention can improve the separation effect of copper and molybdenum. Compared with water glass, it effectively reduces the yield of molybdenum rough concentrate and reduces the copper content in the molybdenum rough concentrate. Furthermore, the modifier described in this invention has the advantage of low dosage; only 10 g / t is needed to achieve good separation results.

[0112] Table 7 shows the results of closed-circuit tests for copper-molybdenum separation flotation using the modifier of this application: Table 7 Results of Closed-Circuit Tests for Copper-Molybdenum Separation and Flotation

[0113] As shown in Table 7, the addition of the modifier significantly reduces the Cu content in the molybdenum concentrate, improving both copper and molybdenum recovery rates. Furthermore, a significant reduction in foam viscosity, improved foam flow properties, and a better metallic luster are observed during flotation. This is particularly beneficial for subsequent pressure filtration. Under the same closed-circuit conditions, using the modifier of this invention (10 g / t) maintains a superior molybdenum concentrate recovery rate compared to conventional water glass, demonstrating the effectiveness of improving copper-molybdenum separation parameters at a lower dosage. Compared to the comparative example, the modifier of this invention achieves superior copper-molybdenum separation while significantly reducing the amount of modifier required, indicating a clear advantage of the modifier in copper-molybdenum separation flotation.

[0114] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0115] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A modifier for flotation of porphyry copper-molybdenum ore, characterized in that, The modifier comprises, based on the total mass of raw materials of 100%, 20%-50% inorganic alkaline compound, 15%-45% water-soluble copolymer, 5%-30% surface complexing agent, 1%-10% dispersing agent, and the balance being a carrier. The inorganic alkaline compound includes at least one of sodium hydroxide, sodium carbonate, and lime; The functional groups of the water-soluble copolymer include at least two of the following: carboxyl groups, sulfonic acid groups, and amide groups; The surface complexing agent includes at least one of carboxylic acid compounds, hydroxamic acid compounds, and sulfur-containing organic ligands; The dispersing agent includes at least one of lignin sulfonate, sodium polyacrylate, and sodium polyacrylate derivatives.

2. The conditioning agent for flotation of porphyry copper-molybdenum ore according to claim 1, characterized in that, The method for preparing the water-soluble copolymer includes: preparing it by copolymerization and / or graft copolymerization of carboxyl-containing monomers, sulfonic acid-containing monomers and amide-containing monomers.

3. The conditioning agent for flotation of porphyry copper-molybdenum ore according to claim 2, characterized in that, Carboxyl-containing monomers include at least one of acrylic acid, methacrylic acid, maleic acid, and itaconic acid.

4. The conditioning agent for flotation of porphyry copper-molybdenum ore according to claim 2, characterized in that, The sulfonic acid-containing monomers include at least one of styrene sulfonic acid and its salts, allyl sulfonic acid and its salts, vinyl sulfonic acid and its salts, and 2-acrylamide-2-methylpropanesulfonic acid.

5. The modifier for flotation of porphyry copper-molybdenum ore according to claim 2, characterized in that, The amide-containing monomer includes at least one of acrylamide, methacrylamide, and N,N-dimethylacrylamide.

6. The conditioning agent for flotation of porphyry copper-molybdenum ore according to claim 1, characterized in that, The number-average molecular weight of the water-soluble copolymer is 1×10⁻⁶. 4 -1×10 7 .

7. The conditioning agent for flotation of porphyry copper-molybdenum ore according to claim 1, characterized in that, At least one of the following conditions must be met: a. The carboxylate compound includes at least one of sodium citrate, sodium tartrate, and sodium oxalate; b. The hydroxamic acid compounds include at least one of octyl hydroxamic acid, benzyl hydroxamic acid, and dodecyl hydroxamic acid; c. The sulfur-containing organic ligand includes at least one of mercaptoacetic acid, diethyl dithiocarbamate, and thioacetamide.

8. A method of using the modifier for flotation of porphyry copper-molybdenum ore as described in claim 1, characterized in that, The modifier is used in mixed flotation and / or copper-molybdenum separation flotation.

9. The method of using the modifier for flotation of porphyry copper-molybdenum ore according to claim 8, characterized in that, The mixed flotation includes: Porphyry copper-molybdenum ore is ground and then mixed with water to obtain porphyry copper-molybdenum ore slurry; the modifier, the first collector and the first frother are added to the porphyry copper-molybdenum ore slurry, the pH value is adjusted to alkaline and copper-molybdenum separation flotation is carried out to obtain the first concentrate and the first tailings; The first collector and the first frother are added to the first tailings for flotation to obtain the second concentrate and the second tailings. And meet at least one of the following conditions: A. In the porphyry copper-molybdenum deposit, the copper grade is 0.20-1.0%, and the molybdenum grade is 0.01-0.1%; B. The pH value is 9-12; C. The first collector includes at least one of xanthates, dithiophosphates, or thiocarbamates; D. The first foaming agent includes at least one of pine oil, methyl isobutyl methanol, or higher alcohols; E. The fineness of the grinding process is such that the proportion of particles with a particle size of -74μm is not less than 60%; F. The concentration of the porphyry copper-molybdenum ore pulp is 25-45 wt%; G. The amount of the modifier is 100-500 grams per ton of the slurry.

10. The method of using the modifier for flotation of porphyry copper-molybdenum ore according to claim 8, characterized in that, The copper-molybdenum separation flotation includes: The modifier, inhibitor, second collector and second frother are added to the copper-molybdenum separation flotation feed slurry to be separated, and the copper-molybdenum separation flotation is carried out to obtain molybdenum crude concentrate and copper crude concentrate. And meet at least one of the following conditions: H. The inhibitor includes at least one of sodium sulfide, sodium sulfite, and sodium bisulfite; I. The second collector includes at least one of xanthates, dithiophosphates, or thiocarbamates; J. The second foaming agent comprises at least one of pine oil, methyl isobutyl alcohol, or higher alcohols; K. The amount of the modifier is 100-500 grams per ton of the slurry.

Images