Copper-molybdenum separation inhibitor from silkworm excrement, preparation method thereof and separation process of copper-molybdenum mixed concentrate

Abstract

The application provides a silkworm excrement source copper-molybdenum separation inhibitor and a preparation method thereof, and a separation process of copper-molybdenum mixed concentrate, and belongs to the technical field of mineral processing reagents. The preparation method of the silkworm excrement source copper-molybdenum separation inhibitor comprises the following steps: crushing silkworm excrement, activating by alkali, and grafting reaction with carbon disulfide, so that the molecule contains active groups such as dithiocarbamic acid, carboxyl, hydroxyl and aromatic heterocycle. The separation process of the copper-molybdenum mixed concentrate comprises the following steps: compounding the silkworm excrement source copper-molybdenum separation inhibitor with sodium thiosulfate, and cooperating on the copper-molybdenum mixed concentrate in an alkaline ore pulp; the sodium thiosulfate removes the surface oxidation film of chalcopyrite and forms a hydrophilic transition layer, the silkworm excrement source copper-molybdenum separation inhibitor is selectively adsorbed on the surface of chalcopyrite, and the chalcopyrite is endowed with strong hydrophilicity. The chalcopyrite is effectively inhibited in the range of pH 8-14, the molybdenite keeps good floatability, and clean and efficient copper-molybdenum separation is realized.

Description

Technical Field

[0001] This invention relates to the field of mineral processing reagents, specifically to a copper-molybdenum separation inhibitor derived from silkworm excrement and its preparation method, as well as a separation process for copper-molybdenum mixed concentrate. Background Technology

[0002] Copper-molybdenum associated minerals are one of the main sources of molybdenum resources, and the separation of copper and molybdenum minerals is usually achieved through flotation. Since chalcopyrite and molybdenite have similar natural floatability, chalcopyrite depressants must be added to achieve selective inhibition. Traditionally, inorganic depressants such as cyanides (e.g., sodium cyanide, potassium cyanide) or sodium hydrosulfide are widely used in industry. While these agents are effective in inhibiting chalcopyrite, cyanides are highly toxic, and their use and tailings treatment are strictly limited. Sodium hydrosulfide releases malodorous gases during use, has high consumption, a narrow pulp potential control window, and poor stability. In recent years, researchers have developed various organic depressants, such as thiol derivatives, dithiocarbamates, polysulfides, and modified natural polymers, some of which have shown good selective inhibition capabilities. However, existing organic depressants still have shortcomings, including complex synthetic routes, high costs, easy decomposition and inactivation under acidic or neutral conditions, insufficient selectivity, or non-specific adsorption of molybdenite. In addition, a large amount of agricultural waste, silkworm excrement, is currently mainly used as fertilizer or cheap feed, and its rich protein, amino acids and various active functional groups have not yet been utilized at a high value.

[0003] Therefore, developing a green, efficient, highly selective chalcopyrite inhibitor system with a wide range of raw material sources is of great significance for achieving clean copper-molybdenum separation and the resource utilization of agricultural waste. Summary of the Invention

[0004] In view of the technical problems existing in the background art, this application provides a silkworm excrement-derived copper-molybdenum separation inhibitor and its preparation method, as well as a separation process for copper-molybdenum mixed concentrates. Utilizing the abundant natural functional groups such as amino, carboxyl, hydroxyl, and aromatic heterocycles in silkworm excrement, a silkworm excrement-derived copper-molybdenum separation inhibitor is prepared by grafting and modifying it with carbon disulfide. By combining it with sodium thiosulfate, the two work synergistically to improve the selectivity of the inhibitor in the separation of copper-molybdenum mixed concentrates, while also possessing good environmental benefits and promising prospects for industrial application.

[0005] To achieve the above objectives, in a first aspect, the present invention proposes a method for preparing a copper-molybdenum separation inhibitor from silkworm excrement, comprising: After crushing the silkworm excrement, add it to an aqueous solution of sodium hydroxide, stir and filter to obtain filter residue; The filter residue was washed with deionized water until neutral, then sodium sulfite aqueous solution was added and kept warm. After separation, it was dried to obtain activated silkworm excrement powder. Activated silkworm excrement powder is dispersed in anhydrous ethanol or isopropanol, and sodium hydroxide is added and stirred to alkalize, resulting in alkalized silkworm excrement slurry. Carbon disulfide was added dropwise to the silkworm excrement alkalization slurry, then heated, stirred, and filtered to obtain a coarse filter cake. Wash the crude filter cake to obtain the crude product; The crude product was dispersed in deionized water, the pH was adjusted to 6.0-7.0, and after stirring and washing, it was filtered to obtain a purified filter cake. The purified filter cake was washed with alcohol, dried to constant weight, and then ground to obtain the silkworm excrement-derived copper-molybdenum separation inhibitor.

[0006] Furthermore, the solid-liquid ratio of silkworm excrement to sodium hydroxide aqueous solution is 1:(5-10), and the mass fraction of sodium hydroxide aqueous solution is 0.5%-2%; and / or, The stirring temperature during stirring filtration is 50℃-80℃, and the stirring time is 1h-3h.

[0007] Furthermore, the solid-liquid ratio of the filter residue to the sodium sulfite aqueous solution is 1:(3-5), and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 1%-5%; and / or, The insulation temperature is 60℃-90℃, and the insulation time is 0.5h-1h; and / or, The drying temperature after separation is 30℃-40℃.

[0008] Furthermore, the solid-liquid ratio of activated silkworm excrement powder to anhydrous ethanol or isopropanol is 1:(4-8); and / or, The mass ratio of sodium hydroxide to activated silkworm excrement powder is (1-3):2; and / or, The temperature for stirring and alkalizing is 20℃-40℃, and the stirring and alkalizing time is 0.5h-1h.

[0009] Furthermore, the mass ratio of carbon disulfide to activated silkworm excrement powder is (4.0-4.5):1; and / or, The heating temperature is 60℃-70℃, and the stirring time is 2h-5h; and / or, The coarse filter cake is washed 2-3 times with anhydrous ethanol.

[0010] Furthermore, the solid-liquid ratio of the crude product to deionized water is 1:(5-10); and / or, Adjust the pH to 6.0-7.0 using 1%-10% dilute hydrochloric acid, and after stirring and washing, filter for 0.5-1 hour of stirring and washing; and / or, The drying temperature after alcohol washing is 40℃-60℃; and / or, The alcohol washing process involves washing the purified filter cake once with an aqueous ethanol solution of 30%-50% by volume and once with anhydrous ethanol.

[0011] Secondly, this invention proposes a silkworm excrement-derived copper-molybdenum separation inhibitor, which is prepared by the above-mentioned method for preparing the silkworm excrement-derived copper-molybdenum separation inhibitor.

[0012] Thirdly, this invention proposes a separation process for copper-molybdenum mixed concentrate, comprising: Provide dry copper-molybdenum mixed concentrate ore, prepare copper-molybdenum mixed concentrate slurry, and then perform copper-molybdenum separation flotation; Add silkworm excrement source copper-molybdenum separation inhibitor and sodium thiosulfate, and then continue to add sodium hydroxide aqueous solution or hydrochloric acid solution to adjust the pH of the slurry system to 8-14; After adding kerosene and methyl isobutyl methanol to the slurry system in sequence, air is introduced, and the process of scraping and adding water is repeated. The floated molybdenum concentrate was collected when the cumulative flotation time was 1 min, 3 min, 6 min and 10 min, resulting in four types of molybdenum concentrate; Four types of molybdenum concentrate were filtered and dried to obtain the finished molybdenum concentrate; among them... In each ton of copper-molybdenum mixed concentrate dry ore, the dosage of silkworm excrement copper-molybdenum separation inhibitor is 3kg-10kg, and the dosage of sodium thiosulfate is 0.5kg-3kg. The silkworm excrement-derived copper-molybdenum separation inhibitor is the aforementioned silkworm excrement-derived copper-molybdenum separation inhibitor.

[0013] Furthermore, in each ton of dry copper-molybdenum mixed concentrate ore, the amount of kerosene used is 50g-100g, and the amount of methyl isobutyl methanol used is 20g-25g; and / or, The interval for scraping bubbles is 3-5 seconds, and the interval for replenishing water is 10-30 seconds.

[0014] Furthermore, the molar concentration of the sodium hydroxide aqueous solution is 0.50 mol / L–0.75 mol / L, and the molar concentration of the hydrochloric acid solution is 0.05 mol / L–0.1 mol / L; and / or, The drying temperature is 40℃-60℃.

[0015] The beneficial effects of this application are as follows: In the technical solution of this application, the inhibitor is prepared by using agricultural waste silkworm excrement as raw material, through alkali activation and carbon disulfide grafting reaction. The molecule contains active groups such as dithiocarbamic acid, carboxyl, hydroxyl, and aromatic heterocycles. The inhibitor thus prepared has a multidentate coordination structure. The thiocarbonyl group in its molecule can be converted into an active thiol group through tautomerism in alkaline slurry. The sulfur atom of the thiol group forms a spatially co-chelating site with the unconjugated nitrogen atom in the original aromatic heterocycle of silkworm excrement. This site can directionally recognize and chelate copper ions on the surface of chalcopyrite, generating a stable cyclic chelate, thereby firmly adsorbing onto the surface of chalcopyrite. The silkworm excrement-derived copper-molybdenum separation inhibitor is compounded with sodium thiosulfate and acts synergistically on copper-molybdenum mixed concentrate in alkaline slurry: sodium thiosulfate removes the oxide film on the surface of chalcopyrite and forms a hydrophilic transition layer, while the silkworm excrement-derived copper-molybdenum separation inhibitor selectively adsorbs onto the surface of chalcopyrite, giving it strong hydrophilicity. This system effectively inhibits chalcopyrite within a pH range of 8-14 while maintaining good floatability of molybdenite, achieving clean and efficient copper-molybdenum separation. The raw materials and reagents used in this system are highly biosafe, aligning with the development direction of green mining and demonstrating significant environmental benefits and promising prospects for industrial application.

[0016] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0018] Figure 1 Experimental photographs of the synthetic silkworm excrement-derived copper-molybdenum separation inhibitor provided by this invention.

[0019] Figure 2 The protonated nuclear magnetic resonance (NMR) spectrum of the copper-molybdenum separation inhibitor from silkworm excrement.

[0020] Figure 3 A flow chart of the separation process of copper-molybdenum mixed concentrate provided by the present invention.

[0021] Figure 4 This invention describes the mechanism of action between the silkworm excrement-derived copper-molybdenum separation inhibitor and chalcopyrite in the separation process of copper-molybdenum mixed concentrate. Detailed Implementation

[0022] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0024] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0025] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0026] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0027] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more (including two sets), and "multiple pieces" refers to two or more (including two pieces).

[0028] Copper-molybdenum associated minerals are one of the main sources of molybdenum resources, and the separation of copper and molybdenum minerals is usually achieved through flotation. Since chalcopyrite and molybdenite have similar natural floatability, chalcopyrite depressants must be added to achieve selective inhibition. Traditionally, inorganic depressants such as cyanides (e.g., sodium cyanide, potassium cyanide) or sodium hydrosulfide are widely used in industry. While these agents are effective in inhibiting chalcopyrite, cyanides are highly toxic, and their use and tailings treatment are strictly limited. Sodium hydrosulfide releases malodorous gases during use, has high consumption, a narrow pulp potential control window, and poor stability. In recent years, researchers have developed various organic depressants, such as thiol derivatives, dithiocarbamates, polysulfides, and modified natural polymers, some of which have shown good selective inhibition capabilities. However, existing organic depressants still have shortcomings, including complex synthetic routes, high costs, easy decomposition and inactivation under acidic or neutral conditions, insufficient selectivity, or non-specific adsorption of molybdenite. Furthermore, a large amount of agricultural waste, silkworm excrement, is currently mainly used as fertilizer or inexpensive feed, while its rich protein, amino acids, and various active functional groups have not yet been utilized at a high value. Therefore, developing a green, efficient, highly selective chalcopyrite inhibitor system with widely available raw materials is of great significance for achieving clean copper-molybdenum separation and the resource utilization of agricultural waste.

[0029] To address the aforementioned technical problems, in a first aspect, embodiments of this application provide a method for preparing a silkworm excrement-derived copper-molybdenum separation inhibitor, comprising: After crushing the silkworm excrement, add it to an aqueous solution of sodium hydroxide, stir and filter to obtain filter residue; The filter residue was washed with deionized water until neutral, then sodium sulfite aqueous solution was added and kept warm. After separation, it was dried to obtain activated silkworm excrement powder. Activated silkworm excrement powder is dispersed in anhydrous ethanol or isopropanol, and sodium hydroxide is added and stirred to alkalize, resulting in alkalized silkworm excrement slurry. Carbon disulfide was added dropwise to the silkworm excrement alkalization slurry, then heated, stirred, and filtered to obtain a coarse filter cake. Wash the crude filter cake to obtain the crude product; The crude product was dispersed in deionized water, the pH was adjusted to 6.0-7.0, and after stirring and washing, it was filtered to obtain a purified filter cake. The purified filter cake was washed with alcohol, dried to constant weight, and then ground to obtain the silkworm excrement-derived copper-molybdenum separation inhibitor.

[0030] It can be noted that silkworm excrement is rich in active functional groups such as amino, carboxyl, hydroxyl, and aromatic heterocycles. These functional groups mainly originate from crude protein, amino acids, soluble polysaccharides, and chlorophyll derivatives. The silkworm excrement is pulverized to 40-80 mesh to uniform particle size and increase the contact area with reagents, thereby improving the reaction rate. Subsequently, alkali is added for activation, breaking down the silkworm excrement fiber structure and exposing and releasing amino groups from the crude protein and amino acids, facilitating nucleophilic addition reactions with carbon disulfide. The filter residue is washed until neutral and then placed in an aqueous sodium sulfite solution for incubation. The sodium sulfite reacts with the lignin in the silkworm excrement to undergo sulfonation, loosening the cell walls and providing channels for subsequent alkali penetration. The activated silkworm excrement powder is dispersed in anhydrous ethanol or isopropanol to promote wetting and enhance the dissolution of active ingredients. Sodium hydroxide is added and stirred to provide a moderately alkaline environment, further disrupting the silkworm excrement fiber structure and promoting the release of active ingredients.

[0031] It can be explained that the abundant free amino groups in silkworm excrement react with carbon disulfide to generate dithiocarbamate groups. Simultaneously, the carboxyl groups retained in the raw material endow the molecule with strong hydration capabilities, while the hydroxyl groups provide additional hydrogen bonding sites. The aromatic ring and nitrogen-containing heterocyclic structure contribute to a large π-conjugated system. The resulting inhibitor is a small-molecule organic compound containing a polydentate coordination structure. In alkaline slurry, the thiocarbonyl group in its molecule can be converted to an active thiol group through tautomerism. The sulfur atom of this thiol group forms a spatially coordinated chelating site with the unconjugated nitrogen atom in the native aromatic heterocycle of silkworm excrement. This site can directionally recognize and chelate copper ions on the surface of chalcopyrite, generating a stable cyclic chelate, thus firmly adsorbing onto the chalcopyrite surface. At the same time, the abundant carboxyl groups retained in the molecule hydrolyze to carboxylate ions under alkaline conditions, and the hydroxyl groups also enhance the hydration layer on the surface of the ore particles, collectively endowing chalcopyrite with strong hydrophilicity. However, due to differences in electronic configuration, molybdenum ions on the surface of molybdenite are difficult to form a stable cyclic structure with this chelating site. Therefore, this inhibitor exhibits excellent selective inhibition ability against chalcopyrite.

[0032] In some embodiments, the solid-liquid ratio of silkworm excrement to sodium hydroxide aqueous solution is 1:(5-10), and the mass fraction of sodium hydroxide aqueous solution is 0.5%-2%.

[0033] In this embodiment, the sodium hydroxide aqueous solution breaks down the structure of silkworm excrement fibers, exposing and releasing the crude protein and amino acids in the silkworm excrement.

[0034] In some embodiments, the stirring temperature in the stirred filtration is 50℃-80℃, and the stirring time in the stirred filtration is 1h-3h.

[0035] In this embodiment, the stirring temperature is controlled at 50℃-80℃. Gentle heating promotes the alkalization reaction of sodium hydroxide on silkworm excrement, which helps maintain the activity of heat-sensitive components, and the reaction is mild and controllable. The stirring time is controlled at 1h-3h to peel off the cell walls of the fibers in the silkworm excrement, accelerate the penetration of the alkali solution into the interior of the silkworm excrement, and improve the extraction efficiency of protein.

[0036] In some embodiments, the solid-liquid ratio of the filter residue to the sodium sulfite aqueous solution is 1:(3-5), and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 1%-5%.

[0037] In this embodiment, sodium sulfite is used to prevent the oxidation of active ingredients in proteins and to assist in the dissolution of lignin. The solid-liquid ratio of the filter residue to the sodium sulfite aqueous solution is controlled at 1:(3-5), and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 1%-5%. Within this range, the concentration of sodium sulfite is suitable, consuming dissolved oxygen in the solution, thereby inhibiting the oxidation of amino, hydroxyl, and carboxyl groups in the active substances.

[0038] In some embodiments, the insulation temperature is 60℃-90℃, and the insulation time is 0.5h-1h.

[0039] In this embodiment, the temperature for heat preservation is controlled at 60℃-90℃ and the heat preservation time is 0.5h-1h. This promotes the sulfonation reaction between sodium sulfite and lignin in silkworm excrement, making the cell wall loose and providing a channel for subsequent alkali solution penetration. The temperature is controlled below the temperature of protein thermal degradation to preserve the integrity of active groups such as amino groups.

[0040] In some embodiments, the drying temperature after separation is 30°C-40°C.

[0041] In this embodiment, the drying temperature after separation is controlled at 30℃-40℃, which is lower than the denaturation temperature of proteins, so as to maintain the activity of amino acids in the crude protein and amino acid components of silkworm excrement.

[0042] In some embodiments, the solid-liquid ratio of activated silkworm excrement powder to anhydrous ethanol or isopropanol is 1:(4-8).

[0043] In this embodiment, the solid-liquid ratio of activated silkworm excrement powder to anhydrous ethanol or isopropanol is controlled to be 1:(4-8). This solid-liquid ratio promotes the wetting of activated silkworm excrement powder and improves the dissolution efficiency of effective ingredients, while reducing the burden on subsequent processes caused by excessive solvent.

[0044] In some embodiments, the mass ratio of sodium hydroxide to activated silkworm excrement powder is (1-3):2.

[0045] In this embodiment, the mass ratio of sodium hydroxide to activated silkworm excrement powder is controlled at (1-3):2 to provide a moderately alkaline environment, which is sufficient to destroy the structure of silkworm excrement fibers and promote the release of effective ingredients, while reducing the degradation of target active substances or the increase of side reactions caused by excessive alkali.

[0046] In some embodiments, the temperature for stirring and alkalizing is 20℃-40℃, and the stirring and alkalizing time is 0.5h-1h.

[0047] In this embodiment, the temperature for stirring and alkalizing is 20℃-40℃, and the stirring and alkalizing time is 0.5h-1h. Within this temperature and time range, the silkworm excrement cell walls are fully disrupted, and the effective components such as proteins and polyphenols are fully dissolved and moderately hydrolyzed, exposing amino groups and promoting subsequent reactions.

[0048] In some embodiments, the mass ratio of carbon disulfide to activated silkworm excrement powder is (4.0-4.5):1.

[0049] In this embodiment, carbon disulfide undergoes nucleophilic addition with the amino groups in activated silkworm excrement powder to generate a grafted product containing dithiocarbamic acid groups. The mass ratio of carbon disulfide to activated silkworm excrement powder is controlled at (4.0-4.5):1. At this mass ratio, the degree of amino grafting is high, resulting in a large number of dithiocarbamic acid groups, which strengthens the chemical adsorption capacity for chalcopyrite and improves the separation efficiency between chalcopyrite and molybdenite.

[0050] In some embodiments, the heating temperature is 60°C-70°C, and the stirring time is 2h-5h.

[0051] In this embodiment, the heating temperature is controlled at 60℃-70℃ to increase the kinetic energy of the reaction between the amino group and carbon disulfide, thereby increasing the reaction rate while protecting the structural integrity of the generated dithiocarbamate group. Under alkaline conditions, the amino group is easily oxidized to nitroso, nitro, or azo compounds, losing its nucleophilic addition ability with carbon disulfide. Nitrogen protection can inhibit the oxidation of the amino group, maintaining its activity, and simultaneously inhibiting the oxidation of the generated dithiocarbamate group. Stirring the reaction for 2-5 hours promotes the combination of the amino group and carbon disulfide, increasing the rate of its nucleophilic addition reaction.

[0052] In some embodiments, the crude filter cake is washed 2-3 times with anhydrous ethanol.

[0053] In this embodiment, the crude filter cake is washed 2-3 times with anhydrous ethanol to remove fat-soluble impurities and increase the relative content of active ingredients.

[0054] In some embodiments, the solid-liquid ratio of crude product to deionized water is 1:(5-10), the pH is adjusted to 6.0-7.0 by using 1%-10% dilute hydrochloric acid, and the stirring and washing time during filtration is 0.5h-1h.

[0055] In this embodiment, the crude product is dispersed in deionized water, and the pH is adjusted to 6.0-7.0 using 1%-10% dilute hydrochloric acid. The stirring and washing time is controlled to be 0.5-1h to remove unreacted carbon disulfide, inorganic salts and free alkali, thereby improving the purity of the product.

[0056] In some embodiments, the drying temperature after alcohol washing is 40°C-60°C.

[0057] In this embodiment, the drying temperature after alcohol washing is 40℃-60℃. While removing the alcohol components, the activity of the organic macromolecules in the silkworm excrement copper-molybdenum separation inhibitor is maintained, the chelation with copper is strengthened, and the selectivity during copper-molybdenum separation is improved.

[0058] In some embodiments, the alcohol washing process includes washing the purified filter cake once with an aqueous ethanol solution of 30%-50% by volume and once with anhydrous ethanol.

[0059] In this embodiment, the purified filter cake is first washed with a 30%-50% aqueous ethanol solution to remove some polar impurities, such as inorganic salts, sugars, water-soluble pigments, low-molecular-weight organic acids, and some proteins. The purified filter cake is then washed again with anhydrous ethanol to remove oils, waxes, chlorophyll, resins, some alkaloids, and water-insoluble organic matter, while retaining the active ingredients in the silkworm excrement copper-molybdenum separation inhibitor.

[0060] Secondly, this invention proposes a silkworm excrement-derived copper-molybdenum separation inhibitor, which is prepared by the above-mentioned method for preparing the silkworm excrement-derived copper-molybdenum separation inhibitor.

[0061] It is understood that the silkworm excrement copper-molybdenum separation inhibitor has all the beneficial effects of the above-mentioned preparation methods of the silkworm excrement copper-molybdenum separation inhibitor, and will not be elaborated here.

[0062] Thirdly, this invention proposes a separation process for copper-molybdenum mixed concentrate, comprising: Provide dry copper-molybdenum mixed concentrate ore, prepare copper-molybdenum mixed concentrate slurry, and then perform copper-molybdenum separation flotation; Add silkworm excrement source copper-molybdenum separation inhibitor and sodium thiosulfate, and then continue to add sodium hydroxide aqueous solution or hydrochloric acid solution to adjust the pH of the slurry system to 8-14; After adding kerosene and methyl isobutyl methanol to the slurry system in sequence, air is introduced, and the process of scraping and adding water is repeated. The floated molybdenum concentrate was collected when the cumulative flotation time was 1 min, 3 min, 6 min and 10 min, resulting in four types of molybdenum concentrate; Four types of molybdenum concentrate were filtered and dried to obtain the finished molybdenum concentrate; among them... In each ton of copper-molybdenum mixed concentrate dry ore, the dosage of silkworm excrement copper-molybdenum separation inhibitor is 3kg-10kg, and the dosage of sodium thiosulfate is 0.5kg-3kg. The silkworm excrement-derived copper-molybdenum separation inhibitor is the aforementioned silkworm excrement-derived copper-molybdenum separation inhibitor.

[0063] In this embodiment, the slurry is placed in an XFG-3 flotation machine for copper-molybdenum separation flotation. Water is added to bring the liquid level to a suitable position. The impeller speed of the flotation machine is set to 2000 r / min, and the slurry is conditioned for 2 minutes to ensure that the minerals to be processed are uniformly dispersed in the slurry, providing favorable conditions for the inhibition of chalcopyrite and the flotation of molybdenum. The silkworm excrement-derived copper-molybdenum separation inhibitor has poor stability under neutral and acidic conditions and is prone to decomposition. Adjusting the pH of the slurry system to 8-14, the resulting inhibitor molecule contains a dithiocarbamic acid structure. In alkaline slurry, it can release active thiol groups through tautomerism, forming spatially coordinated chelate sites with nitrogen atoms in the native aromatic heterocycles of silkworm excrement. This allows for the directional recognition and firm chelation of copper ions on the surface of chalcopyrite, generating stable cyclic chelates. Chalcopyrite is effectively inhibited while molybdenite retains good natural floatability, achieving excellent copper-molybdenum separation. Kerosene and methyl isobutyl methanol were used for flotation separation. The timing and dosage of reagent addition were controlled, and the floated molybdenum concentrate was collected periodically to achieve multiple and efficient recovery of molybdenum ore, thereby improving the recovery rate. The concentrate was then dried to obtain the finished molybdenum concentrate.

[0064] It can be explained that the silkworm excrement-derived copper-molybdenum separation inhibitor is a small-molecule organic compound containing a polydentate coordination structure. In alkaline slurry, the thiocarbonyl group in its molecule can be converted into an active thiol group through tautomerism. The sulfur atom of this thiol group forms a spatially coordinated chelating site with the unconjugated nitrogen atom in the original aromatic heterocycle of silkworm excrement. This site can directionally recognize and chelate copper ions on the surface of chalcopyrite, generating a stable cyclic chelate, thus firmly adsorbing onto the chalcopyrite surface. Simultaneously, the abundant carboxyl groups in the molecule hydrolyze to carboxylate ions under alkaline conditions, and the hydroxyl groups also enhance the hydration layer on the particle surface, collectively endowing chalcopyrite with strong hydrophilicity. However, due to differences in electronic configuration, molybdenum ions on the surface of molybdenite are difficult to form a stable cyclic structure with this chelating site. Therefore, this inhibitor exhibits excellent selective inhibition ability against chalcopyrite.

[0065] It can be explained that sodium thiosulfate, as a complexing agent for copper ions, can moderately remove the hydrophobic copper oxide film formed on the surface of chalcopyrite due to oxidation. Simultaneously, by forming a soluble copper thiosulfate complex, it provides a clean and activated adsorption interface for the silkworm excrement copper-molybdenum separation inhibitor, reducing the steric hindrance of inhibitor adsorption. Sodium thiosulfate, by stabilizing the slurry potential, prevents premature oxidative decomposition of the dithiocarbamic acid structure in the silkworm excrement copper-molybdenum separation inhibitor, thereby extending the effective action window of the inhibitor. Controlling the dosage of the silkworm excrement copper-molybdenum separation inhibitor to 3-10 kg per ton of copper-molybdenum concentrate ensures high binding efficiency of the inhibitor to the active sites on the chalcopyrite surface without excessive dosage, maintaining the hydrophobic properties of molybdenite and achieving a balance in the separation of chalcopyrite and molybdenite. Sodium thiosulfate has a strong complexing ability and can partially dissolve copper ions on the surface of chalcopyrite to form soluble copper thiosulfate complexes. By controlling the amount of sodium thiosulfate in each ton of copper-molybdenum concentrate to 0.5 kg-3 kg, it is beneficial to maintain the chelated adsorption layer formed on the surface of chalcopyrite by the silkworm excrement copper-molybdenum separation inhibitor, thereby enhancing the inhibitory effect of the silkworm excrement copper-molybdenum separation inhibitor on chalcopyrite.

[0066] In some embodiments, the amount of kerosene used in each ton of copper-molybdenum mixed concentrate dry ore is 50g-100g, and the amount of methyl isobutyl methanol used is 20g-25g.

[0067] In this embodiment, the slurry is prepared in stages. First, sufficient kerosene is dispersed in the slurry according to the specified ratio, causing it to collide with molybdenite particles to form a film and anchor them. After 1 minute, a foaming agent, methyl isobutyl methanol, is added in the same ratio, allowing it to adsorb onto the surface of the mineral-loaded bubbles and form a hydration film. After 3 minutes, air is introduced to provide an air-water interface, maintaining the uniform and fine state of the bubbles, increasing the mineral adhesion area, stabilizing the foam structure, and improving the efficiency of scraping and collecting the mineral particles loaded on the bubbles.

[0068] In some embodiments, the interval for scraping bubbles is 3s-5s, and the interval for replenishing water is 10s-30s.

[0069] In this embodiment, the flotation foam is scraped off every 3-5 seconds to evenly control its thickness and uniformity, thereby reducing foam accumulation on the slurry surface and improving the flotation effect. Water is added every 10-30 seconds to ensure sufficient water in the flotation equipment, providing favorable conditions for the successful flotation of molybdenum ore.

[0070] In some embodiments, the molar concentration of the sodium hydroxide aqueous solution is 0.50 mol / L-0.75 mol / L, and the molar concentration of the hydrochloric acid solution is 0.05 mol / L-0.1 mol / L.

[0071] In this embodiment, the molar concentration of sodium hydroxide aqueous solution is controlled at 0.50 mol / L-0.75 mol / L, and the molar concentration of hydrochloric acid solution is controlled at 0.05 mol / L-0.1 mol / L. The pH of the slurry system is uniformly and gently regulated to maintain the system in a stable state and preserve the activity of the functional groups in the silkworm excrement copper-molybdenum separation inhibitor.

[0072] In some embodiments, the drying temperature is 40°C-60°C.

[0073] In this embodiment, the drying temperature is controlled at 40℃-60℃, which preserves the sulfur content in molybdenum disulfide while evaporating moisture, inhibiting its oxidative decomposition and helping to maintain the quality of the finished molybdenite product.

[0074] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0075] I. Preparation Method Example 1 1. Preparation of a copper-molybdenum separation inhibitor derived from silkworm excrement: The dried silkworm excrement was pulverized to 40 mesh and added to a 1% sodium hydroxide aqueous solution at a solid-liquid ratio of 1:9. The mixture was stirred at 60°C for 3 hours, filtered, and the filter residue was collected. The filter residue was washed with deionized water until neutral, and then a 5% sodium sulfite aqueous solution was added at a solid-liquid ratio of 1:4. The mixture was kept at 60°C for 1 hour, centrifuged, and the resulting solid was vacuum dried at 30°C to obtain activated silkworm excrement powder. Activated silkworm excrement powder was dispersed in anhydrous ethanol at a solid-liquid ratio of 1:5, and sodium hydroxide solid of the same mass as the activated silkworm excrement powder was added. The mixture was stirred and alkalized at 30°C for 1 hour to obtain alkalized silkworm excrement slurry. Carbon disulfide was added dropwise to the alkalized silkworm excrement slurry. The amount of carbon disulfide added was 4 times the mass of the activated silkworm excrement powder. Then the temperature was raised to 60°C and the reaction was continued to be stirred for 4 hours under nitrogen protection. The mixture was then filtered and the crude filter cake was washed 3 times with anhydrous ethanol to obtain the crude product. The crude product was dispersed in deionized water at a solid-liquid ratio of 1:10. The pH was adjusted to 6.0 with 5% hydrochloric acid. After stirring and washing for 30 minutes, the mixture was filtered. The purified filter cake was washed once each with 50% aqueous ethanol and anhydrous ethanol. The washed solid was then dried in a vacuum drying oven at 40°C to constant weight and ground through a 100-mesh sieve to obtain the silkworm excrement copper-molybdenum separation inhibitor of Example 1.

[0076] 2. Separation processes for copper-molybdenum mixed concentrates, such as... Figure 3 As shown: 1 kg of copper-molybdenum mixed concentrate dry ore was provided, and 3 L of copper-molybdenum mixed concentrate slurry was prepared. The slurry was then placed in an XFG-3 flotation machine for copper-molybdenum separation flotation. The impeller speed of the flotation machine was set to 2000 r / min, and the slurry was conditioned for 2 minutes. Add 2kg / t 混精矿 Sodium thiosulfate and 5 kg / t 混精矿 The copper-molybdenum separation inhibitor from silkworm excrement was used to adjust the pH of the slurry system to 8 using a 0.75 mol / L sodium hydroxide aqueous solution, wherein kg / t 混精矿 This indicates the amount of the substance used per ton of dry copper-molybdenum mixed concentrate. First, add 100g / t to the slurry system 混精矿 Add 25g / t of kerosene after 1 minute. 混精矿 Methyl isobutyl methanol, of which g / t 混精矿 This indicates the amount of the substance used per ton of dry copper-molybdenum mixed concentrate. After adding methyl isobutyl methanol for 3 minutes, open the air valve to introduce air and begin flotation. Skim off the bubbles every 5 seconds and add water every 30 seconds, repeating the process. Collect the floated molybdenum concentrate at cumulative flotation times of 1 minute, 3 minutes, 6 minutes, and 10 minutes, respectively, to obtain four batches of molybdenum concentrate. The molybdenum concentrate was filtered, dried in an oven at 60℃, weighed, and the recovery rate was calculated. The recovery rate of molybdenite was calculated by dividing the total mass of molybdenite in the molybdenum concentrate by the total mass of molybdenite in the original copper-molybdenum mixed concentrate. The recovery rate of chalcopyrite was calculated by dividing the mass of chalcopyrite in the molybdenum concentrate by the total mass of chalcopyrite in the original copper-molybdenum mixed concentrate. The content of each component in the mixed concentrate was determined, and the results are shown in Table 1 below.

[0077] Table 1. Measurement results of mineral content in copper-molybdenum mixed concentrate. Comparative Example 1 Unlike Example 1, no silkworm excrement-derived copper-molybdenum separation inhibitor was added during the separation of the copper-molybdenum mixed concentrate. Otherwise, it was largely the same as Example 1 and will not be repeated here. The recovery rates of molybdenite and chalcopyrite in Comparative Example 1 were calculated.

[0078] Comparative Examples 2-5 Unlike Example 1, the type of copper-molybdenum separation inhibitor added in the separation of the copper-molybdenum mixed concentrate is different. Otherwise, it is roughly the same as Example 1 and will not be repeated here. The recovery rates of molybdenite and chalcopyrite in Comparative Examples 2-5 are calculated.

[0079] The effects of different copper-molybdenum separation inhibitors prepared in Example 1 and Comparative Examples 1-5 on the recovery rate are shown in Table 2.

[0080] Table 2. Effect of Inhibitor Type on Recovery Rate Table 2 shows that without the introduction of a copper-molybdenum separation inhibitor, kerosene, as a collector, preferentially collects chalcopyrite. The introduction of traditional inorganic chalcopyrite inhibitors is inefficient in inhibiting chalcopyrite, thus failing to achieve copper-molybdenum separation. However, the copper-molybdenum separation reagent system in Example 1, consisting of sodium thiosulfate and a silkworm excrement-derived copper-molybdenum separation inhibitor, can efficiently inhibit chalcopyrite. The molybdenum recovery rate in the molybdenum concentrate reaches 85%, while the chalcopyrite recovery rate is only 12% of the total chalcopyrite content. This achieves highly efficient and selective inhibition of chalcopyrite, thereby achieving the goal of copper-molybdenum separation.

[0081] Examples 2-7 Unlike Example 1, the pH of the slurry system in the separation of copper-molybdenum mixed concentrate is different. Otherwise, it is roughly the same as Example 1 and will not be repeated here. The recovery rates of molybdenite and chalcopyrite in Examples 2-18 are calculated.

[0082] The effect of pH on the recovery rate of different slurry systems prepared in Examples 1-7 is shown in Table 3.

[0083] Table 3 Effect of pH on recovery rate Table 3 shows that as the slurry pH increased from 8 to 14, the recovery rate of chalcopyrite gradually decreased from 12% to 8% and then stabilized, while the recovery rate of molybdenite increased from 85% to 89% and then remained at that level. This indicates that under alkaline conditions, the selective inhibition ability of the silkworm excrement-derived copper-molybdenum separation inhibitor and sodium thiosulfate synergistic system on chalcopyrite increases with increasing pH. When the pH reaches 10 and above, the recovery rate of chalcopyrite drops below 9%, while the recovery rate of molybdenite reaches 89% and above, maintaining high floatability. This indicates that the pH range of 11-14 is the optimal separation range. Considering both the inhibition effect and the convenience of industrial operation, the preferred pH range is 8-14.

[0084] Examples 8-11 and Comparative Examples 6-11 The difference from Example 1 is the amount of sodium thiosulfate used in the separation of copper-molybdenum mixed concentrate. The rest is roughly the same as in Example 1, and will not be repeated here. The recovery rates of molybdenite and chalcopyrite in Examples 2-18 are calculated.

[0085] The effects of different amounts of sodium thiosulfate used in Examples 1, 8-11, and Comparative Examples 6-11 on the recovery rate are shown in Table 4.

[0086] Table 4 Effect of sodium thiosulfate dosage on recovery rate Table 4 shows that the dosage of sodium thiosulfate has a significant impact on the copper-molybdenum separation effect. In Comparative Example 6, the dosage of sodium thiosulfate was 0, resulting in a chalcopyrite recovery rate as high as 31% and a molybdenite recovery rate of only 74%. This indicates that without the addition of sodium thiosulfate, the silkworm excrement-derived copper-molybdenum separation inhibitor, when used alone, has a weak inhibitory effect on chalcopyrite, and molybdenite is also inhibited to some extent, resulting in an unsatisfactory copper-molybdenum separation effect. In Examples 8-11, as the dosage of sodium thiosulfate increased from 0.5 kg / t... 混精矿 Increased to 3kg / t 混精矿 The recovery rate of chalcopyrite gradually decreased from 15% to 7%, while the recovery rate of molybdenite increased from 80% to 92%, indicating that an appropriate amount of sodium thiosulfate can synergistically enhance the selective inhibition of chalcopyrite by inhibiting the copper-molybdenum separation of silkworm excrement. In particular, in Comparative Example 9, the sodium thiosulfate dosage was 3.5 kg / t. 混精矿 The brass recovery rate was similar to that of Example 11, where the sodium thiosulfate dosage was 3.0 kg / t. 混精矿 Inconsistent timing actually leads to waste of reagents. In Comparative Examples 10-11, the amount of sodium thiosulfate used exceeded 3.5 kg / t. 混精矿 Subsequently, the chalcopyrite recovery rate actually rebounded from 7% to 24%. This is because excess sodium thiosulfate has a strong complexing ability, which can partially dissolve copper ions on the surface of chalcopyrite, forming soluble copper thiosulfate complexes. This disrupts the stable chelated adsorption layer formed on the chalcopyrite surface by the silkworm excrement copper-molybdenum separation inhibitor. Therefore, the suitable dosage range for sodium thiosulfate is 0.5-3 kg / t. 混精矿 Preferred weight: 2-3 kg / t 混精矿 .

[0087] Examples 12-14 and Comparative Examples 12-15 Unlike Example 1, the amount of silkworm excrement copper-molybdenum separation inhibitor used in the separation of copper-molybdenum mixed concentrate is different. Other aspects are roughly the same as in Example 2, and will not be repeated here. The recovery rates of molybdenite and chalcopyrite in Examples 12-14 and Comparative Examples 12-15 are calculated.

[0088] The effects of different amounts of silkworm excrement copper-molybdenum separation inhibitors prepared in Examples 12-14 and Comparative Examples 12-15 on the recovery rate are shown in Table 5.

[0089] Table 5. Effect of the dosage of the separation inhibitor for copper-molybdenum separation from silkworm excrement on the recovery rate. Table 5 shows that the dosage of the silkworm excrement-derived copper-molybdenum separation inhibitor directly affects the copper-molybdenum separation effect. In Comparative Example 12, the dosage of the silkworm excrement-derived copper-molybdenum separation inhibitor was 0, yet the chalcopyrite recovery rate was as high as 41%, while the molybdenite recovery rate was only 69%, indicating that chalcopyrite was not effectively inhibited without the addition of the silkworm excrement-derived copper-molybdenum separation inhibitor, and the floatability of molybdenite was also poor. As the dosage of the silkworm excrement-derived copper-molybdenum separation inhibitor in Comparative Example 13 and Examples 12-14 increased from 2.5 kg / t... 混精矿 Increased to 10 kg / t 混精矿 The recovery rate of chalcopyrite decreased continuously from 21% to 6%, while the recovery rate of molybdenite increased from 78% to 94%. This indicates that appropriately increasing the dosage of the silkworm excrement-derived copper-molybdenum separation inhibitor can significantly enhance the selective inhibition of chalcopyrite, while also benefiting the flotation recovery of molybdenite. In Example 13, the dosage of the silkworm excrement-derived copper-molybdenum separation inhibitor reached 7.5 kg / t. 混精矿 The recovery rate of chalcopyrite has decreased to 8%, while the recovery rate of molybdenite has increased to 90%; in Example 14, the dosage of the silkworm excrement copper-molybdenum separation inhibitor was further increased to 10 kg / t. 混精矿 The recovery rate of chalcopyrite further decreased to 6%, while the recovery rate of molybdenite increased to 94%. However, in Comparative Examples 14 and 15, the dosage of copper-molybdenum separation inhibitor from silkworm excrement was 12.5 kg / t. 混精矿 and 20kg / t 混精矿 More than 10kg / t 混精矿 At that time, the recovery rate of chalcopyrite remained unchanged at 6%, and the recovery rate of molybdenite also remained at 94%, indicating that further increasing the dosage would not only fail to improve the separation effect but would also result in a waste of reagents. Therefore, the appropriate dosage range for the silkworm excrement copper-molybdenum separation inhibitor is 3-10 kg / t. 混精矿 Preferred weight: 7.5-10 kg / t 混精矿 .

[0090] Experimental photographs of the synthetic silkworm excrement-derived copper-molybdenum separation inhibitor provided by this invention are shown below. Figure 1 As shown, Figure a is a photograph of the raw material silkworm excrement, Figure b is a photograph of the grafting reaction of activated silkworm excrement powder with carbon disulfide, Figure c is a photograph of the crude product after washing, filtration and purification, and Figure d is a photograph of the separation inhibitor of copper and molybdenum from silkworm excrement.

[0091] Due to the structural fragment [-NC(=S)-S] in the molecule of the silkworm excrement copper-molybdenum separation inhibitor under alkaline conditions. - It does not contain any directly bonded hydrogen atoms, therefore its conventional nuclear magnetic resonance hydrogen spectrum (NMR 1H) 1The proton signal of this group cannot be directly observed by ¹H NMR. It must be protonated to combine the lone pair electrons on the nitrogen atom with a proton, forming a detectable [-NC(=S)-SH] group. Based on this, the preparation and measurement steps of the protonated NMR sample of the silkworm excrement copper-molybdenum separation inhibitor of this invention are as follows: Weigh 50 mg of dry inhibitor powder, slowly add 20 mL of hydrochloric acid, control the pH ≤ 3, and sonicate for 5 min to complete protonation. Add the protonated silkworm excrement copper-molybdenum separation inhibitor to 2.5 mL of deuterated dimethyl sulfoxide (DMSO-d6) and sonicate for 30 min. Measure using a 400 MHz NMR spectrometer. 1 1H NMR spectrum. The proton NMR spectrum is shown below. Figure 2 As shown, although the chemical composition of the silkworm excrement copper-molybdenum separation inhibitor is complex and there is a lot of overlapping interference in the spectrum, after protonation treatment, the [-N] dithiocarbamate group can be clearly identified in the δ6.5-8.0ppm region. + H2-C(=S)-S - The broad peak signal of the [-N-CH2-] proton attached to the dithiocarbamic acid usually appears around δ4.2-4.5ppm, thus confirming the existence of the dithiocarbamic acid structure in the inhibitor molecule and its successful grafting with the silkworm excrement skeleton.

[0092] The mechanism of action between the silkworm excrement-derived copper-molybdenum separation inhibitor and chalcopyrite in the separation process of the copper-molybdenum mixed concentrate of this invention is as follows: Figure 4 As shown, step a represents the process of breaking down the silkworm excrement fiber structure and releasing amino groups, step b represents the process of generating dithiocarbamate groups, and step c represents the process of adding the silkworm excrement-derived copper-molybdenum separation inhibitor to the slurry system for copper-molybdenum separation. In the aqueous system, the active groups on the silkworm excrement-derived copper-molybdenum inhibitor molecules coordinate with free copper ions, thereby fixing chalcopyrite; while in the kerosene system, molybdenite particles, due to their hydrophobic and oleophilic nature, are preferentially wetted by kerosene and form agglomerates, thus separating from the aqueous phase.

[0093] This invention uses silkworm excrement, an agricultural waste, as raw material to prepare a copper-molybdenum separation inhibitor derived from silkworm excrement through alkali activation and carbon disulfide grafting reaction. It fully utilizes the abundant natural amino, carboxyl, hydroxyl, and aromatic heterocyclic active functional groups in silkworm excrement. The prepared inhibitor molecule contains a dithiocarbamic acid structure, which can release active thiol groups through tautomerism in alkaline slurry. These thiol groups form spatially coordinated chelating sites with nitrogen atoms in the native aromatic heterocycles of silkworm excrement, thereby directionally recognizing and firmly chelating copper ions on the surface of chalcopyrite, generating stable cyclic chelates. Simultaneously, the large number of carboxyl and hydroxyl groups retained in the molecule endow the chalcopyrite surface with strong hydrophilicity, achieving highly efficient and selective inhibition of chalcopyrite while having almost no effect on molybdenite.

[0094] A copper-molybdenum separation process was implemented by further combining the aforementioned silkworm excrement-derived copper-molybdenum separation inhibitor with sodium thiosulfate to form a synergistic reagent system. Sodium thiosulfate pre-removes the hydrophobic oxide film on the surface of chalcopyrite, providing a clean and activated adsorption interface for the silkworm excrement-derived copper-molybdenum separation inhibitor; simultaneously, it reduces the oxidative decomposition of the silkworm excrement-derived copper-molybdenum separation inhibitor in the early stages of flotation by stabilizing the pulp potential. The synergistic effect of both effectively inhibits chalcopyrite while maintaining good natural floatability of molybdenite, achieving excellent copper-molybdenum separation within a pH range of 8-14. This system is green, non-toxic, biodegradable, and the tailings after separation are easy to treat, demonstrating significant environmental, economic, and industrial-scale application prospects.

[0095] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method for preparing a copper-molybdenum separation inhibitor derived from silkworm excrement, characterized in that, include: After crushing the silkworm excrement, add it to an aqueous solution of sodium hydroxide, stir and filter to obtain filter residue; The filter residue was washed with deionized water until neutral, then sodium sulfite aqueous solution was added and kept warm. After separation and drying, activated silkworm excrement powder was obtained. The activated silkworm excrement powder is dispersed in anhydrous ethanol or isopropanol, and sodium hydroxide is added and stirred to alkalize, resulting in an alkalized silkworm excrement slurry. Carbon disulfide was added dropwise to the alkalized silkworm excrement slurry, then heated, stirred, and filtered to obtain a coarse filter cake. The crude filter cake is washed to obtain the crude product; The crude product was dispersed in deionized water, the pH was adjusted to 6.0-7.0, and after stirring and washing, it was filtered to obtain a purified filter cake. The purified filter cake was washed with alcohol, dried to constant weight, and then ground to obtain the silkworm excrement-derived copper-molybdenum separation inhibitor.

2. The preparation method of the silkworm excrement-derived copper-molybdenum separation inhibitor according to claim 1, characterized in that, The solid-liquid ratio of the silkworm excrement to the sodium hydroxide aqueous solution is 1:(5-10), and the mass fraction of the sodium hydroxide aqueous solution is 0.5%-2%; and / or, The stirring temperature in the stirring filtration process is 50℃-80℃, and the stirring time is 1h-3h.

3. The preparation method of the silkworm excrement-derived copper-molybdenum separation inhibitor according to claim 1, characterized in that, The solid-liquid ratio of the filter residue to the sodium sulfite aqueous solution is 1:(3-5), and the mass fraction of sodium sulfite in the sodium sulfite aqueous solution is 1%-5%; and / or, The insulation temperature is 60℃-90℃, and the insulation time is 0.5h-1h; and / or, The drying temperature after separation is 30℃-40℃.

4. The preparation method of the silkworm excrement-derived copper-molybdenum separation inhibitor according to claim 1, characterized in that, The solid-liquid ratio of the activated silkworm excrement powder to the anhydrous ethanol or isopropanol is 1:(4-8); and / or, The mass ratio of sodium hydroxide to activated silkworm excrement powder is (1-3):2; and / or, The temperature for stirring and alkalizing is 20℃-40℃, and the time for stirring and alkalizing is 0.5h-1h.

5. The method for preparing the silkworm excrement-derived copper-molybdenum separation inhibitor according to claim 1, characterized in that, The mass ratio of carbon disulfide to activated silkworm excrement powder is (4.0-4.5):1; and / or, The heating temperature is 60℃-70℃, and the stirring time is 2h-5h; and / or, The crude filter cake is washed 2-3 times with anhydrous ethanol.

6. The preparation method of the silkworm excrement-derived copper-molybdenum separation inhibitor according to claim 1, characterized in that, The solid-liquid ratio of the crude product to the deionized water is 1:(5-10); and / or, The pH adjustment to 6.0-7.0 is achieved using 1%-10% dilute hydrochloric acid; the stirring and washing time during filtration after stirring and washing is 0.5-1 hour; and / or, The drying temperature after alcohol washing is 40℃-60℃; and / or, The alcohol washing process includes washing the purified filter cake once with an aqueous ethanol solution of 30%-50% by volume and once with anhydrous ethanol.

7. A copper-molybdenum separation inhibitor derived from silkworm excrement, characterized in that, It is prepared by the method for preparing the silkworm excrement source copper-molybdenum separation inhibitor according to any one of claims 1-6.

8. A separation process for a copper-molybdenum mixed concentrate, characterized in that, include: Provide dry copper-molybdenum mixed concentrate ore, prepare copper-molybdenum mixed concentrate slurry, and then perform copper-molybdenum separation flotation; Add silkworm excrement source copper-molybdenum separation inhibitor and sodium thiosulfate, and then continue to add sodium hydroxide aqueous solution or hydrochloric acid solution to adjust the pH of the slurry system to 8-14; After adding kerosene and methyl isobutyl methanol to the slurry system in sequence, air is introduced, and the process of scraping and adding water is repeated. The floated molybdenum concentrate was collected when the cumulative flotation time was 1 min, 3 min, 6 min and 10 min, resulting in four types of molybdenum concentrate; The molybdenum concentrate is filtered and dried to obtain the finished molybdenum concentrate; wherein... In each ton of the copper-molybdenum mixed concentrate dry ore, the amount of the silkworm excrement source copper-molybdenum separation inhibitor is 3kg-10kg, and the amount of sodium thiosulfate is 0.5kg-3kg. The silkworm excrement copper-molybdenum separation inhibitor is the silkworm excrement copper-molybdenum separation inhibitor as described in claim 7.

9. The separation process for copper-molybdenum mixed concentrate according to claim 8, characterized in that, In each ton of the copper-molybdenum mixed concentrate dry ore, the amount of kerosene used is 50g-100g, and the amount of methyl isobutyl methanol used is 20g-25g; and / or, The interval for scraping bubbles is 3s-5s, and the interval for replenishing water is 10s-30s.

10. The separation process for copper-molybdenum mixed concentrate according to claim 8, characterized in that, The sodium hydroxide aqueous solution has a molar concentration of 0.50 mol / L to 0.75 mol / L, and the hydrochloric acid solution has a molar concentration of 0.05 mol / L to 0.1 mol / L. And / or, The drying temperature is 40℃-60℃.

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