Zinc mineral inhibitor and flotation separation method of copper-zinc sulfide ore

Abstract

The invention relates to the technical field of mineral separation, in particular to a zinc mineral inhibitor and a flotation separation method of copper-zinc sulfide ore. The zinc mineral inhibitor comprises oxidized konjac glucomannan, the oxidized konjac glucomannan is obtained by oxidizing konjac glucomannan through a TEMPO / NaBr / NaClO system, the oxidation system can selectively oxidize 6 # site primary hydroxyl in the konjac glucomannan into carboxyl, the carboxyl can be complexed with metal ions, activation of sphalerite by Cu < 2 + > released by chalcopyrite due to ore grinding or dissolution is avoided, and the zinc mineral inhibitor can be used for preparing the zinc mineral inhibitor. And strong chemical adsorption with the surface of the sphalerite can be generated, so that flotation of the sphalerite is remarkably inhibited. According to the flotation separation method, bis (hydroxymethyl) ethylene thiourea and N, N-diethyldithiocarbamide are adopted as copper mineral collecting agents and are matched with the zinc mineral inhibitor provided by the invention for flotation separation of the copper-zinc sulphide ores, the floatability difference between copper minerals and zinc minerals in the copper-zinc sulphide ores can be remarkably expanded, and the zinc grade in copper concentrate in the copper-zinc separation process is effectively reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a flotation separation method of a zinc mineral inhibitor and a copper-zinc sulfide ore. Background Art

[0002] Mineral resources are the material basis for social and economic development and play a vital role in social and economic activities. Among them, copper and zinc are widely used in electronics, chemicals, military, automobiles, construction, shipbuilding, light industry and other fields due to their unique physical and chemical properties. They are important mineral resources that are indispensable to modern industry and life. Chalcopyrite and sphalerite are the most important sources of copper and zinc. These two ores often coexist closely together in nature and are difficult to separate. At present, flotation is the most effective copper and zinc ore separation technology. However, during the grinding process, the fluid inclusions in chalcopyrite will be destroyed and a large amount of Cu will be released. 2+ , which will significantly activate sphalerite, reduce the floatability difference between chalcopyrite and sphalerite, and increase the difficulty of copper and zinc flotation separation.

[0003] To achieve efficient flotation separation of copper-zinc sulfide ores, inhibitors are added to selectively reduce the surface hydrophobicity of a particular mineral. Because chalcopyrite naturally floats better than sphalerite, flotation processes that suppress zinc and flot copper are often employed. Therefore, the development of sphalerite inhibitors has always been a core component of copper-zinc flotation separation. Sphalerite inhibitors can be primarily categorized as inorganic and organic. Inorganic inhibitors such as zinc sulfate, sulfites, sulfates, cyanides, pyrophosphates, and metaphosphates have been widely used in industrial production practices. However, these inorganic inhibitors pose challenges such as high dosage, severe environmental pollution, and significant health risks.

[0004] Chinese patent application CN115894318A discloses a method for preparing and applying zinc N-methoxypropyldithiocarbamate, a copper-zinc separation inhibitor. This inhibitor effectively inhibits sphalerite and reduces zinc intercalation in copper concentrate. However, the preparation process is complex and costly, making it difficult to commercialize and apply.

[0005] Chinese patent application CN101428250A discloses a copper-zinc separation beneficiation method. This method uses a depressant composed of lime, sodium sulfide, zinc sulfate, and sodium sulfite, which can address the problem of excessive zinc content in copper concentrate or excessive copper content in zinc concentrate. However, the high dosage of this depressant causes severe environmental pollution, which does not meet the development requirements of the "dual carbon" strategy. Therefore, the development of an environmentally friendly and efficient zinc mineral depressant and copper-zinc flotation separation method is crucial.

[0006] In view of this, the present invention is proposed. Summary of the Invention

[0007] The first object of the present invention is to provide a zinc mineral inhibitor, comprising a TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) / NaBr / NaClO system for oxidizing konjac gum. The TEMPO / NaBr / NaClO system can selectively oxidize the primary hydroxyl group at position 6 in konjac gum to a carboxyl group. The carboxyl group at this position has strong activity and can complex with metal ions, thereby preventing the release of Cu from chalcopyrite due to grinding or dissolution. 2+ On the other hand, it can activate sphalerite and undergo strong chemical adsorption on the sphalerite surface, significantly inhibiting the flotation of sphalerite.

[0008] A second object of the present invention is to provide a flotation separation method for copper-zinc sulfide ore, which uses the zinc mineral depressant as described above for flotation separation.

[0009] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted: A zinc mineral inhibitor comprises oxidized konjac gum, wherein the oxidized konjac gum is obtained by oxidizing konjac gum through a TEMPO / NaBr / NaClO system.

[0010] Preferably, the preparation method of the oxidized konjac gum comprises the following steps: S1. The konjac gum, TEMPO, NaBr and water were mixed, stirred and dissolved in dark conditions, and a base was added to adjust the pH value; S2 is added to the solution after adjusting the pH in step S1 NaClO reaction, adding alkali to maintain a stable pH value during the reaction; S3. After the reaction is completed, ethanol is added to the reaction system, and an acid is added to adjust the pH value, and then separated and purified to remove by-products and salts; S4. The material obtained after the separation and purification is subjected to evaporation concentration, solid-liquid separation and drying to obtain the oxidized konjac gum.

[0011] Preferably, in step S1, the mass ratio of the konjac gum, the TEMPO and the NaBr is 100:3-5:30-40.

[0012] Preferably, in step S1, the concentration of the konjac gum is 5-20 g / L.

[0013] Preferably, in step S1, the pH value after adding the base is adjusted to 9-11.

[0014] Preferably, in step S2, the mass ratio of the konjac gum to the NaClO is 10:3-12.

[0015] Preferably, in step S2, the reaction time is 2-4 hours.

[0016] Preferably, in step S2, the pH value of the reaction process is 9-11.

[0017] Preferably, in step S3, the mass concentration of the ethanol is 90%-99%, and the ratio of the amount of the ethanol added to the amount of the water in step S1 is 0.5-2 mL / L.

[0018] Preferably, in step S3, the pH value after adding the acid to adjust is 4-5.

[0019] Preferably, in step S3, the separation and purification is performed by dialysis.

[0020] A flotation separation method for copper-zinc sulfide ore, which uses a zinc mineral depressant and a copper mineral collector for flotation separation; Wherein, the zinc mineral inhibitor is the zinc mineral inhibitor described in any one of the aforementioned embodiments; and the copper mineral collector includes di(hydroxymethyl)ethylenethiourea and ethylthiocarbamide.

[0021] Preferably, in the copper mineral collector, the di(hydroxymethyl)ethylenethiourea is 6-8 parts, and the ethylthiocyanate is 2-4 parts by mass.

[0022] Preferably, the flotation separation method of the copper-zinc sulfide ore comprises the following steps: S1. The copper-zinc sulfide ore is crushed and ground to obtain a flotation pulp; S2. The copper mineral collector, the zinc mineral inhibitor and the frother are added to the flotation slurry for roughing copper and zinc separation to obtain a roughing concentrate and roughing tailings; S3. Adding the zinc mineral inhibitor to the rougher concentrate for copper-zinc separation and concentration to obtain a copper concentrate and selected middlings; The copper mineral collector and the foaming agent are added to the roughing tailings to carry out copper and zinc separation scavenging to obtain scavenged ore and tailings.

[0023] Preferably, in step S1, the copper grade of the copper-zinc sulfide ore is 0.5%-2%, and the zinc grade is 0.5%-3%.

[0024] Preferably, in step S1, the grinding fineness is -0.074 mm, accounting for 80%-95%.

[0025] Preferably, in step S1, the mass concentration of the slurry is 27%-35%.

[0026] Preferably, in step S2, the amount of the copper mineral collector added is 60-150 g / t.

[0027] Preferably, in step S2, the amount of the zinc mineral inhibitor added is 400-800 g / t.

[0028] Preferably, in step S2, the amount of the foaming agent used is 60-110 g / t.

[0029] Preferably, in step S3, the number of selections is 2-4 times.

[0030] Preferably, in step S3, the amount of the zinc mineral inhibitor added each time during the concentration is 100-350 g / t.

[0031] Preferably, in step S3, the scanning is performed 2-5 times.

[0032] Preferably, in step S3, the amount of the copper mineral collector added each time is 20-90 g / t.

[0033] Preferably, in step S3, the amount of the foaming agent added each time is 10-50 g / t.

[0034] Compared with the prior art, the present invention has the following beneficial effects: (1) The zinc mineral inhibitor provided by the present invention is obtained by selective oxidation modification of konjac gum. Konjac gum itself is a plant-derived, biodegradable natural macromolecular agent with relatively low raw material cost and is non-toxic and harmless. The TEMPO / NaBr / NaClO system can selectively oxidize the primary hydroxyl group at position 6 in konjac gum to a carboxyl group. The carboxyl group can complex with metal ions on the one hand, thereby preventing the release of Cu from chalcopyrite due to grinding or dissolution. 2+ On the other hand, it can activate sphalerite and undergo strong chemical adsorption with the sphalerite surface, significantly inhibiting the flotation of sphalerite. In oxidized konjac gum, the carboxyl group at position 6 is more active, and selective oxidation of the hydroxyl group at position 6 to a carboxyl group has a better inhibitory effect.

[0035] (2) The copper mineral collector used in the present invention has a short alkyl chain and a strong polar group, and has a strong selectivity for chalcopyrite, and can promote the flotation separation of chalcopyrite and sphalerite.

[0036] (3) The zinc mineral inhibitor in the present invention can be selectively adsorbed on the surface of the zinc mineral and will not affect the adsorption of the copper mineral collector on the surface of the copper mineral. When used in conjunction with the copper mineral collector provided by the present invention, it can significantly increase the floatability difference between copper minerals and zinc minerals in the copper-zinc sulfide ore, and effectively reduce the zinc grade in the copper concentrate during the copper-zinc separation process. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0038] Figure 1 This is a flow chart of the flotation separation of copper-zinc sulfide ore provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0039] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0040] The first aspect of the present invention provides a zinc mineral inhibitor, comprising oxidized konjac gum, wherein the oxidized konjac gum is obtained by oxidizing konjac gum through a TEMPO / NaBr / NaClO system.

[0041] The present invention adopts konjac glucomannan as raw material, and it is plant-derived, biodegradable, relatively cheap in raw material cost, and nontoxic and harmless. The primary hydroxyl group at position 6 in konjac glucomannan can be selectively oxidized to carboxyl group by TEMPO / NaBr / NaClO oxidation system, and the carboxyl group activity at this position is strong, and on the one hand, it can be complexed with metal ions, and the Cu that chalcopyrite releases due to grinding or dissolving is avoided. 2+ It can activate sphalerite and, on the other hand, undergo strong chemical adsorption with the sphalerite surface, significantly inhibiting the flotation of sphalerite. It has an excellent inhibitory effect on zinc minerals and can be used for the flotation separation of zinc-containing minerals.

[0042] In some specific embodiments of the present invention, the preparation method of oxidized konjac gum specifically comprises the following steps: S1. Konjac gum, TEMPO, NaBr and water were mixed and dissolved under stirring at room temperature in the dark, and a base was added to adjust the pH value; S2 is added to the solution after adjusting the pH in step S1 NaClO reaction, adding alkali to maintain a stable pH value during the reaction; S3. After the reaction is completed, ethanol is added to the reaction system, and an acid is added to adjust the pH value, and then separated and purified to remove by-products and salts; S4. The material obtained after separation and purification is subjected to evaporation concentration, solid-liquid separation and drying to obtain the oxidized konjac gum.

[0043] In some specific embodiments of the present invention, in step S1, the mass ratio of konjac gum, TEMPO and NaBr is 100:3-5:30-40, for example, it can be any point value among 100:3:30, 100:3:35, 100:3:40, 100:4:30, 100:4:35, 100:4:40, 100:5:30, 100:5:35, 100:5:40, or a range value consisting of any two point values.

[0044] In some specific embodiments of the present invention, in step S1, in the solution obtained after konjac glucomannan, TEMPO, NaBr and water are mixed, the concentration of konjac glucomannan is 5-20g / L, for example, it can be any point value among 5g / L, 10g / L, 15g / L, 20g / L or the range value consisting of any two point values; if the concentration is too low, the product concentration after the reaction is low, and the cost of obtaining the oxidized konjac glucomannan solid by evaporation and concentration in the later stage is higher; if the concentration is too high, the solution is too viscous, which is not convenient for separation and purification in the later stage, and therefore the concentration of konjac glucomannan needs to be reasonably controlled during the reaction.

[0045] In some specific embodiments of the present invention, in step S1, the pH value after adding alkali is adjusted to 9-11. For example, the pH value can be any point value among 9, 9.5, 10, 10.5, 11, or a range value consisting of any two point values; as an example, the alkali used to adjust the pH can be NaOH.

[0046] In some specific embodiments of the present invention, in step S2, the amount of NaClO is measured according to the mass ratio of konjac glucomannan and NaClO being 10:3-12. For example, the mass ratio of konjac glucomannan and NaClO can be any point value among 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, 10:10, 10:11, and 10:12, or a range value consisting of any two point values. If the amount of NaClO is too little, the oxidation is not thorough, and it is difficult to oxidize the hydroxyl group at position 6 of konjac glucomannan into a carboxyl group. In addition, the molecular weight of the oxidized konjac glucomannan is large, and the inhibitory effect on zinc minerals is poor. If the amount of NaClO is too much, the cost is high, and the difficulty of separation and purification will be increased.

[0047] In some specific embodiments of the present invention, in step S2, NaClO is added in the form of a solution, and the mass concentration of the NaClO solution is 3%-15%. For example, it can be any value among 3%, 5%, 8%, 10%, 12%, 18%, or a range consisting of any two values.

[0048] In some specific embodiments of the present invention, in step S2, the reaction time is 2-4 hours, for example, it can be any point value among 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or a range value consisting of any two point values.

[0049] In some specific embodiments of the present invention, in step S2, the pH value of the reaction process is 9-11, for example, it can be any point value among 9, 9.5, 10, 10.5, 11 or a range value consisting of any two point values; as an example, the base added during the reaction process can be NaOH.

[0050] In some specific embodiments of the present invention, in step S3, the mass concentration of ethanol used is 90%-99%, for example, it can be any point value among 90%, 92%, 95%, 97%, 99%, or a range value consisting of any two point values; the ratio of the amount of ethanol added to the amount of water added in step S1 is 0.5-2 mL / L, for example, it can be any point value among 0.5 mL / L, 0.8 mL / L, 1 mL / L, 1.2 mL / L, 1.5 mL / L, 1.8 mL / L, 2 mL / L, or a range value consisting of any two point values.

[0051] In some specific embodiments of the present invention, in step S3, the pH value after adding acid for adjustment is 4-5, for example, any value among 4, 4.2, 4.5, 4.8, and 5, or a range consisting of any two values; the purpose of adding ethanol and acid is to facilitate separation and purification. As an example, the acid used to adjust the pH can be HCl.

[0052] In some specific embodiments of the present invention, in step S3, separation and purification are performed by dialysis using a dialysis bag; as an example, the dialysis bag used can be a 500Da dialysis bag.

[0053] In some specific embodiments of the present invention, in step S4, the solid-liquid separation is performed by centrifugal separation.

[0054] In some specific embodiments of the present invention, the average molecular weight of the konjac glucomannan used is 200,000-800,000. For example, the molecular weight of the konjac glucomannan can be any value among 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, and 800,000, or a range consisting of any two values.

[0055] A second aspect of the present invention provides a flotation separation method for copper-zinc sulfide ore, which uses a zinc mineral depressant and a copper mineral collector for flotation separation; The zinc mineral inhibitor is any one of the zinc mineral inhibitors described in the foregoing embodiments; and the copper mineral collector includes di(hydroxymethyl)ethylenethiourea and ethylthiourea.

[0056] The zinc mineral inhibitor used in the present invention can be selectively adsorbed on the surface of the zinc mineral and will not affect the adsorption of the copper mineral collector on the surface of the copper mineral. The copper mineral collector used has a short alkyl chain and a strong polar group, and has a strong selectivity for chalcopyrite. The zinc mineral inhibitor and the copper mineral collector in the present invention are used in conjunction to significantly increase the floatability difference between copper minerals and zinc minerals in copper-zinc sulfide ores, and effectively reduce the zinc grade in the copper concentrate during the copper-zinc separation process.

[0057] In some specific embodiments of the present invention, the mass fraction of di(hydroxymethyl)ethylenethiourea in the copper mineral collector is 6-8 parts, for example, it can be any value among 6 parts, 6.5 parts, 7 parts, 7.5 parts, and 8 parts, or a range value consisting of any two values; the mass fraction of ethyl thiocyanate is 2-4 parts, for example, it can be any value among 2 parts, 2.5 parts, 3 parts, 3.5 parts, and 4 parts, or a range value consisting of any two values.

[0058] like Figure 1 As shown, in some specific embodiments of the present invention, the flotation separation method of the copper-zinc sulfide ore includes the following steps: S1. Crushing and grinding the copper-zinc sulfide ore (raw ore) to obtain flotation pulp; S2. A copper mineral collector, a zinc mineral inhibitor, and a frother are added to the flotation slurry for roughing copper and zinc separation to obtain a roughing concentrate and roughing tailings; S3. Adding a zinc mineral inhibitor to the rougher concentrate for copper-zinc separation and concentration to obtain a copper concentrate and a selected middlings; Copper mineral collector and foaming agent are added to the roughing tailings to carry out copper and zinc separation scavenging to obtain scavenged ore and tailings.

[0059] By using the zinc mineral inhibitor and copper mineral collector provided by the present invention in combination with a frother for roughing, concentrating and scavenging, the copper concentrate obtained has a high copper recovery rate and high grade, the zinc grade in the copper concentrate is low, and the copper-zinc separation effect is good. In some specific embodiments, the concentrating middlings obtained in the concentrating process and the scavenging middlings obtained in the scavenging process can be respectively returned to the roughing step for repeated flotation separation.

[0060] In some specific embodiments of the present invention, in step S1, the copper grade of the copper-zinc sulfide ore is 0.5%-2%, and the zinc grade is 0.5%-3%.

[0061] In some specific embodiments of the present invention, in step S1, the fineness after grinding is -0.074 mm, accounting for 80%-95%, for example, it can be any point value among 80%, 82%, 85%, 87%, 90%, 92%, 95%, or a range value consisting of any two point values; on the one hand, the copper-zinc sulfide ore needs to be crushed and ground to achieve effective monomer dissociation, and on the other hand, the mineral content of the -0.074 mm part of the ore pulp entering flotation should account for 80% to 95%. The grinding fineness at this time is conducive to the interaction between mineral particles and reagents to form a stable mineralized foam.

[0062] In some specific embodiments of the present invention, in step S1, water can be added after grinding to form a slurry, or water can be added during grinding to perform wet grinding to obtain a slurry. The mass concentration of the obtained slurry is 27%-35%, for example, it can be any point value among 27%, 29%, 30%, 32%, 34%, 35%, or a range value consisting of any two point values.

[0063] In some specific embodiments of the present invention, in step S2, the amount of the copper mineral collector added is 60-150 g / t, for example, it can be any point value among 60 g / t, 70 g / t, 80 g / t, 90 g / t, 100 g / t, 110 g / t, 120 g / t, 130 g / t, 140 g / t, and 150 g / t, or a range value consisting of any two point values.

[0064] In some specific embodiments of the present invention, in step S2, the amount of zinc mineral inhibitor added is 400-800 g / t, for example, any value among 400 g / t, 500 g / t, 600 g / t, 700 g / t, and 800 g / t, or a range consisting of any two values.

[0065] In some specific embodiments of the present invention, in step S2, the amount of foaming agent added is 60-110 g / t, for example, it can be any value among 60 g / t, 70 g / t, 80 g / t, 90 g / t, 100 g / t, 110 g / t, or a range value consisting of any two values.

[0066] In some specific embodiments of the present invention, in step S3, the number of selections is 2-4 times, for example, 2 times, 3 times or 4 times.

[0067] In some specific embodiments of the present invention, in step S3, the amount of zinc mineral inhibitor added in each concentrating process is 100-350 g / t, for example, any value among 100 g / t, 130 g / t, 150 g / t, 180 g / t, 200 g / t, 230 g / t, 260 g / t, 300 g / t, and 350 g / t, or a range consisting of any two values.

[0068] In some specific embodiments of the present invention, in step S3, the number of scanning is 2-5 times, for example, 2 times, 3 times, 4 times or 5 times.

[0069] In some specific embodiments of the present invention, in step S3, the amount of the copper mineral collector added during each sweeping process is 20-90 g / t, for example, it can be any value among 20 g / t, 30 g / t, 40 g / t, 50 g / t, 60 g / t, 70 g / t, 80 g / t, 90 g / t, or a range value consisting of any two value points.

[0070] In some specific embodiments of the present invention, in step S3, the amount of foaming agent added during each scanning process is 10-50 g / t, for example, it can be any point value among 10 g / t, 15 g / t, 20 g / t, 30 g / t, 40 g / t, 50 g / t or a range value consisting of any two point values.

[0071] In some specific embodiments of the present invention, the foaming agent in step S2 and the foaming agent in step S3 are independently selected from at least one of methyl isobutyl carbinol and pine oil.

[0072] In the present invention, the amount of reagent added is relative to the amount of the original ore.

[0073] The following describes some embodiments of the present invention in detail with reference to specific examples. The raw materials used in the examples can be purchased from the market unless otherwise specified.

[0074] Example 1 The present embodiment provides a zinc mineral inhibitor, which is oxidized konjac gum using a TEMPO / NaBr / NaClO system. The preparation method comprises the following steps: S1. Weigh 10g of konjac gum, 0.3g of TEMPO, and 3g of NaBr into a flask, add 1L of ultrapure water, stir thoroughly to dissolve, and then add NaOH solution to adjust the pH to 10. S2 was added to the solution obtained in step S1 20ml of a 20% concentration of NaClO solution and the reaction was continued for 2h, while NaOH solution was continuously added dropwise to maintain the pH value at around 10; S3. After the reaction is complete, 0.8 ml of 95% ethanol is added to the flask, followed by adjusting the pH to 5 by adding HCl solution, and dialyzing the mixture in a 500 Da dialysis bag for 2 d. S4. Evaporate and concentrate the dialyzed solution, then centrifuge it and dry the lower layer.

[0075] Example 2 The present embodiment provides a zinc mineral inhibitor, which is oxidized konjac gum using a TEMPO / NaBr / NaClO system. The preparation method comprises the following steps: S1. Weigh 10g of konjac gum, 0.4g of TEMPO, and 3.5g of NaBr into a flask, add 1L of ultrapure water, stir thoroughly to dissolve, and then add NaOH solution to adjust the pH to 10. S2 was added to the solution obtained in step S1 30ml of a 20% concentration of NaClO solution and the reaction was continued for 3h, while NaOH solution was continuously added dropwise to maintain the pH value at around 10; S3. After the reaction is complete, 1 ml of 95% ethanol was added to the flask, followed by adjusting the pH to 5 by adding HCl solution. The mixture was dialyzed in a 500 Da dialysis bag for 2 d. S4. Evaporate and concentrate the dialyzed solution, then centrifuge it and dry the lower layer.

[0076] Example 3 The present embodiment provides a zinc mineral inhibitor, which is oxidized konjac gum using a TEMPO / NaBr / NaClO system. The preparation method comprises the following steps: S1. Weigh 10g of konjac gum, 0.5g of TEMPO, and 4g of NaBr into a flask, add 1L of ultrapure water, stir thoroughly to dissolve, and then add NaOH solution to adjust the pH to 10. S2 was added to the solution obtained in step S1 40ml of a 20% concentration of NaClO solution and the reaction was continued for 4h, while NaOH solution was continuously added dropwise to maintain the pH value at around 10; S3. After the reaction is complete, 1.2 ml of 95% ethanol is added to the flask, followed by adjusting the pH to 5 by adding HCl solution. The mixture is then dialyzed in a 500 Da dialysis bag for 2 days. S4. Evaporate and concentrate the dialyzed solution, then centrifuge it and dry the lower layer.

[0077] Example 4 flotation separation of copper-zinc sulfide ore using the zinc mineral depressant prepared in Example 1; The copper mineral collector is composed of 6 parts of di(hydroxymethyl)ethylenethiourea and 4 parts of ethylthiourea by mass; The test ore is a copper-zinc sulfide ore from a place in Inner Mongolia, containing 0.69% copper and 1.12% zinc. The copper in the ore mainly exists in the form of chalcopyrite, and the zinc mainly exists in the form of sphalerite. In addition, the ore also contains metallic minerals such as pyrite, arsenopyrite, and pyrrhotite. The gangue minerals are mainly quartz, calcite, and feldspar. The ore has complex properties and fine particle size distribution, making flotation separation difficult.

[0078] The flotation separation steps of copper-zinc sulfide ore are as follows: S1. 500g of crushed ore was wet-ground in a ball mill with water to obtain flotation slurry. The grinding fineness was controlled to -0.074mm, accounting for 92%, and the slurry concentration was 28%. S2. The slurry is removed from the ball mill and placed in a flotation cell. A copper collector, zinc inhibitor, and frother (methyl isobutyl carbinol) are added sequentially to perform rough separation of copper and zinc, yielding a rougher concentrate and rougher tailings. The copper collector, zinc inhibitor, and frother are added at a dosage of 120 g / t, 800 g / t, and 90 g / t, respectively. S3. Adding a zinc mineral depressant to the rougher concentrate for copper-zinc separation and concentrating three times. The selected middlings from the first, second, and third stages are returned to the copper-zinc separation and roughing operations. The zinc mineral depressant dosage for the first stage is 300g / t, the dosage for the second stage is 200g / t, and the dosage for the third stage is 150g / t. Copper mineral collector and foaming agent (methyl isobutyl carbinol) are added to the roughing tailings for copper-zinc separation scavenging. The scavenging times are three times, and the scavenged minerals obtained from scavenging one, scavenging two and scavenging three are returned to the copper-zinc separation roughing operation; among them, the amount of copper mineral collector in scavenging one is 60g / t, and the amount of foaming agent is 40g / t; the amount of copper mineral collector in scavenging two is 30g / t, and the amount of foaming agent is 20g / t; the amount of copper mineral collector in scavenging three is 30g / t, and the amount of foaming agent is 15g / t.

[0079] Example 5 flotation separation of copper-zinc sulfide ore using the zinc mineral depressant prepared in Example 2; The copper mineral collector is composed of 7 parts of di(hydroxymethyl)ethylenethiourea and 3 parts of ethylthiourea by mass; The test ore is a copper-zinc sulfide ore from a place in Guangxi, containing 0.60% copper and 0.52% zinc. The metal minerals in the ore are mainly sphalerite, chalcopyrite, pyrite, marcasite and arsenopyrite. The copper-zinc sulfide ores are densely coexisting and the embedded particle size is relatively fine.

[0080] The flotation separation steps of copper-zinc sulfide ore are as follows: S1. Take 500g of crushed ore, add water, and grind it in a ball mill (wet grinding) to obtain flotation slurry. The grinding fineness is controlled to -0.074mm, accounting for 85%, and the mass concentration of the slurry is 30%. S2. The slurry is removed from the ball mill and placed in a flotation cell. A copper collector, a zinc inhibitor, and a frother (methyl isobutyl carbinol) are added sequentially to perform rough separation of copper and zinc, yielding a rougher concentrate and rougher tailings. The copper collector, zinc inhibitor, and frother are added at a dosage of 80 g / t, 600 g / t, and 80 g / t, respectively. S3. Adding a zinc mineral depressant to the rougher concentrate for copper-zinc separation and concentrating three times. The selected middlings from the first, second, and third stages are returned to the copper-zinc separation and roughing operations. The zinc mineral depressant dosage for the first stage is 200 g / t, the dosage for the second stage is 100 g / t, and the dosage for the third stage is 100 g / t. Copper mineral collector and foaming agent (methyl isobutyl carbinol) are added to the roughing tailings for copper-zinc separation scavenging. The scavenging times are three times, and the scavenged minerals obtained from scavenging one, scavenging two and scavenging three are returned to the copper-zinc separation roughing operation; wherein, the amount of copper mineral collector in scavenging one is 50g / t, and the amount of foaming agent is 30g / t; the amount of copper mineral collector in scavenging two is 25g / t, and the amount of foaming agent is 20g / t; the amount of copper mineral collector in scavenging three is 20g / t, and the amount of foaming agent is 15g / t.

[0081] Example 6 flotation separation of copper-zinc sulfide ore using the zinc mineral depressant prepared in Example 3; The copper mineral collector is composed of 8 parts of di(hydroxymethyl)ethylenethiourea and 2 parts of ethylthiourea by mass; The test ore is a copper-zinc sulfide ore from a location in Yunnan, containing 1.98% copper and 1.36% zinc. The main metallic minerals in the ore are chalcopyrite, sphalerite, pyrite, and pyrrhotite; in addition, there are small amounts of bornite, chalcocite, malachite, hematite, and galena. The main gangue minerals are quartz, feldspar, sericite, and chlorite.

[0082] The flotation separation steps of copper-zinc sulfide ore are as follows: S1. Take 500g of crushed ore, add water, and grind it in a ball mill (wet grinding) to obtain flotation slurry. The grinding fineness is controlled to -0.074mm, accounting for 90%, and the mass concentration of the slurry is 32%. S2. The slurry is removed from the ball mill and placed in a flotation cell. A copper collector, a zinc inhibitor, and a frother (methyl isobutyl carbinol) are added sequentially to perform rough separation of copper and zinc, yielding a rougher concentrate and rougher tailings. The copper collector, zinc inhibitor, and frother are added at a dosage of 100 g / t, 700 g / t, and 80 g / t, respectively. S3. Adding a zinc mineral depressant to the rougher concentrate for copper-zinc separation and concentrating three times. The selected middlings from the first, second, and third stages are returned to the copper-zinc separation and roughing operations. The zinc mineral depressant dosage for the first stage is 260 g / t, the dosage for the second stage is 180 g / t, and the dosage for the third stage is 130 g / t. Copper mineral collector and frother (methyl isobutyl carbinol) were added to the roughing tailings for copper-zinc separation scavenging. The scavenging times were three times, and the scavenged minerals obtained from scavenging one, two and three times were returned to the copper-zinc separation roughing operation. Among them, the amount of copper mineral collector in scavenging one was 65g / t, and the amount of frother was 35g / t; the amount of copper mineral collector in scavenging two was 35g / t, and the amount of frother was 20g / t; the amount of copper mineral collector in scavenging three was 30g / t, and the amount of frother was 15g / t.

[0083] Comparative Example 1 Comparative Example 1 is similar to Example 4, except that the zinc mineral inhibitor is replaced by an equal amount of zinc sulfate, and the copper mineral collector is replaced by an equal amount of butyl xanthate. The other conditions are the same as those in Example 1.

[0084] Comparative Example 2 Comparative Example 2 is similar to Example 4, except that a mixture of konjac glucomannan and NaClO is used as the zinc mineral inhibitor, the amounts of konjac glucomannan and NaClO are the same as those in Example 1, and the other flotation separation conditions are the same as those in Example 4.

[0085] Comparative Example 3 Comparative Example 3 is similar to Example 4, except that the di(hydroxymethyl)ethylenethiourea in the copper mineral collector is replaced with an equal amount of butyl xanthate, and the other conditions are the same as those in Example 4.

[0086] Comparative Example 4 Comparative Example 4 is similar to Example 5, except that the zinc mineral inhibitor is replaced with an equal amount of sodium sulfite, and the other conditions are the same as those of Example 5.

[0087] Comparative Example 5 Comparative Example 5 is similar to Example 5, except that the di(hydroxymethyl)ethylenethiourea in the copper mineral collector is replaced with an equal amount of butylammonium chloride, and the other conditions are the same as those in Example 5.

[0088] Comparative Example 6 Comparative Example 6 is similar to Example 6, except that the zinc mineral inhibitor is replaced with an equal amount of sodium sulfide, and the other conditions are the same as those of Example 6.

[0089] Comparative Example 7 Comparative Example 7 is similar to Example 6, except that the di(hydroxymethyl)ethylenethiourea in the copper mineral collector is replaced with an equal amount of ethyl xanthate, and the other conditions are the same as those in Example 6.

[0090] Test example The yields, copper and zinc grades, and copper and zinc recoveries of the copper concentrates and floating copper tailings obtained in Examples 4-6 and Comparative Examples 1-7 were tested respectively. The test results are shown in Table 1.

[0091] Table 1

[0092] From the data in Table 1, it can be seen that compared with Example 4, the yield of the copper concentrate obtained in Comparative Examples 1 and 2 increased, and the copper grade and recovery rate decreased significantly. The yield of the copper concentrate obtained in Comparative Example 3 decreased, the copper grade decreased, and the copper recovery rate decreased significantly. Compared with Example 5, the yield of the copper concentrate obtained in Comparative Example 4 increased, the copper grade and recovery rate decreased, the yield of the copper concentrate obtained in Comparative Example 5 decreased, the copper grade and copper recovery rate decreased significantly. Compared with Example 6, the yield of the copper concentrate obtained in Comparative Example 6 increased, the copper grade decreased significantly, and the copper recovery rate decreased. The yield of the copper concentrate obtained in Comparative Example 7 decreased, the copper grade decreased, and the copper recovery rate decreased significantly. It can be seen that the methods of Examples 4, 5, and 6 of the present invention can more fully separate copper and zinc in the raw ore compared to Comparative Examples 1 to 3, Comparative Examples 4 to 5, and Comparative Examples 6 to 7, respectively. Meanwhile, although comparative example 1,2,4,6 gained copper concentrate yield has increased, its grade and recovery rate all decline, explanation is compared with inhibitor provided by the present invention, when using the mixture of zinc sulfate, konjac glucomannan and NaClO, sodium sulfite, sodium sulfide as inhibitor, its selective inhibition to zinc mineral is relatively weak, causes impurities in concentrate to increase.On the other hand comparative example 3,5,7 gained copper concentrate yield and the copper grade and the recovery rate of gained copper concentrate all decline, explanation is compared with collector provided by the present invention, when using butyl xanthate, butylammonium black medicine, ethyl xanthate as collector, its collecting effect to copper mineral is relatively poor, and part copper mineral fails to be captured and is lost in tailings.

[0093] Although the present invention has been illustrated and described using specific embodiments, it should be appreciated that the above embodiments are merely intended to illustrate the technical solutions of the present invention rather than to limit them. Those skilled in the art should understand that the technical solutions described in the above embodiments may be modified, or some or all of the technical features thereof may be replaced by equivalents, without departing from the spirit and scope of the present invention. However, these modifications or replacements do not deviate from the essence of the corresponding technical solutions within the scope of the technical solutions of the embodiments of the present invention. Therefore, this means that all such replacements and modifications within the scope of the present invention are included in the appended claims.

Claims

1. A zinc mineral inhibitor, characterized in that The invention comprises oxidized konjac gum, which is obtained by oxidizing konjac gum through a TEMPO / NaBr / NaClO system.

2. The zinc mineral inhibitor according to claim 1, characterized in that The preparation method of described oxidized konjac gum comprises the following steps: S1. The konjac gum, TEMPO, NaBr and water were mixed, stirred and dissolved under dark conditions, and a base was added to adjust the pH value; S2. NaClO is added to the solution after adjusting the pH in step S1 to react, and a base is added during the reaction to maintain a stable pH value; S3. After the reaction is completed, ethanol is added to the reaction system, and an acid is added to adjust the pH value, and then the mixture is separated and purified to remove by-products and salts; S4. The material obtained after the separation and purification is evaporated and concentrated, solid-liquid separated and dried to obtain the oxidized konjac gum.

3. The zinc mineral inhibitor according to claim 2, characterized in that In step S1, at least one of the following characteristics is met: (1) The mass ratio of the konjac gum, the TEMPO and the NaBr is 100:3-5:30-40; (2) The concentration of the konjac gum is 5-20 g / L; (3) The pH value after adding the alkali is adjusted to 9-11.

4. The zinc mineral inhibitor according to claim 2, characterized in that In step S2, at least one of the following characteristics is met: (1) The mass ratio of the konjac gum to the NaClO is 10:3-12; (2) The reaction time is 2-4 hours; (3) The pH value of the reaction process is 9-11.

5. The zinc mineral inhibitor according to claim 2, characterized in that In step S3, at least one of the following characteristics is met: (1) The mass concentration of the ethanol is 90%-99%, and the ratio of the amount of the ethanol added to the amount of the water in step S1 is 0.5-2 mL / L; (2) the pH value after adding the acid is adjusted to 4-5; (3) The separation and purification is carried out by dialysis.

6. A flotation separation method for copper-zinc sulfide ore, characterized in that: Flotation separation using zinc mineral depressants and copper mineral collectors; Wherein, the zinc mineral inhibitor is the zinc mineral inhibitor according to any one of claims 1 to 5; and the copper mineral collector comprises 6 to 8 parts of di(hydroxymethyl)ethylene thiourea and 2 to 4 parts of ethyl thiourea by mass.

7. The flotation separation method of copper-zinc sulfide ore according to claim 6, characterized in that: The flotation separation method of the copper-zinc sulfide ore comprises the following steps: S1. crushing and grinding the copper-zinc sulfide ore to obtain a flotation slurry; S2. adding the copper mineral collector, the zinc mineral inhibitor and the frother to the flotation slurry to perform roughing of copper and zinc to obtain a roughing concentrate and a roughing tailing; S3. adding the zinc mineral inhibitor to the rougher concentrate to separate and concentrate copper and zinc to obtain a copper concentrate and a concentrated middling; The copper mineral collector and the frother are added to the roughing tailings to carry out copper-zinc separation and scavenging to obtain scavenged roughing tailings and tailings.

8. The flotation separation method of copper-zinc sulfide ore according to claim 7, characterized in that: In step S1, at least one of the following characteristics is met: (1) The copper grade of the copper-zinc sulfide ore is 0.5%-2%, and the zinc grade is 0.5%-3%; (2) The grinding fineness is -0.074mm accounting for 80%-95%; (3) The mass concentration of the slurry is 27%-35%.

9. The flotation separation method of copper-zinc sulfide ore according to claim 7, characterized in that: In step S2, at least one of the following characteristics is met: (1) The amount of the copper mineral collector added is 60-150 g / t; (2) The amount of zinc mineral inhibitor added is 400-800 g / t; (3) The dosage of the foaming agent is 60-110 g / t.

10. The flotation separation method of copper-zinc sulfide ore according to claim 7, characterized in that: In step S3, at least one of the following characteristics is met: (1) The number of times of selection is 2-4 times; (2) The amount of zinc mineral inhibitor added each time is 100-350 g / t; (3) The scanning is performed 2 to 5 times; (4) The amount of the copper mineral collector added each time is 20-90 g / t; (5) The amount of the foaming agent added each time is 10-50 g / t.

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