Combined reagent system for flotation and magnesium reduction of talc-containing copper-molybdenum ore and application of combined reagent system

Abstract

The invention relates to the technical field of mineral processing, and particularly provides a combined reagent system for flotation and magnesium reduction of talc-containing copper-molybdenum ore and application of the combined reagent system. The combined reagent system comprises a flotation collecting agent (faint yellow to orange transparent liquid, 40%-50% of active ingredients and less than or equal to 3% of free alkali) with active ingredients in the formula 1 and a flotation depressing agent (light yellow powder, extracellular polysaccharide extract of xanthomonas, the weight-average molecular weight of 1000-1500000 Daltons and rich in hydroxyl, carboxyl and pyruvic acid groups) with a structural formula in the formula 2, and the flotation depressing agent comprises extracellular polysaccharide extract of xanthomonas, the weight-average molecular weight of xanthomonas and the weight-average molecular weight of xanthomonas and is rich in hydroxyl, carboxyl and pyruvic acid groups. Through the synergistic adsorption effect of the combined reagent, the flotation grade and the recovery rate of the copper sulfide molybdenum ore are remarkably improved under the condition that the pH is 8-11. The combined reagent system has the advantages of being high in flotation efficiency, high in selectivity, low in reagent cost, environmentally friendly, high in industrial applicability and the like.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing technology, and specifically relates to a combined reagent system for flotation and magnesium reduction of talc-containing copper-molybdenum ore and its application. Background Technology

[0002] Copper and molybdenum mineral resources are closely related to human society. my country possesses abundant copper and molybdenum resources, but they are mainly low-grade, fine-grained, and complex polymetallic ores. With rapid and high-quality economic development, complex copper and molybdenum resources are gradually entering the scope of mining and utilization, such as high-talc copper-molybdenum ores, which have extremely low copper and molybdenum ore grades and extremely fine grain sizes. Furthermore, both molybdenite and talc have layered crystal structures; after separation, they expose new end faces and basal planes, and they also have similar grain size distributions and physicochemical properties, making their separation inherently complex. This will pose significant challenges to subsequent smelting and refining operations.

[0003] Flotation separation of copper-molybdenum ore and talc minerals with similar properties requires extremely high selectivity of flotation reagents and precision of process conditions. Existing research shows that it is difficult to achieve ideal performance with a single collector or depressant. To achieve efficient separation and comprehensive recovery of high-talc copper-molybdenum ore resources, it is necessary to use highly selective collectors and depressants in synergistic regulation to improve the recovery efficiency of copper-molybdenum resources. Summary of the Invention

[0004] To address the technical challenge of separating molybdenite from gangue mineral talc in high-talc copper-molybdenum ores due to the flotation process's tendency for talc to become brittle and muddy, resulting in sticky froth, this invention provides a combined reagent system for flotation and magnesium reduction in talc-containing copper-molybdenum ores. This combined reagent system enables highly efficient and selective flotation separation of sulfide copper-molybdenum ores and talc.

[0005] The second objective of this invention is to provide an application of a combined reagent system for flotation of talc-containing copper-molybdenum ore to reduce magnesium content.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a combined reagent system for flotation and magnesium reduction of talc-copper-molybdenum ore, comprising a flotation collector having an active ingredient of Formula 1 and a flotation inhibitor having a structure of Formula 2.

[0008] Formula 1

[0009] Formula 2

[0010] In the flotation collector, the mass fraction of the active ingredient of Formula 1 is 40%~50%;

[0011] In the combined reagent system, the mass ratio of flotation collector to flotation inhibitor is 1~10:5~40, preferably 1~3:5~15.

[0012] Selective adsorption of reagents on the surfaces of copper-molybdenum ore and talc is key to ensuring flotation effectiveness. The combined reagent system of this invention has the following advantages in the flotation of high-talc copper-molybdenum ore: First, it has strong collecting ability, effectively enriching copper-molybdenum minerals and ensuring the target metal grade; second, it has strong selectivity, accurately identifying the target minerals and gangue minerals; and third, it has strong inhibition performance, significantly blocking talc from entering the concentrate system, thereby improving the flotation recovery rate and grade of sulfide copper-molybdenum minerals and significantly reducing the talc content in the concentrate.

[0013] In this invention, the flotation collector used is a pale yellow to orange transparent liquid. In addition to the active ingredient, it also contains the liquid solvent dibutylamine, as well as NaOH, NaSO4, and Na2CO3. It is characterized by being easily soluble in water, non-toxic, non-polluting, and highly efficient. The flotation inhibitor is a light yellow powder, which is characterized by being green, biodegradable, and biocompatible.

[0014] Preferably, the mass fraction of free alkali (NaOH) in the flotation collector is ≤3%. Experiments have shown that controlling the mass fraction of free alkali in the flotation collector within the range of this invention results in the best flotation effect. If the mass fraction of free alkali is too high, it will reduce the stability of the collector and the reactivity of the active ingredients, causing corrosion to the storage container and increasing safety risks.

[0015] Preferably, the flotation inhibitor is an extracellular polysaccharide extract of Xanthomonas.

[0016] Preferably, the weight-average molecular weight of the flotation inhibitor is between 10 million and 15 million Daltons. Experiments have shown that flotation performance is optimal when using flotation inhibitors with a molecular weight between 10 million and 15 million Daltons. This is because excessively high molecular weights can lead to non-selective adsorption of molybdenite due to steric hindrance, reducing the selectivity for talc inhibition; while excessively low molecular weights cannot form a stable and dense hydration film on the talc surface, thus weakening its inhibitory ability. Both factors significantly reduce the inhibitory effect on talc.

[0017] In this invention, the Xanthomonas bacillus used has the preservation number Xc BNCC-188197 and was purchased from the Henan Provincial Engineering Technology Research Center for Industrial Microbial Strains.

[0018] In a further preferred embodiment, the process of obtaining the flotation inhibitor is as follows: Xanthomonas aeruginosa is inoculated into a culture medium for cultivation. After cultivation, the fermentation broth is centrifuged to obtain the supernatant. The extracellular polysaccharide extract is obtained by extracting from the supernatant.

[0019] In a further preferred embodiment, the culture conditions for Xanthomonas are: inoculum size 5-15%, temperature 25-35°C, initial pH 6-8, and culture time 24-72 h.

[0020] In a further preferred embodiment, the culture medium comprises 40-50 g / L corn starch, 2-4 g / L yeast extract, and 1-3 g / L calcium carbonate. Using this preferred culture medium composition and under the above-mentioned culture conditions, the microbial extracellular polysaccharide yield, polysaccharide molecular weight, and content of active functional groups in the polysaccharide structure are highest.

[0021] The flotation inhibitor provided by this invention is rich in hydroxyl, carboxyl, and pyruvate groups, which can be effectively adsorbed onto the surface of talc through strong hydration and electrostatic repulsion, significantly enhancing its hydrophilicity and inhibiting its hydrophobic aggregation, thereby achieving high-efficiency inhibition.

[0022] The present invention also provides an application of a combined reagent system for flotation of talc-containing copper-molybdenum ore to reduce magnesium content, wherein the combined reagent system is applied to the flotation separation of high-talc copper-molybdenum ore.

[0023] Preferably, during the flotation separation, the pH is controlled at 3-13; more preferably 5-12; further preferably 7-11; and even more preferably 8-11.

[0024] Experiments showed that controlling the appropriate flotation pH helps to further improve the separation performance of the combined reagent system for copper-molybdenum sulfide ore and talc. When the combined reagent system is at pH 8-11, it significantly improves the flotation grade and recovery rate of copper-molybdenum sulfide ore, while significantly inhibiting talc from entering the concentrate.

[0025] Preferably, during the flotation separation, the total amount of flotation collector is 10~100 g / t, preferably 20~60 g / t, and the total amount of flotation inhibitor is 50~400 g / t, preferably 100~300 g / t.

[0026] Preferably, the flotation collector in the combined reagent system is added at least during the grinding operation. This invention has found that adding the active ingredient during the grinding operation helps reduce collector consumption in the flotation system, further synergistically enhances the selective collection of copper-molybdenum sulfide ores by the combined reagent system, and helps improve the recovery rate and grade of the target mineral.

[0027] Preferably, the flotation separation process includes the following steps:

[0028] (1) Grind the raw ore. During the grinding process, add pH adjuster and flotation collector. In step (1), the amount of pH adjuster added is 100~3000 g / t, and the amount of flotation collector used is 10~100 g / t.

[0029] (2) After the raw ore is ground, a frother is added and pre-flotation is performed to obtain frothy product No. 1 rough concentrate and No. 1 slurry. In step (2), the amount of the frother is 10~50 g / t.

[0030] (3) Add flotation collector to No. 1 slurry and perform one scavenging to obtain No. 2 rough concentrate and No. 1 tailings. In step (3), the amount of flotation collector used is 5~30 g / t.

[0031] (4) Combine No. 1 rough concentrate and No. 2 rough concentrate for fine cleaning. During the fine cleaning process, flotation inhibitor is added to obtain No. 1 concentrate and No. 2 tailings. The amount of flotation inhibitor used is 100~300 g / t.

[0032] For complex copper-molybdenum sulfide ores with high talc content (Cu≥0.47%, Mo≥0.004%, talc content 5%~15%), the above-mentioned flotation separation process can improve the recovery rate of molybdenite to over 82%, while reducing the talc grade in the concentrate to below 2.15%.

[0033] The above process can efficiently separate sulfide minerals (chalcopyrite, chalcocite, covellite, molybdenite) from gangue (quartz, talc, and other magnesium silicate minerals) and obtain a copper-molybdenum mixed concentrate with high recovery rate. Steps (1)-(3) ensure the initial recovery rate of copper and molybdenum by enriching sulfide minerals and separating them from gangue minerals such as some pyrite and most quartz through flotation. Then, step (4) aims to suppress easily floatable talc and ensure the recovery rate of copper and molybdenum (especially molybdenum) while controlling the MgO content in the mixed concentrate.

[0034] In the above process, the order of adding the combined reagent system is crucial. If an inhibitor is added in step (3), molybdenum will be lost in the tailings, while if a collector is used in step (4), talc will easily enter the concentrate, deteriorating the product quality.

[0035] Furthermore, the pH adjuster is selected from one or more of calcium oxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sulfuric acid, and hydrochloric acid.

[0036] Furthermore, the foaming agent is selected from one or more of n-butanol, pine oil, butyl ether alcohol, methyl isobutyl methanol, or heteropolyols.

[0037] Compared with the prior art, the features and beneficial effects of the present invention are as follows:

[0038] 1. The combined reagent system provided by the present invention, wherein the flotation inhibitor exhibits a highly efficient selective inhibition effect on talc during the flotation of high-talc copper-molybdenum ore. Even with excessive addition of the inhibitor, the recovery rate of copper sulfide in the mixed copper-molybdenum concentrate is not affected, the loss rate of molybdenite is significantly reduced, and the recovery rate and grade of gangue mineral talc are reduced to extremely low levels.

[0039] 2. This invention also reveals that the reagent formulation formed by the combination of the inhibitor and the collector exhibits excellent synergistic selectivity. Even with excessive addition of collectors or inhibitors, the flotation system remains stable, and the separation effect of each reagent is unaffected. In particular, excessive addition of collectors does not lead to a significant increase in the content of the gangue mineral talc in the mixed concentrate.

[0040] 3. The combined reagent system provided by this invention is simple, easy to operate, has low requirements for the flotation environment, and is highly applicable. It can achieve efficient flotation of copper-molybdenum sulfide ores and efficient selective suppression of gangue mineral talc. Furthermore, based on its unique synergistic selectivity, this system significantly reduces reagent consumption in the flotation system while ensuring efficient separation of copper-molybdenum sulfide ores and talc and stability of the flotation system. It combines environmental friendliness and low cost, making it particularly suitable for industrial applications.

[0041] In summary, the novel, highly efficient, and selective combined reagent system provided by this invention can achieve efficient separation of copper-molybdenum sulfide ore from gangue mineral talc, increasing the recovery rate of molybdenite to over 82% while reducing the talc grade in the concentrate to below 2.15%. This provides a new approach and method to address the current challenges of efficient recovery and utilization of molybdenite from high-talc copper-molybdenum ores and the excessively high talc content in the target mineral concentrate obtained from current flotation systems. The technical solution of this invention, through the selective adsorption of the target mineral by the active components in each reagent structure, maximizes the positive synergistic effect of the combined reagent system, effectively improving the flotation recovery and utilization rate of copper-molybdenum sulfide ore, and significantly reducing the grade and content of talc in the concentrate product. It achieves highly efficient and selective flotation separation of copper-molybdenum sulfide ore from gangue mineral talc while simplifying the reagent system and saving reagent costs. Attached Figure Description

[0042] Figure 1 This is a flotation flow chart of high talc-type copper-molybdenum ore according to Embodiment 2 of the present invention. Detailed Implementation

[0043] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments and accompanying drawings. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0044] The combined reagent systems used in Examples 1 and 2 below include a flotation collector having an active ingredient of Formula 1 and a flotation inhibitor having a structure of Formula 2;

[0045] Formula 1

[0046] Formula 2

[0047] The flotation collector, by mass ratio, has the following composition: 45% active ingredient (Formula 1), 11.5% dibutylamine, 1.5% NaOH, 40% NaSO4, and 2% Na2CO3.

[0048] The flotation inhibitor in Formula 2 is an extracellular polysaccharide extract of Xanthomonas, and the weight-average molecular weight of the flotation inhibitor used is 12 million Daltons.

[0049] The specific extraction method for the flotation inhibitor is as follows: Xanthomonas aeruginosa (preservation number Xc BNCC-188197, purchased from the Henan Provincial Industrial Microbial Culture Research Center) was inoculated into a culture medium (composition: corn starch 45 g / L, yeast extract 3 g / L, calcium carbonate 2 g / L) and cultured at 30℃ (inoculation temperature: 30℃, inoculation amount: 10%, initial pH: 7, growth period: 48 h). After culture, the fermentation broth was centrifuged to obtain the supernatant. Extracellular polysaccharides were then extracted from the supernatant. The extraction process was as follows: First, 5 mL of fermentation broth was diluted with an equal volume of distilled water and thoroughly mixed. The mixture was centrifuged at 10000 r / min for 25 minutes, and the supernatant was extracted. Then, three times the volume of ethanol was added and shaken to fully precipitate the extracellular polysaccharides. The mixture was centrifuged again at 10000 r / min for 25 minutes, and the supernatant was discarded. This step was repeated three times. Finally, the substrate was dried at 60℃ to constant weight to obtain the extracellular polysaccharides.

[0050] Example 1

[0051] The effects of this invention are illustrated using a binary blend of molybdenite and talc (mass ratio 1:1) as an example. Before mixing, the materials consisted of 96% molybdenite and talc with a fineness of -0.074 mm, a molybdenite purity of 99%, a molybdenum (Mo) grade of 59.7%, a talc purity of 98%, and a silicon (Si) grade of 27.49%. After thorough artificial mixing, the molybdenum grade in the binary blend was 27.14%, and the silicon grade was 14.08%.

[0052] The mineral processing flow and reagent system of this embodiment are as follows. The flotation adopts a one-step separation process of artificial mixed ore, and the specific operation is as follows: 2 g of binary mixed ore is mixed with 40 mL of deionized water to form a slurry, and the combined reagents of this invention are added in the following order: first, 30 mg / L flotation inhibitor is added, with an interval of 3 minutes; then, 50 mg / L flotation collector is added, with an interval of 3 minutes; finally, an appropriate amount of frother methyl isobutyl methanol (MIBC) is added, and after an interval of 1 minute, flotation separation is performed for 3 minutes.

[0053] The flotation test results of Example 1 are shown in Table 1.

[0054] Comparative Example 1

[0055] Unlike Example 1, in one separation step, butyl xanthate and carboxymethyl cellulose (CMC) were used instead of the flotation collector and flotation depressant, respectively. The remaining steps, reagent dosages, and raw material composition were the same as in Example 1. The flotation test results are shown in Comparative Example 1 in Table 1.

[0056] Comparative Example 2

[0057] Unlike Example 1, in one separation step, butyl xanthate was used instead of the flotation collector; the remaining steps, reagent dosages, and raw material composition were the same as in Example 1. The flotation test results are shown in Comparative Example 2 in Table 1.

[0058]

[0059] Based on the inventors' previous experimental results, the separation efficiency of molybdenite and talc reached its optimal level using the combined reagent system of this invention, with a flotation collector dosage of 50 mg / L and a flotation depressant dosage of 30 mg / L. Table 1 shows that the separation effect of Mo and Si was optimal in Example 1 (this invention). Molybdenite was efficiently enriched in the concentrate, while talc was effectively suppressed from entering the tailings. The Mo grade in the concentrate reached 59.35%, and the Mo recovery rate reached 94.72%; simultaneously, the Si grade in the concentrate was only 1.21%, and the Si recovery rate was as low as 4.08%. Comparative Example 2 (replacing the collector with butyl xanthate): The Mo grade in the concentrate decreased to 57.75%, while the Si grade increased to 3.27%, and the Si recovery rate increased to 13.74%. Comparative Example 1 (replacing the collector with butyl xanthate and the depressant with CMC): The Si grade in the concentrate increased significantly to 6.56%, and the Mo recovery rate decreased significantly to 15.60%. The above results fully demonstrate that the reagent system of the present invention can efficiently separate molybdenite and talc, which have extremely similar properties. While ensuring high grade and high recovery of molybdenite, it can achieve strong selective inhibition of talc minerals, effectively preventing them from entering the frothy concentrate.

[0060] Example 2

[0061] A copper-molybdenum sulfide ore containing a large amount of talc has a copper grade of 0.47% and a molybdenum grade of 0.014%. The copper sulfide minerals in the ore are mainly chalcopyrite, chalcocite and covellite, while the molybdenum minerals are mainly molybdenite. The talc content in the gangue minerals reaches 5.0% to 10.0%.

[0062] The mineral processing flow and reagent system of this embodiment 2 are as follows: Figure 1 As shown.

[0063] (1) During the grinding stage, calcium oxide (1000 g / t) and flotation collector (40 g / t) are added to the raw ore so that the flotation collector preferentially acts on the surface of the target mineral under pH 9.5 conditions.

[0064] (2) After the raw ore is ground, methyl isobutyl methanol (MIBC) is added as a frother and pre-flotation is carried out to obtain froth products No. 1 rough concentrate and No. 1 slurry. The frothing agent dosage is 40 g / t.

[0065] (3) Add the No. 1 slurry to the flotation collector and perform the first scavenging to obtain No. 2 rough concentrate and No. 2 slurry (tailings 1). The amount of flotation collector used in the first scavenging is 10 g / t.

[0066] (4) The No. 1 rough concentrate and the No. 2 rough concentrate are combined for fine cleaning. During the fine cleaning process, flotation inhibitors are added to obtain mixed concentrate and No. 2 slurry (tailings 2). During the fine cleaning, the amount of flotation inhibitor used is 150 g / t.

[0067] Comparative Example 3

[0068] Unlike Example 2, Comparative Example 3 used CMC instead of a flotation depressant and a mixed ester instead of a flotation collector in a single separation step. The remaining steps, reagent dosages, and raw material composition were the same as in Example 2. The CMC is a composite polymeric depressant, and the mixed ester is a sulfide ore collector that has been successfully applied in a high-talc skarn copper-molybdenum deposit. The flotation test results of the high-talc copper-molybdenum ore in Comparative Example 3 are shown in Table 2.

[0069]

[0070] As shown in Table 2 and Figure 1As shown, Example 2, employing the reagent system of this invention, exhibits significant advantages in the actual beneficiation of complex high-talc copper-molybdenum ore: the resulting mixed concentrate has a Cu grade of 1.92% and a Mo grade of 0.055%, while the talc (calculated as Mg) grade drops to 2.15%, and the Mg recovery rate is as low as 5.66%. In contrast, the mixed concentrate of Comparative Example 3 has a Cu grade of only 1.83% and a Mo grade of only 0.053%, while the talc Mg grade is as high as 5.21%, and the Mg recovery rate is 14.22%. This result confirms that the combined reagent system of this invention has three core characteristics: (1) strong collecting ability: effectively enriches copper-molybdenum minerals and ensures the target metal grade; (2) strong selectivity: accurately identifies the target minerals and gangue minerals; (3) strong inhibition ability: significantly blocks talc from entering the concentrate system. Based on this, this invention, while maintaining a high copper-molybdenum recovery rate, achieves efficient enrichment of copper-molybdenum metals by deeply inhibiting gangue minerals, ultimately improving the utilization rate of complex ore resources and creating considerable economic benefits for the beneficiation plant.

Claims

1. A combined reagent system for flotation and magnesium reduction of talc-containing copper-molybdenum ore, characterized in that: Including flotation collectors having the active ingredient of Formula 1 and flotation inhibitors having the structure of Formula 2; Formula 1 Formula 2 In the flotation collector, the mass fraction of the active ingredient of Formula 1 is 40%~50%; In the combined reagent system, the mass ratio of flotation collector to flotation inhibitor is 1~10:5~40.

2. The combined reagent system for flotation and magnesium reduction of talc-containing copper-molybdenum ore according to claim 1, characterized in that: The mass fraction of free alkali in the flotation collector is ≤3%.

3. The combined reagent system for flotation of talc-containing copper-molybdenum ore to reduce magnesium content according to claim 1, characterized in that: The flotation inhibitor is an extracellular polysaccharide extract of Xanthomonas aeruginosa; The weight-average molecular weight of the flotation inhibitor is between 10 million and 15 million Daltons.

4. The application of the combined reagent system for flotation of talc-containing copper-molybdenum ore to reduce magnesium content according to any one of claims 1-3, characterized in that: The combined reagent system was applied to the flotation separation of high-talc copper-molybdenum ores.

5. The application of the combined reagent system for flotation magnesium reduction of talc-containing copper-molybdenum ore according to claim 4, characterized in that: During the flotation separation, the pH is controlled at 3-13.

6. The application of the combined reagent system for flotation magnesium reduction of talc-containing copper-molybdenum ore according to claim 4, characterized in that: During the flotation separation, the total amount of flotation collector is 10~100 g / t, and the total amount of flotation depressant is 50~400 g / t.

7. The application of the combined reagent system for flotation magnesium reduction of talc-containing copper-molybdenum ore according to claim 4, characterized in that: The flotation collector in the combined reagent system is added at least during the grinding operation.

8. The application of the combined reagent system for flotation of talc-containing copper-molybdenum ore to reduce magnesium content according to claim 4, characterized in that: The flotation separation process includes the following steps: (1) Grind the raw ore and add pH adjuster and flotation collector during the grinding process. In step (1), the amount of pH adjuster added is 100~3000 g / t and the amount of flotation collector is 10~100 g / t. (2) After the raw ore is ground, a frother is added and pre-flotation is performed to obtain frothy product No. 1 rough concentrate and No. 1 slurry. In step (2), the amount of the frother is 10~50 g / t. (3) Add flotation collector to No. 1 slurry and perform one scavenging to obtain No. 2 rough concentrate and No. 1 tailings. In step (3), the amount of flotation collector used is 5~30 g / t. (4) Combine No. 1 rough concentrate and No. 2 rough concentrate for fine cleaning. During the fine cleaning process, flotation inhibitor is added to obtain No. 1 concentrate and No. 2 tailings. The amount of flotation inhibitor used is 100~300 g / t.

9. The application of the combined reagent system for flotation magnesium reduction of talc-containing copper-molybdenum ore according to claim 8, characterized in that: The pH adjuster is selected from one or more of calcium oxide, sodium carbonate, sodium hydroxide, sulfuric acid, and hydrochloric acid.

10. The application of the combined reagent system for flotation of talc-containing copper-molybdenum ore to reduce magnesium content according to claim 8, characterized in that: The foaming agent is selected from one or more of n-butanol, pine oil, butyl ether alcohol, methyl isobutyl methanol, or heteropolyols.

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