Composite depressor for copper sulphide ores, depression method and copper-molybdenum separation method and its flotation reagents

Abstract

This invention belongs to the field of flotation, specifically relating to a composite inhibitor for copper sulfide ore, an inhibition method, a copper-molybdenum separation method, and flotation reagents. The composite inhibitor for copper sulfide ore comprises components A, B, C, and D in a weight ratio of 3-7:1-2:1-2:1-3; component A is a compound of formula 1 (); component B is a compound of formula 2 (); component C is konjac mannan; and component D is a compound of formula 3 (). This invention demonstrates that the innovative combination of components A through D, based on the synergistic effect of the special functional groups between components A and D, can unexpectedly achieve high selectivity in inhibiting the flotation of copper sulfide ore.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation, specifically relating to the field of flotation inhibition of copper sulfide ores. Background Technology

[0002] Chalcopyrite (CuFeS2) and molybdenite (MoS2) are the main mineral resources for obtaining these two metals. They often coexist closely in nature, forming copper-molybdenum sulfide ores. Flotation is the most economical and effective method for separating copper and molybdenum. Its core lies in the selective suppression of chalcopyrite while efficiently floating molybdenite. Because molybdenite has good natural floatability, and chalcopyrite also has relatively strong floatability, separating the two is challenging, placing higher demands on the strength and selectivity of the depressant.

[0003] Traditional chalcopyrite depressants used for copper-molybdenum separation mainly include sodium sulfide, sodium hydrosulfide, cyanides (such as NaCN and KCN), Knox reagents (phosphorox and arsenox), and sodium thioglycolate. For example, patent document CN102513220A discloses a reagent composition for recovering copper and molybdenum concentrates from a mixed copper-molybdenum concentrate slurry, where the copper mineral depressant mainly includes sodium thioglycolate and industrial sulfuric acid. Patent document CN103949351A discloses a flotation depressant and its preparation and application method, which is a liquid organic reagent obtained by chemical reaction using thioglycolic acid, gallic acid, and sodium hydroxide as raw materials. Furthermore, Chinese patent document CN109482357A discloses the preparation and application of a copper-molybdenum separation depressant, in which the disclosed depressant is N-(2-hydroxyethyl)-2-mercaptoacetamide.

[0004] However, these reagents have some shortcomings in practical applications. For example, sodium sulfide reagents require large quantities, are easily oxidized and decomposed, resulting in high costs and poor stability; cyanide is extremely toxic, posing a serious threat to the environment and safe production, and its use is being increasingly restricted by regulations; Knox reagents introduce harmful elements such as arsenic and phosphorus, affecting the quality of molybdenum concentrate; and while sodium thioacetate has a good inhibitory effect, its selectivity in complex slurry environments needs improvement. Therefore, developing a novel, efficient, environmentally friendly, and highly selective composite inhibitor for chalcopyrite is of great significance for improving the comprehensive utilization rate of copper and molybdenum resources. Summary of the Invention

[0005] To address the problem of unsatisfactory selectivity of depressants for copper sulfide ores, the primary objective of this invention is to provide a composite depressant for copper sulfide ores (also referred to as a composite depressant in this invention) aimed at improving the flotation depressant selectivity of copper sulfide ores.

[0006] A second objective of this invention is to provide a method for inhibiting copper sulfide ore, which aims to selectively inhibit copper sulfide ore using the aforementioned composite inhibitor.

[0007] The third objective of this invention is to provide a method and flotation reagent for copper-molybdenum separation based on the aforementioned composite inhibitor, aiming to improve the inhibition selectivity of copper sulfide ores and improve the separation selectivity of copper-molybdenum.

[0008] A composite inhibitor for copper sulfide ore comprises components A, B, C, and D in a weight ratio of 3-7:1-2:1-2:1-3; wherein component A is a compound of formula 1; component B is a compound of formula 2; component C is konjac mannan; and component D is a compound of formula 3.

[0009] Formula 1;

[0010] Formula 2;

[0011] Formula 3;

[0012] In Formula 1, M is H, Na, K or NH4;

[0013] In Formula 2, R1 is a C1~C4 alkylene group, Y is H, Na, K, Ca, Mg or NH4; m is the valence of Y;

[0014] In Formula 3, R2 is a C1-C4 alkyl group, and X is H, Na, K or NH4.

[0015] This invention demonstrates that by innovatively combining components A through D, and based on the synergistic effect of the special groups in components A through D, the flotation of copper sulfide ores can be unexpectedly suppressed with high selectivity.

[0016] In this invention, component A contains multiple thiol groups and aromatic ring structures, while component B contains -COO groups. - And thiol groups, the special sugar rings and glycosidic bonds in component C, and the multiple -O groups in component D. - and -COO - The combination of these components can form highly selective targeted structural domains for copper sulfide minerals based on the synergistic complementarity of active groups and structures, thereby improving the flotation inhibition effect of copper sulfide minerals.

[0017] Preferably, M in Formula 1 can be Na.

[0018] Preferably, Y in Formula 2 can be Ca, m can be 2, and R1 can be methylene or ethylene.

[0019] Preferably, component C can be commercially available konjac glucomannan extracted naturally.

[0020] Preferably, in Formula 3, R2 is methyl or ethyl, and X is H or Na.

[0021] In this invention, the weight ratio of component A, component B, component C, and component D is 4~6:1~2:1~2:2~3.

[0022] For example, in the composite inhibitor described in this invention, the content of component A can be 30-70 wt.%, more preferably 40-60 wt.%; the content of component B can be 10-20 wt.%; the content of component C can be 10-20 wt.%; and the balance is component D.

[0023] The present invention also provides a method for inhibiting the flotation of copper sulfide ore, wherein the inhibitor comprises the composite inhibitor described in the present invention.

[0024] In this invention, the flotation inhibitor can synergistically and selectively inhibit copper sulfide, thereby enabling reverse flotation enrichment of copper sulfide. In addition, it can also achieve the separation of sulfide ores and other minerals, such as minerals with natural floatability.

[0025] The present invention also provides a flotation reagent for copper-molybdenum separation, which comprises a composite inhibitor of the copper sulfide ore.

[0026] In this invention, the flotation inhibitor can selectively inhibit copper sulfide ores and has virtually no inhibitory effect on molybdenum sulfide ores, thus enabling selective separation of molybdenum and copper.

[0027] In this invention, molybdenum sulfide ore has excellent natural floatability, and it can achieve selective separation of molybdenum and copper by effectively inhibiting copper with a composite inhibitor, while having virtually no inhibitory properties on molybdenum.

[0028] To further optimize the copper-molybdenum separation efficiency, the flotation reagent may also include at least one of the following: frother, collector, pH adjuster, and dispersant.

[0029] In this invention, the foaming agent can be a conventional foaming component in the industry, such as No. 2 oil, terpineol, BK201, methyl isobutyl methanol, methyl pentanol, 2-ethylhexanol, C6-C8 mixed fatty alcohols, mixed hexacarbon alcohols, C5-C7 mixed secondary alcohols, 1,1,3-triethoxybutane, methyl alcohol ether, ethyl alcohol ether, butyl alcohol ether, C5-C6 mixed fatty acid ethyl esters, C5-C9 mixed fatty acid ethyl esters, diethyl phthalate, BK series foaming agents, RB series foaming agents, and 730 series foaming agents.

[0030] In this invention, the collector is a conventional molybdenum sulfide ore collector, which includes at least one of non-polar hydrocarbon oil collectors, polar collectors, and combined collectors.

[0031] The non-polar hydrocarbon oil collectors include at least one of kerosene, diesel oil, emulsified hydrocarbon oil, and complex hydrocarbon oil; the polar collectors include at least one of the following: a compound product of kerosene and a polar agent, CMOZ, LKD-3 (the active ingredients are 2,3,5-trimethylnaphthalene and decadecyl alcohol), thiomonoglycerate, agent F, TBC-114, CSU31, xanthate, alkylphenol polyoxyethylene ether, tall oil, phthalate, and hydrocarbon oxycarbonyl thiourea; the combined collectors include at least one of the following: a complex of coal tar extract and a conventional hydrocarbon oil collector, a nanoemulsion collector, and a combination of the above agents.

[0032] In this invention, the pH adjuster is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium oxide, ammonia, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, or oxalic acid.

[0033] In this invention, the dispersant is at least one of sodium silicate, sodium hexametaphosphate, sodium carbonate, carboxymethyl cellulose, starch, sodium polyacrylate, or tannic acid.

[0034] In this invention, the flotation reagent may also contain auxiliary inhibitors, which may be selected from water glass, potassium silicate, aluminum silicate, sodium fluorosilicate, sodium fluorosilicate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, disodium hydrogen phosphate, sodium fluoride, ammonium fluoride, calcium fluoride, sodium sulfide, sodium thiosulfate, sodium sulfite, sodium carbonate, sodium oxalate, sodium molybdate, sodium tungstate, oxalic acid, citric acid, tartaric acid, malic acid, maleic acid, malonic acid, gluconic acid, lactic acid, salicylic acid, aminotrimethylphosphonic acid, hydroxyethylidene diphosphonic acid, mercaptoacetic acid, dithiocarbamate, tannic acid, gallic acid, tannic acid, humic acid, starch, dextrin, carboxymethyl starch, oxidized starch, carboxymethyl cellulose, guar gum, sodium lignosulfonate, calcium lignosulfonate, sulfonated lignin, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyethylene glycol, gelatin, peptone, soy protein, and at least one of the above-mentioned substances or their combinations or modified products.

[0035] Preferably, the flotation reagent includes the composite inhibitor, collector, pH adjuster, and frother.

[0036] The present invention also provides a method for separating copper and molybdenum, wherein the minerals to be separated, including copper sulfide ore and molybdenum sulfide ore, are mixed with the flotation reagents described in the present invention and subjected to flotation to obtain tailings enriched with copper sulfide ore and concentrate enriched with molybdenum sulfide ore.

[0037] In this invention, thanks to the innovative use of the special composite inhibitor, highly selective inhibition of copper sulfide ore can be achieved, thus enabling selective separation of copper and molybdenum.

[0038] In this invention, copper sulfide and copper sulfide ores refer to chalcopyrite. Molybdenum sulfide ores refer to molybdenite.

[0039] In this invention, the candidate minerals may also include other sulfide minerals and / or gangue minerals, such as quartz and calcite. The composite inhibitor can preferentially adsorb onto the surface of chalcopyrite in this complex slurry system, achieving selective inhibition.

[0040] In this invention, during the flotation process, the pH of the pulp is 2-12, preferably 4-10, and more preferably 6-10. The method of this invention can achieve excellent copper selectivity inhibition under a wide range of pH conditions.

[0041] In this invention, the flotation temperature is 5~40℃, preferably 10~30℃, and more preferably 15~25℃. The flotation scheme described in this invention can function stably at room temperature and within a slightly wider temperature range.

[0042] Preferably, the amount (concentration) of the composite inhibitor in the flotation pulp is 10~300 mg / L, more preferably 60~200 mg / L; and even more preferably 100~150 mg / L.

[0043] In this invention, as an optional embodiment, the flotation reagent may include a composite inhibitor, a frother, a collector, and a pH adjuster. Depending on actual needs, dispersants or auxiliary inhibitors may also be selectively added.

[0044] As an optional approach, when the flotation reagents include collectors and frothers, considering processing costs, the amount of collector in the flotation pulp should be ≤500 mg / L, and further can be 10~100 mg / L considering costs; the amount of frother in the flotation pulp should be ≤100 mg / L, and further can be 1~20 mg / L considering costs.

[0045] In this invention, the flotation reagents can be added in any order as needed, or they can be pre-prepared as a mixed reagent before being added.

[0046] Beneficial effects

[0047] 1. The composite inhibitor of the present invention can selectively inhibit copper sulfide minerals.

[0048] 2. The composite inhibitor described in this invention can not only selectively inhibit copper sulfide ores, but also hardly affect the floatability of molybdenum sulfide ores, thereby significantly improving the separation selectivity of molybdenum and copper, and improving the grade and recovery rate of copper sulfide ores and molybdenum sulfide ores.

[0049] 3. The composite inhibitor and flotation reagent of this invention can stably exert their inhibitory effect over a wide pH and temperature range. It is environmentally friendly and highly selective, avoiding the problems of large dosage, poor environmental performance, and poor selectivity associated with traditional inhibitors. This method can effectively improve the comprehensive utilization rate of copper and molybdenum resources, combining economic benefits with environmental advantages, and has promising prospects for industrial application. Detailed Implementation

[0050] The effects of this invention are illustrated using single-mineral and artificially blended ore samples (chalcopyrite and molybdenite in a 1:1 weight ratio) as examples. Unless otherwise stated, the mineral compositions used in the following examples are shown in Table 1:

[0051] Table 1. Mineral sample content (%)

[0052] ;

[0053] In the following examples, the flotation pH refers to the pH of the pulp during the flotation stage, and the acidic adjuster in the pH adjuster can be hydrochloric acid, and the alkaline adjuster can be sodium hydroxide.

[0054] In this invention, in addition to the addition of a composite inhibitor, the flotation reagent may also contain, as needed, a collector, a foaming agent, a pH adjuster, and other components.

[0055] In the following examples, the collectors, foaming agents, and pH adjusters mentioned can be corresponding compounds commonly used in the industry.

[0056] As an optional option, component A is typically illustrated using Equation 1A.

[0057] Component B is illustrated by Formula 2A as a typical example.

[0058] Component D is illustrated with 3A as a typical example.

[0059] Formula 1A.

[0060] Equation 2A.

[0061] Formula 3A.

[0062] Example 1

[0063] To verify the flotation effect of the chalcopyrite composite depressant, single mineral flotation experiments were first conducted using chalcopyrite and molybdenite (Table 1) at a flotation temperature of 25°C. The chalcopyrite composite depressant and flotation reagents used in this case were used for flotation. Except for the amount of composite depressant, the amounts of other reagents and flotation process parameters were the same in each group of cases. In this embodiment, kerosene was added as a collector, terpineol as a frother, and hydrochloric acid and sodium hydroxide as pH adjusters (added as needed).

[0064] In this embodiment, the weight ratio of the chalcopyrite composite inhibitors (Formula 1A, Formula 2A, konjac mannan, and Formula 3A) is 4:2:2:2.

[0065] The specific operation of the single mineral flotation process is as follows: The single pure mineral ore (particle size of 3 mm to 0.5 mm) in Table 1 is dry ball-milled. For each group, 2.0 g of the milled single mineral sample with a particle size of 0.074 to 0.038 mm is weighed and poured into a 40 mL flotation cell. A pH adjuster is added to adjust the pulp to pH = 8. After adding 35 mL of deionized water, the chalcopyrite composite inhibitor of this embodiment is added and stirred for 3 min. Kerosene (dosage of 30 mg / L) is added as a collector and stirred for 3 min. Terpineol (10 mg / L) is added as a frother and stirred for 1 min. The frothing begins and frothing is carried out for 3 min. The concentrate is scraped to the concentrate basin along with the froth. The tailings remain in the flotation cell. The concentrate and tailings are filtered, dried, and weighed separately. The recovery rate is calculated. Each group of experiments is conducted in three parallel groups, and the average value is taken. Table 2 shows the recovery rates of chalcopyrite and molybdenite in Example 1 at different amounts of chalcopyrite composite inhibitor (0~150 mg / L).

[0066] Table 2 Flotation results of Example 1

[0067] ;

[0068] Experimental results (Table 2) show that when the pulp pH is 8, the composite inhibitors all exhibit significant selective inhibition on chalcopyrite. For example, when the composite inhibitor dosage is 100 mg / L, the chalcopyrite recovery rate further decreases to 32.4%, demonstrating a significant inhibitory effect, while the molybdenite recovery rate remains above 97%, with a difference of approximately 65%, exhibiting excellent selectivity. Furthermore, when the composite inhibitor dosage is 150 mg / L, the chalcopyrite recovery rate decreases to 20.5%, while the molybdenite recovery rate remains above 90%, with a difference of approximately 70%. These results confirm that the composite inhibitors of this invention have strong selective inhibitory ability on chalcopyrite over a wide dosage range, with minimal impact on the floatability of molybdenite, effectively achieving efficient flotation separation of chalcopyrite and molybdenite.

[0069] Example 2

[0070] To verify the effect of pulp pH control on the flotation effect of the chalcopyrite composite inhibitor and flotation reagents, single mineral flotation experiments were conducted using high-purity chalcopyrite and molybdenite (Table 1). The chalcopyrite composite inhibitor used in this case was used to collect the pure minerals, and the flotation temperature was 15℃. Flotation was carried out using the chalcopyrite composite inhibitor and flotation reagents used in this case. Except for pulp pH, the flotation reagent system and flotation process parameters were the same for each group of cases. In this embodiment, kerosene was added as a collector, terpineol as a frother, and hydrochloric acid and sodium hydroxide as pH adjusters (added as needed).

[0071] In this embodiment, the weight ratio of the chalcopyrite composite inhibitors (Formula 1A, Formula 2A, konjac mannan, and Formula 3A) is 4:2:2:2.

[0072] The specific operation of the single-mineral flotation process is as follows: Pure mineral ore (particle size 3 mm~0.5 mm) is dry-milled. For each group, 2.0 g of the milled single-mineral sample with a particle size range of 0.074~0.038 mm is weighed and poured into a 40 mL flotation cell. A pH adjuster is added to adjust the pulp pH to 4, 6, 7, 8, and 10 respectively. After adding 35 mL of deionized water, the chalcopyrite composite inhibitor (125 mg / L) of this embodiment is added and stirred for 3 min. Kerosene (30 mg / L) is added as a collector and stirred for 3 min. Terpineol (10 mg / L) is added as a frother and stirred for 1 min. Foaming begins and continues for 3 min. The concentrate is scraped to the concentrate basin along with the foam, while the tailings remain in the flotation cell. The concentrate and tailings are filtered, dried, and weighed separately. The recovery rate is calculated. Each experiment is performed in triplicate, and the average value is taken. Table 3 shows the recovery rates of chalcopyrite and molybdenite under different pulp pH conditions in Example 2.

[0073] Table 3 Flotation results of Example 2

[0074] ;

[0075] As shown in Table 3, within a relatively wide pulp pH range of 4–10, the composite inhibitor of this invention exhibits significant differences in selective inhibition against chalcopyrite and molybdenite. Flotation results show that the recovery rate of molybdenite remains above 94%, while the recovery rate of chalcopyrite is below 26%, with the difference in recovery rates remaining stable between 71.8% and 73.0%. Particularly under weakly alkaline conditions of pH 8–10, the difference in recovery rates reaches over 72.9%, indicating even better selective inhibition. These results verify that the composite inhibitor of this invention has good applicability across a wide pH range, achieving high selectivity and strong inhibition of chalcopyrite without affecting the recovery rate of molybdenite.

[0076] Example 3

[0077] To verify the flotation performance of the chalcopyrite composite depressant and flotation reagent in the flotation of mixed ores, high-purity chalcopyrite and molybdenite samples with particle sizes ranging from 0.074 to 0.038 mm were mixed in a 1:1 ratio to obtain an artificial mixed ore (Table 1). Flotation experiments were conducted on the mixed ore at a flotation temperature of 20°C. The chalcopyrite flotation reagent used in this case was used to float the mixed ore. The pulp pH was 8. Hydrochloric acid and sodium hydroxide were used as pH adjusters in all examples. Except for the differences in the composition, ratio, and dosage of the flotation reagents, all other flotation process parameters were the same in each group of cases. The copper-molybdenum flotation reagent in this example contains a composite depressant, a collector, and a frother, the composition, ratio, and dosage of which are as follows:

[0078] Example 3-1: A composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 4:2:2:2; dosage 125 mg / L), a collector (kerosene; dosage 30 mg / L), and a foaming agent (terpineol; dosage 10 mg / L).

[0079] Example 3-2: A composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 6:1:1:2; dosage 125 mg / L), a collector (kerosene; dosage 30 mg / L), and a foaming agent (terpineol; dosage 10 mg / L).

[0080] Example 3-3: Composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 5:1:1:3; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L);

[0081] Examples 3-4: Composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 4:2:2:2; dosage 100 mg / L), collector (kerosene and diesel in a weight ratio of 1:1; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0082] Examples 3-5: Composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 4:2:2:2; dosage 100 mg / L), collector (kerosene; dosage 20 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0083] Examples 3-6: Composite inhibitors (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 4:2:2:2; dosage 100 mg / L), foaming agent (terpineol; dosage 30 mg / L).

[0084] Examples 3-7: Composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 4:2:2:2; dosage 100 mg / L), collector (kerosene; dosage 30 mg / L).

[0085] The specific operation of the mixed ore flotation process is as follows: 2.0 g of the mixed ore sample is weighed into a 40 mL flotation cell for each group. A pH adjuster is added to adjust the pulp to pH = 8. After adding 35 mL of deionized water, the flotation reagents for each group are added. The mixture is stirred for 3 minutes, and then the foam is scraped off. After 3 minutes of foam scraping, the concentrate is scraped to the concentrate basin along with the foam, while the tailings remain in the flotation cell. The concentrate and tailings are filtered, dried, and weighed separately. The recovery rate is calculated. Each group of experiments is performed in triplicate, and the average value is taken. Table 4 shows the Mo grade and molybdenite recovery rate of the mixed ore in Example 3 after using different flotation reagents.

[0086] Table 4. Flotation results of mixed ore in Example 3

[0087] ;

[0088] As shown in Table 4, the flotation reagents of this invention exhibit excellent separation effects in the flotation of artificially mixed ores. In all examples, the recovery rate of molybdenite reached over 93%, with a maximum of 99.0%, confirming the highly efficient collection ability of the selected collector for molybdenite. Simultaneously, the molybdenum concentrate grade remained above 50%, reaching a maximum of 56.2%, indicating that the composite inhibitor exhibited high selectivity and strong inhibition on chalcopyrite, achieving effective separation of chalcopyrite and molybdenite. Regarding the reagent ratios, Example 3-1 (weight ratio of Formula 1A, Formula 2A, konjac mannan, and Formula 3A 4:2:2:2) achieved a molybdenum grade of 55.1% while maintaining a recovery rate of 99.0%, demonstrating excellent overall performance. Example 3-3 achieved the highest grade of 56.2% with a recovery rate of 93.3%, suitable for situations requiring higher grades. Regarding the collector formulation, Examples 3-4 used a mixture of kerosene and diesel oil, achieving a stable grade while maintaining a high recovery rate. However, in Examples 3-5, the recovery rate decreased after reducing the collector dosage. Examples 3-6 and 3-7 confirmed that, with appropriate dosages, adding either the frother or the collector in the copper-molybdenum flotation reagent of this invention yields a higher concentrate grade (56.5% with only frother and 57.2% with only collector), but the recovery rate is lower (91.9% with only frother and 93.1% with only collector). These results indicate that the flotation reagent of this invention can flexibly control the separation parameters by adjusting the ratio of the composite inhibitor and the collector regime, achieving both high recovery and high grade, providing a reliable solution for the efficient separation of copper-molybdenum ore.

[0089] Comparative Example 1

[0090] Compared with Example 3-1, the only difference lies in the composition, ratio, and dosage of the flotation reagent. The composition, ratio, and dosage of the copper-molybdenum flotation reagent in this comparative example are as follows:

[0091] Comparative Example 1-1: Inhibitor (Formula 1A; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L);

[0092] Comparative Examples 1-2: Inhibitor (Formula 2A; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), frother (terpineol; dosage 10 mg / L);

[0093] Comparative Examples 1-3: Inhibitor (Formula 3A; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L);

[0094] Comparative Examples 1-4: Inhibitor (konjac mannan; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L);

[0095] Comparative Examples 1-5: Compound inhibitor (only lacking Formula 1A, the proportions and total dosages of the remaining three components are the same as in Examples 3-1), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0096] Comparative Examples 1-6: Compound inhibitor (only lacking Formula 2A, the proportions and total dosages of the remaining three components are the same as in Examples 3-1), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0097] Comparative Examples 1-7: Composite inhibitor (only lacking konjac mannan, the proportions and total dosages of the remaining three components are the same as in Examples 3-1), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0098] Comparative Examples 1-8: Compound inhibitor (only lacking Formula 3A, the proportions and total dosages of the remaining three components are the same as in Examples 3-1), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0099] Comparative Examples 1-9: Composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 1:5:2:2; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L);

[0100] Comparative Examples 1-10: Composite inhibitor (Formula 1A, Formula 2A, konjac mannan and Formula 3A in a weight ratio of 2:1:4:3; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L).

[0101] Comparative Examples 1-11: Compound inhibitor (weight ratio of Formula 1A, Formula 2A, hydroxypropyl methylcellulose and Formula 3A is 4:2:2:2; dosage is 125 mg / L), collector (kerosene; dosage is 30 mg / L), foaming agent (terpineol; dosage is 10 mg / L);

[0102] Comparative Examples 1-12: Composite inhibitor (Formula 1A, Comparative Formula A, konjac mannan and Formula 3A in a weight ratio of 4:2:2:2; dosage 125 mg / L), collector (kerosene; dosage 30 mg / L), foaming agent (terpineol; dosage 10 mg / L);

[0103] Comparison A;

[0104] All other operations and parameters are the same as in Example 3, and the flotation results of each group are shown in Table 5.

[0105] Table 5. Flotation results of mixed ore in Example 3

[0106] ;

[0107] As shown in Table 5, the flotation results of Comparative Example 1 reveal the influence of different inhibitor compositions on the separation of copper and molybdenum. When using a single component as an inhibitor, Comparative Examples 1-1 to 1-4 all exhibited significant drawbacks: Single component 1A (Comparative Example 1-1) achieved a recovery rate of 93.5%, but the molybdenum grade was only 45.2%, indicating insufficient selectivity; Single component 2A (Comparative Example 1-2) had some inhibitory ability, but the molybdenite recovery rate was only 70.6%, resulting in significant losses; Single component 3A (Comparative Example 1-3) achieved the required recovery rate (93.2%), but the grade was as low as 38.2%, indicating poor inhibitory selectivity; Single component konjac mannan (Comparative Example 1-4) had a high recovery rate (95.9%), but the grade was even lower (35.8%), resulting in even worse inhibitory selectivity.

[0108] Comparative Examples 1-5 to 1-8 were found to lack one component from Formula 1A, Formula 2A, konjac mannan, or Formula 3A, respectively. The results showed that the absence of any key component led to a significant deterioration in the separation effect, and it was difficult to maintain both the grade and the recovery rate, indicating that the three components must work synergistically.

[0109] Although Comparative Examples 1-9 and 1-10 contain all four components, their proportions exceed the preferred range of this invention. Specifically, Comparative Examples 1-9 (1:5:2:2) has a grade of 54.2% but a recovery rate of only 84.5%, while Comparative Examples 1-10 (2:1:4:3) has a recovery rate of 98.7% but a grade of only 46.2%. Neither of them can simultaneously achieve high grade and high recovery rate.

[0110] When konjac mannan was replaced with the common polysaccharide inhibitor hydroxymethyl cellulose (Comparative Examples 1-11), the grade and recovery rate of Mo decreased significantly, down to 47.7% and 82.5%, respectively. When Formula 2A was replaced with Comparative Formula A, the grade and recovery rate of Mo both showed a decreasing trend, down to 50.9% and 89.7%, respectively. A comparison of the examples and comparative examples shows that the composite inhibitor and flotation reagent of the present invention have significant advantages. For example, Example 3-1 achieved a recovery rate as high as 99.0% while maintaining a molybdenum grade of 55.1%, achieving a balance between high recovery and high grade. The absence of any component of the copper mineral composite inhibitor described in this invention, or substitution with similar substances, or the component ratio not falling within the stated range (3~7:1~2:1~2:1~3), all lead to a significant deterioration in the flotation separation efficiency of copper and molybdenum minerals, making it difficult to simultaneously achieve the desired grade or recovery rate.

[0111] The above comparison fully demonstrates that the composite inhibitor constructed by the present invention, through precise control of the synergistic ratio of the four components of Formula 1A, Formula 2A, konjac mannan and Formula 3A, can efficiently inhibit chalcopyrite while maximizing the flotation recovery of molybdenite, achieving efficient separation of the two. Its comprehensive performance is significantly better than the control scheme with a single component, missing components or improper ratio.

Claims

1. A composite inhibitor for copper sulfide ores, characterized in that, It contains components A, B, C, and D in a weight ratio of 3~7:1~2:1~2:1~3; wherein, component A is a compound of formula 1; component B is a compound of formula 2; component C is konjac mannan; and component D is a compound of formula 3. Formula 1; Formula 2; Formula 3; In Formula 1, M is H, Na, K or NH4; In Formula 2, R1 is a C1~C4 alkylene group, Y is H, Na, K, Ca, Mg or NH4; m is the valence of Y; In Formula 3, R2 is a C1-C4 alkyl group, and X is H, Na, K or NH4.

2. The composite inhibitor for copper sulfide ore as described in claim 1, characterized in that, In Equation 1, M represents Na; In Formula 2, Y represents Ca, m represents 2, and R1 represents methylene or ethylene. In Formula 3, R2 is methyl or ethyl, and X is H or Na; The weight ratio of component A, component B, component C, and component D is 4~6:1~2:1~2:2~3.

3. A method for inhibiting the flotation of copper sulfide ore, characterized in that, The inhibitor comprises the compound inhibitor according to any one of claims 1 to 2.

4. A flotation reagent for copper-molybdenum separation, characterized in that, A composite inhibitor comprising the copper sulfide ore as described in any one of claims 1 to 2.

5. The flotation reagent for copper-molybdenum separation as described in claim 4, characterized in that, It also contains at least one of the following: foaming agent, collector, pH adjuster, and dispersant.

6. The flotation reagent for copper-molybdenum separation as described in claim 5, characterized in that, The foaming agent is at least one of the following: No. 2 oil, terpineol, BK201, methyl isobutyl methanol, methyl pentanol, 2-ethylhexanol, C6-C8 mixed fatty alcohols, mixed hexacarbon alcohols, C5-C7 mixed secondary alcohols, 1,1,3-triethoxybutane, methyl alcohol ether, ethyl alcohol ether, butyl alcohol ether, C5-C6 mixed fatty acid ethyl ester, C5-C9 mixed fatty acid ethyl ester, diethyl phthalate, BK series foaming agents, RB series foaming agents, and 730 series foaming agents. The collector is a molybdenum sulfide ore collector, which includes at least one of non-polar hydrocarbon oil collectors, polar collectors, and combined collectors; The pH adjuster is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium oxide, ammonia, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, or oxalic acid. The dispersant is at least one of sodium silicate, sodium hexametaphosphate, sodium carbonate, carboxymethyl cellulose, starch, sodium polyacrylate, or tannic acid.

7. A method for separating copper and molybdenum, characterized in that, The candidate minerals, which contain copper sulfide and molybdenum sulfide, are mixed with the flotation reagents described in any one of claims 4 to 6 and subjected to flotation to obtain tailings enriched with copper sulfide and concentrate enriched with molybdenum sulfide.

8. The copper-molybdenum sorting method as described in claim 7, characterized in that, During the flotation process, the pH of the pulp is 2-12, the flotation temperature is 5-40℃, and the dosage of the composite inhibitor for copper sulfide ore is 10-300 mg / L.

9. The copper-molybdenum sorting method as described in claim 8, characterized in that, During the flotation process, the pH of the pulp is 4-10, the flotation temperature is 10-30℃, and the dosage of the composite inhibitor for copper sulfide ore is 60-200 mg / L.

10. The method for copper-molybdenum sorting as described in any one of claims 7 to 9, characterized in that, When flotation reagents contain collectors and frothers, the amount of collector in the flotation pulp should be ≤500 mg / L; the amount of frother in the flotation pulp should be ≤100 mg / L.

Images