Chalcopyrite inhibitor and its application

Abstract

The present application provides a chalcopyrite inhibitor and its application, belonging to the field of copper-molybdenum separation. The chalcopyrite inhibitor is an amino acid derivative derived from both amino and carboxyl groups; the amino acid includes one of glycine, alanine, valine, and leucine. The present application introduces a hydrophilic cyclic aliphatic oxygen heterocycle and a solid-philic disulfide carbonyl group by deriving the active amino and carboxyl groups of simple and readily available amino acids. The hydrophilic cyclic aliphatic oxygen heterocycle can achieve the dissolution of the chalcopyrite inhibitor in the aqueous phase; the solid-philic disulfide carbonyl group can achieve the selective chelation of the chalcopyrite inhibitor with copper ions in chalcopyrite in the selected mineral; at the same time, the hydrophilic cyclic aliphatic oxygen heterocycle forms a hydrophilic film on the surface of the chalcopyrite, further achieving effective inhibition of chalcopyrite and achieving the purpose of copper-molybdenum separation.

Description

Technical Field

[0001] The present invention relates to the technical field of copper-molybdenum separation, and in particular to a chalcopyrite inhibitor and application thereof. Background Art

[0002] With the development of my country's economy, the demand for copper and molybdenum resources is increasing. Copper and molybdenum mineral resources often exhibit characteristics such as poor resource endowment, fine particle size, numerous associated components, similar floatability, and high smelting difficulty, making separation of copper and molybdenum difficult. High copper content in molybdenum concentrate not only reduces its quality but also results in a loss of copper resources.

[0003] Inhibitors are one of the core elements to ensure mineral processing production indicators. Currently, traditional chalcopyrite inhibitors used in copper-molybdenum separation mainly include sodium sulfide, sodium hydrosulfide, sodium cyanide, etc. Sodium sulfide and sodium hydrosulfide are used in large quantities and have high agent costs; sodium cyanide is highly toxic and the subsequent environmental protection management costs are high, making it difficult to meet increasingly stringent environmental protection requirements; at the same time, traditional chalcopyrite inhibitors are difficult to achieve directional inhibition of chalcopyrite in complex ore systems. Summary of the Invention

[0004] In view of the technical problems existing in the background technology, the present application provides a chalcopyrite inhibitor and its application, aiming to solve the technical problems of strong toxicity and poor inhibition effect of traditional chalcopyrite inhibitors.

[0005] In a first aspect, an embodiment of the present application provides a chalcopyrite inhibitor, which is an amino acid derivative derived from both an amino group and a carboxyl group; the amino acid comprises one of glycine, alanine, valine, and leucine; and the structural formula of the chalcopyrite inhibitor is one of A1-A4;

[0006] .

[0007] In the technical solution of the embodiment of the present application, a hydrophilic heterocycle and a solid-philic disulfide carbonyl are introduced by derivatizing the active amino group and carboxyl group of a simple and readily available amino acid. The hydrophilic heterocycle can achieve the dissolution of the chalcopyrite inhibitor in the aqueous phase; the solid-philic disulfide carbonyl can achieve the selective chelation of the chalcopyrite inhibitor with the copper ions in the chalcopyrite in the mineral to be selected; at the same time, the hydrophilic heterocycle forms a hydrophilic film on the surface of the chalcopyrite, further achieving effective inhibition of the chalcopyrite and achieving the purpose of copper-molybdenum separation.

[0008] In a second aspect, the present invention provides a method for separating copper and molybdenum, comprising the following steps:

[0009] Add the copper-molybdenum mixed concentrate into the flotation equipment, and then add the chalcopyrite inhibitor, pH regulator, collector and frother in sequence, and react for the preset time; open the inflation valve to let air in for flotation.

[0010] In the technical solution of the embodiment of the present application, the copper-molybdenum mixed concentrate is first added to the flotation equipment to form a slurry; then, a chalcopyrite inhibitor, a pH regulator, a collector and a frother are added to the slurry in sequence, and the pH regulator adjusts the slurry to an appropriate pH condition, and the hydrophilic group and the solid-philic group of the chalcopyrite inhibitor cooperate with each other to achieve effective inhibition of chalcopyrite; after the collector collects the molybdenum ore, the frother and the collector cooperate with each other to form a foam layer required for flotation on the slurry surface, thereby achieving the floating of the molybdenum ore, thereby achieving the separation of copper and molybdenum.

[0011] In some embodiments, the amount of chalcopyrite inhibitor added is 0.5-15 kg / t.

[0012] In this embodiment, efficient chalcopyrite inhibition is achieved by properly controlling the amount of chalcopyrite inhibitor added.

[0013] In some embodiments, the pH adjuster adjusts the slurry to a pH of 8-12.

[0014] In this embodiment, by properly controlling the pH value of the slurry, the chalcopyrite inhibitor is stably present in the slurry and reacts with the chalcopyrite to achieve efficient chalcopyrite inhibition.

[0015] In some embodiments, the pH adjuster is one of NaOH solution and hydrochloric acid solution; the collector is kerosene, and the amount used is 80-120 g / t; and the foaming agent is methyl isobutyl carbinol, and the amount used is 20-30 g / t.

[0016] In this embodiment, the flotation of molybdenum ore is successfully achieved by reasonably setting the type and concentration of the pH regulator, the type and addition amount of the collector, and the type and addition amount of the frother.

[0017] In some embodiments, during the flotation process, bubbles are scraped off every 4-6 seconds and water is added every 25-35 seconds.

[0018] In this embodiment, the flotation foam is scraped out evenly every 4-6 seconds, effectively controlling the thickness and uniformity of the foam, thereby preventing foam accumulation on the pulp surface and improving the flotation effect; water is added every 25-35 seconds to ensure sufficient water in the flotation equipment, providing favorable conditions for the smooth flotation of molybdenum ore.

[0019] In some embodiments, the rotation speed of the flotation device is 1000-3000 r / min, and the slurry adjustment time is 1-3 min.

[0020] In this embodiment, by reasonably controlling the rotation speed and slurry adjustment time of the flotation equipment, the minerals to be selected are uniformly dispersed in the slurry, providing favorable conditions for the effective suppression of chalcopyrite and the flotation of molybdenum ore.

[0021] In some embodiments, the frother is added 0.5-1.5 minutes after the collector is added, and the inflation valve is opened 2.5-3.5 minutes later to allow air to flow for flotation.

[0022] In this embodiment, by reasonably controlling the addition time of different reagents, the different reagents can fully exert their effects, further achieving effective suppression of chalcopyrite and efficient flotation of molybdenum ore.

[0023] In some embodiments, during the flotation process, the floating molybdenum concentrate is collected at 1 minute, 3 minutes, 6 minutes and 10 minutes respectively.

[0024] In this embodiment, the molybdenum ore obtained by flotation is collected in a specific manner to achieve multiple and efficient recovery of the molybdenum ore and improve the recovery rate of the molybdenum ore.

[0025] In some embodiments, the recovery rate of molybdenum ore is as high as 90%, and the recovery rate of chalcopyrite is as low as 7%.

[0026] In this embodiment, by adding the chalcopyrite inhibitor of the specific structure of the present application to the flotation process, efficient recovery of molybdenum ore was achieved. At the same time, the recovery rate of chalcopyrite was low, indicating that the chalcopyrite inhibitor of the present application has a good inhibitory effect on chalcopyrite.

[0027] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] To more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings used in this application. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0029] Figure 1 This is a diagram showing the mechanism of action of the chalcopyrite inhibitor in the examples of this application;

[0030] Figure 2 This is a process flow chart for separation of copper and molybdenum in the embodiment of the present application;

[0031] Figure 3 This is a flow chart for preparing the chalcopyrite inhibitor A1 in Example 1;

[0032] Figure 4 This is the H NMR spectrum of chalcopyrite inhibitor A1. DETAILED DESCRIPTION

[0033] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0035] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0036] Copper and molybdenum mineral resources often exhibit numerous associated components and similar floatability, making copper-molybdenum separation difficult. Conventional chalcopyrite inhibitors currently used in copper-molybdenum separation are highly toxic, leading to high costs for subsequent environmental remediation. Furthermore, targeted chalcopyrite inhibition in complex ore systems is difficult to achieve, resulting in poor inhibition effectiveness.

[0037] In order to solve the technical problems of strong toxicity and poor inhibition effect of traditional chalcopyrite inhibitors, the present application provides a chalcopyrite inhibitor and its preparation method and application, wherein, by regulating the specific molecular skeleton spatial structure of the chalcopyrite inhibitor, designing the types of functional groups, and the mutual cooperation between the two types of functional groups, efficient and selective inhibition of chalcopyrite in copper and molybdenum associated ores is achieved, thereby achieving the purpose of copper and molybdenum separation.

[0038] In a first aspect, an embodiment of the present application provides a chalcopyrite inhibitor, which is an amino acid derivative derived from both an amino group and a carboxyl group; the amino acid comprises one of glycine, alanine, valine, and leucine; and the structural formula of the chalcopyrite inhibitor is one of A1-A4;

[0039] .

[0040] In the technical solution of the embodiment of the present application, Figure 1 As shown, by derivatizing the active amino and carboxyl groups of simple and readily available amino acids, functional heterocycles with special structures (i.e. Figure 1 Functional group B) and dithiocarbonyl (i.e. Figure 1 The functionalized functional group A in the molecular skeleton of the chalcopyrite inhibitor plays two different roles. Specifically, the hydroxyl group and the cyclic aliphatic oxygen heterocycle act as hydrophilic groups to achieve the dissolution of the chalcopyrite inhibitor in the aqueous phase; secondly, the dithiocarbonyl group acts as a solid-philic group to achieve the interface chemical adsorption between the chalcopyrite inhibitor and the chalcopyrite in the mineral to be selected. In this process, the dithiocarbonyl S - The lone pair electrons on the N group selectively chelate with the copper ions in chalcopyrite, achieving a strong bond between the chalcopyrite and the chalcopyrite inhibitor. Simultaneously, the hydroxyl group and the cyclic aliphatic oxygen heterocycle form a hydrophilic film on the chalcopyrite surface, stabilizing the chalcopyrite in the slurry and effectively inhibiting chalcopyrite. Furthermore, the steric effect of the cyclic aliphatic oxygen heterocycle positions the different groups in the chalcopyrite inhibitor in specific locations. Specifically, the cyclic aliphatic oxygen heterocycle imparts a unique spatial position to the chalcopyrite inhibitor's molecular structure, enabling the synergistic interaction of the two functional groups, thereby achieving targeted chelation of copper ions and ultimately separating chalcopyrite from molybdenite (e.g., molybdenite). Specifically, by regulating the specific spatial structure of the chalcopyrite inhibitor's molecular skeleton, designing the types of functional groups, and synergizing the two functional groups, the present invention achieves efficient and selective inhibition of chalcopyrite in copper-molybdenum associated ores, thereby achieving the goal of copper-molybdenum separation. In addition, the chalcopyrite inhibitor is an amino acid derivative. The amino acid raw material is widely available, non-toxic and easily degradable, thus avoiding the problems of traditional chalcopyrite inhibitors such as difficulty in degradation and high toxicity.

[0041] In a second aspect, the present invention provides a method for separating copper and molybdenum, comprising the following steps:

[0042] Add the copper-molybdenum mixed concentrate into the flotation equipment, and then add the chalcopyrite inhibitor, pH regulator, collector and frother in sequence, and react for the preset time; open the inflation valve to let air in for flotation.

[0043] In the technical solution of the embodiment of the present application, the copper-molybdenum mixed concentrate is first added to the flotation equipment, and the copper-molybdenum mixed concentrate and the water in the flotation equipment form a slurry; then, a chalcopyrite inhibitor, a pH regulator, a collector and a frother are added to the slurry in sequence, and the pH regulator adjusts the slurry to an appropriate pH condition. The hydrophilic group of the chalcopyrite inhibitor realizes the dissolution of the agent in the aqueous phase, and at the same time, the solid-philic group realizes the selective chelation of the agent with the chalcopyrite in the mineral, and the hydrophilic group forms a hydrophilic film on the surface of the chalcopyrite, so that the chalcopyrite is stably present in the slurry, thereby realizing effective inhibition of the chalcopyrite; after the collector collects the molybdenum ore, the frother and the collector cooperate with each other to form a foam layer required for flotation on the slurry surface, thereby realizing the floating of the molybdenum ore, thereby obtaining the molybdenum ore and realizing the separation of copper and molybdenum.

[0044] In some embodiments, the amount of chalcopyrite inhibitor added is 0.5-15 kg / t. Specifically, 0.5-15 kg of chalcopyrite inhibitor is added per ton of copper-molybdenum mixed concentrate.

[0045] In the technical solution of the embodiment of the present application, by reasonably controlling the amount of chalcopyrite inhibitor added, it is avoided that the chalcopyrite inhibitor is too little and has no inhibitory effect, and at the same time, it is avoided that the chalcopyrite inhibitor is too much and causes waste and increases the difficulty of subsequent treatment.

[0046] In some embodiments, the pH adjuster adjusts the slurry to a pH of 8-12.

[0047] In the technical solution of the embodiment of the present application, by reasonably controlling the pH value of the slurry, the chalcopyrite inhibitor is stably present in the slurry and reacts with the chalcopyrite to achieve efficient inhibition of chalcopyrite.

[0048] In some embodiments, the pH adjuster is one of a NaOH solution and a hydrochloric acid solution; the collector is kerosene at a dosage of 80-120 g / t; and the frother is methyl isobutyl carbinol (MIBC) at a dosage of 20-30 g / t. Specifically, the concentration of the NaOH solution is 500 g / L; the hydrochloric acid solution is a mixture of hydrochloric acid and water in a volume ratio of 1:1; and 80-120 g of kerosene and 20-30 g of MIBC are added to each ton of copper-molybdenum mixed concentrate.

[0049] In the technical solutions of the embodiments of this application, by rationally setting the type and concentration of the pH adjuster, selecting an appropriate pH adjuster based on the type of ore to be selected, and adjusting the slurry to an appropriate pH, the chalcopyrite inhibitor effectively inhibits chalcopyrite. By rationally controlling the type and amount of the collector, molybdenum ore recovery is successfully achieved. By rationally controlling the type and amount of the frother, and leveraging the synergistic effect of the collector and frother, molybdenum ore flotation is successfully achieved.

[0050] In some embodiments, during the flotation process, bubbles are scraped off every 4-6 seconds and water is added every 25-35 seconds.

[0051] In the technical solution of the embodiment of the present application, the foam is scraped out evenly every 4-6 seconds, effectively controlling the thickness and uniformity of the foam, thereby preventing the foam from accumulating on the pulp surface and improving the flotation effect; water is added every 25-35 seconds to ensure sufficient water in the flotation equipment, providing favorable conditions for the smooth flotation of molybdenum ore.

[0052] In some embodiments, the rotation speed of the flotation device is 1000-3000 r / min, and the slurry adjustment time is 1-3 min.

[0053] In the technical solution of the embodiment of the present application, by reasonably controlling the rotation speed and slurry adjustment time of the flotation equipment, the minerals to be selected are evenly dispersed in the slurry, providing favorable conditions for the effective suppression of chalcopyrite and the flotation of molybdenum ore.

[0054] In some embodiments, the frother is added 0.5-1.5 minutes after the collector is added, and the inflation valve is opened 2.5-3.5 minutes later to allow air to flow for flotation.

[0055] In the technical solution of the embodiment of the present application, by reasonably controlling the addition time of different reagents, different reagents can fully exert their effects, further achieving effective suppression of chalcopyrite and efficient flotation of molybdenum ore.

[0056] In some embodiments, during the flotation process, the floating molybdenum concentrate is collected at 1 minute, 3 minutes, 6 minutes and 10 minutes respectively.

[0057] In the technical solution of the embodiment of the present application, the floating molybdenum concentrate is collected at 1 minute, 3 minutes, 6 minutes and 10 minutes respectively, and the molybdenum ore obtained by flotation is collected regularly to achieve multiple and efficient recovery of the molybdenum ore and improve the recovery rate of the molybdenum ore.

[0058] In some embodiments, the recovery rate of molybdenum ore is as high as 90%, while the recovery rate of chalcopyrite is as low as 7%. Specifically, the recovery rate of molybdenum ore = the total mass of molybdenum ore in the molybdenum concentrate obtained by flotation / the total mass of molybdenum ore in the copper-molybdenum mixed concentrate; the recovery rate of chalcopyrite = the total mass of chalcopyrite in the molybdenum concentrate obtained by flotation / the total mass of chalcopyrite in the copper-molybdenum mixed concentrate. A higher recovery rate of molybdenum ore and a lower recovery rate of chalcopyrite indicate a lower copper content in the molybdenum concentrate obtained by flotation and a better chalcopyrite inhibitor's inhibitory effect on chalcopyrite.

[0059] In the technical solution of the embodiment of the present application, by adding the chalcopyrite inhibitor of the specific structure of the present application to the flotation process, efficient recovery of molybdenum ore is achieved. At the same time, the recovery rate of chalcopyrite is low, indicating that the chalcopyrite inhibitor of the present application has a good inhibitory effect on chalcopyrite.

[0060] Some specific examples are listed below. It should be noted that the examples described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0061] Example 1

[0062] A process for separating copper and molybdenum, such as Figure 2 As shown, the following steps are included:

[0063] S1. Grind the copper-molybdenum mixed concentrate so that the portion of the ore powder with a particle size of less than 0.074 mm accounts for 80% of the total mass of the ore powder; add water to 1000 g of the copper-molybdenum mixed concentrate to prepare a 3 L slurry, and place the slurry in an XFG-3 flotation machine. When the water level in the flotation machine reaches an appropriate position, set the impeller speed of the flotation machine to 2000 r / min, and mix the slurry for 2 minutes to obtain a slurry. Specifically, the mineral species and contents of the copper-molybdenum mixed concentrate are shown in Table 1.

[0064] S2. Add 10 kg / t of chalcopyrite inhibitor A1 to the slurry, immediately adjust the slurry pH to 8 with NaOH solution, add 100 g / t of kerosene after 3 minutes, and add 25 g / t of MIBC after 1 minute.

[0065] S3. Add the frother MIBC and allow it to react for 3 minutes. Then, open the air valve to allow air in and begin flotation. Scrape the foam every 5 seconds and add water every 30 seconds, repeating this process. Collect the floating molybdenum concentrates at 1 minute, 3 minutes, 6 minutes, and 10 minutes of cumulative flotation time to obtain four types of molybdenum concentrates. Combine the four types of molybdenum concentrates, filter them, and dry them in a 60°C oven. Then weigh them. The molybdenite and chalcopyrite contents in the flotation concentrates were determined, and the recoveries of the molybdenite and chalcopyrite were calculated.

[0066] The recovery rate of molybdenite = the total mass of molybdenite in the molybdenum concentrate obtained by flotation / the total mass of molybdenite in the copper-molybdenum mixed concentrate; the recovery rate of chalcopyrite = the total mass of chalcopyrite in the molybdenum concentrate obtained by flotation / the total mass of chalcopyrite in the copper-molybdenum mixed concentrate.

[0067] Among them Figure 3 As shown, the preparation method of chalcopyrite inhibitor A1 comprises the following steps:

[0068] (1) Add 1 mol of glycine and 1.5 mol of isosorbide to a 3 L round-bottom flask, add 2 L of 1+10 sulfuric acid solution (i.e., the volume ratio of concentrated sulfuric acid to water is 1:10), heat under reflux at 100 ° C, and stir for 3 h. After the reaction is completed, adjust the pH value of the reaction solution to neutral with 0.5 M sodium hydroxide solution. Extract repeatedly with ethyl acetate, collect the organic phase, and vacuum evaporation to remove ethyl acetate to obtain glycine isosorbide ester with a yield of 27%-30%.

[0069] (2) Mix 0.05 mol of isosorbide glycine, 0.04 mol of carbon disulfide and 0.08 mol of sodium hydroxide, stir at 40°C for 2 h, add water and ultrasonically dissolve, filter, collect the aqueous phase, and distill under reduced pressure to obtain chalcopyrite inhibitor A1 with a yield of 82%-87%. Figure 4Shown is the 1H NMR (D2O, 400 MHz) pattern of the chalcopyrite inhibitor A1, specifically: δ 3.20~3.30(2H), 3.45~3.55(1H), 3.80~4.00(3H), 4.09(2H), 4.30~4.38(1H), 4.39~4.45(1H), 4.46~4.70(1H).

[0070] The preparation methods of chalcopyrite inhibitors A2-A4 are similar to the preparation method of chalcopyrite inhibitor A1, except that glycine is replaced by alanine, valine, and leucine, respectively, which will not be repeated here.

[0071] Table 1 Measurement results of mineral content in copper-molybdenum mixed concentrate

[0072]

[0073] Examples 2-4 and Comparative Examples 1-11

[0074] A process method for separating copper and molybdenum is provided, which differs from Example 1 in that, in step S2, the type of chalcopyrite inhibitor is different. The other steps are substantially the same as Example 1 and will not be described in detail here.

[0075] The copper-molybdenum separation effects of the chalcopyrite inhibitors used in Examples 1-4 and Comparative Examples 1-11 are shown in Table 2.

[0076] Table 2 Copper-molybdenum separation effects of Examples 1-4 and Comparative Examples 1-11

[0077]

[0078]

[0079] As shown in Table 2, the chalcopyrite inhibitors used in Examples 1-4 resulted in a molybdenite recovery rate exceeding 80%, while the chalcopyrite recovery rate was only 9%-13%. This indicates that the chalcopyrite inhibitors used in Examples 1-4 can achieve selective and efficient chalcopyrite inhibition, thereby achieving the purpose of copper-molybdenum separation. This phenomenon can be attributed to the interaction between the hydrophilic hydroxyl groups, the cyclic aliphatic oxygen heterocycles, and the quasi-philic dithiocarbonyl groups in chalcopyrite inhibitors A1-A4. In addition, Examples 1-4 show that as the steric hindrance of the amino acid side chains used in chalcopyrite inhibitors A1-A4 increases, the chalcopyrite recovery rate increases, indicating that the inhibitory effect of the chalcopyrite inhibitor on chalcopyrite is weakened. This may be because the increased steric hindrance of the side chain groups reduces the stability of the copper chelate and the inhibitory effect on copper.

[0080] When the chalcopyrite inhibitor was omitted (Comparative Example 1), the kerosene collector preferentially captured chalcopyrite while also collecting a significant amount of molybdenite, making copper-molybdenum separation difficult. When conventional sodium sulfide, sodium cyanide, thiosulfate, and ferrous cyanide were used as chalcopyrite inhibitors (Comparative Examples 2-5), the recoveries of chalcopyrite and molybdenite in the molybdenum concentrate obtained by flotation were essentially identical. This indicates that copper and molybdenum coexist in the molybdenum concentrate obtained by flotation, making it impossible to effectively suppress chalcopyrite and achieve copper-molybdenum separation.

[0081] When only the amino group in the amino acid was derivatized, that is, no heterocyclic group was present in the chalcopyrite inhibitor (Comparative Examples 6-9), the recovery rates of molybdenite in the molybdenum concentrate obtained by flotation were all lower than 70%, and the recovery rate of chalcopyrite was higher, indicating that Comparative Examples 6-9 could not achieve the separation of copper and molybdenum. It can be seen that the lack of an aliphatic ring structure cannot achieve selective chelation of chalcopyrite.

[0082] When only the carboxyl groups in the amino acids were derivatized, meaning that the dithiocarbonyl groups were absent from the chalcopyrite inhibitor (Comparative Example 10), the recovery of molybdenite in the molybdenum concentrate obtained by flotation was 90%, and the recovery of chalcopyrite was as high as 91%. This indicates that Comparative Example 10 failed to separate copper from molybdenum, demonstrating that the lack of dithiocarbonyl groups precluded selective chelation of chalcopyrite. When only the heterocyclic structure was replaced with another aliphatic cyclic fragment (Comparative Example 11), the recovery of molybdenite in the molybdenum concentrate obtained by flotation was only 35%, while the recovery of chalcopyrite was as high as 62%. This indicates that Comparative Example 11 failed to separate copper from molybdenum, demonstrating that the lack of the hydrophilic aliphatic cyclic structure precluded selective chelation of chalcopyrite. Comparative Examples 6-11 demonstrate that the chalcopyrite inhibitor of the present application, through the synergistic effect of the specific heterocyclic structure, amino acid type, and dithiocarbonyl groups, effectively inhibits chalcopyrite, thereby achieving the goal of separating copper from molybdenum.

[0083] Examples 5-8 and Comparative Examples 12-13

[0084] A process method for separating copper and molybdenum is provided, which is different from Example 1 in that, in step S2, the pH value of the slurry is different. The other steps are substantially the same as Example 1 and will not be described in detail here.

[0085] The copper-molybdenum separation effects of Examples 5-8 and Comparative Examples 12-13 are shown in Table 3.

[0086] Table 3 Copper-molybdenum separation effects of Examples 5-8 and Comparative Examples 12-13

[0087]

[0088] As can be seen from Table 3, the chalcopyrite inhibitor A1 of Example 1 has a recovery rate of more than 85% for molybdenite in the range of 8 to 12 pH values of the pulp, which is a high recovery rate. At the same time, the recovery rate of chalcopyrite is ≤10%, that is, selective separation of copper and molybdenum can be achieved, indicating that the chalcopyrite inhibitor has a wide window of use in an alkaline environment. When the pH value of the pulp is 7, effective separation of copper and molybdenum cannot be achieved. This may be because the carboxyl group and heterocyclic structure in the molecular structure of the chalcopyrite inhibitor exist in a protonated form at this time, and the activation site is not activated and cannot undergo a chelating reaction with copper ions. When the pH of the pulp is ≥13, the chalcopyrite content in the molybdenum concentrate obtained by flotation is high, indicating that the copper-molybdenum separation effect is poor. This may be because the OH groups in the pulp at this time - When the concentration is too high, some copper ions and iron ions on the surface of chalcopyrite are converted into copper hydroxide, cuprous hydroxide, ferric hydroxide, ferrous hydroxide and other forms respectively. However, the chalcopyrite inhibitor is difficult to react with these alkaline substances to form a chelate reaction, and cannot inhibit copper hydroxide or cuprous hydroxide, resulting in some copper being floated along with molybdenum, causing the copper-molybdenum separation effect to deteriorate.

[0089] Examples 9-13 and Comparative Examples 14-16

[0090] A process method for separating copper and molybdenum using a chalcopyrite inhibitor is provided. Compared with Example 1, the difference lies in that in step S2, the amount of the chalcopyrite inhibitor A1 is different. The rest is substantially the same as Example 1 and will not be described again.

[0091] The copper-molybdenum separation effects of Examples 9-13 and Comparative Examples 14-16 are shown in Table 4.

[0092] Table 4 Copper-molybdenum separation effects of Examples 9-13 and Comparative Examples 14-16

[0093]

[0094] Table 4 shows that chalcopyrite inhibitor A1 can achieve highly effective chalcopyrite suppression at relatively low dosages, achieving copper-molybdenum separation. When the dosage of chalcopyrite inhibitor A1 is less than 0.5 kg / t, the insufficient amount of chalcopyrite inhibitor A1 prevents effective suppression, resulting in a high chalcopyrite recovery rate. When the dosage of chalcopyrite inhibitor A1 is higher than 15 kg / t, the chalcopyrite suppression effect remains essentially stable as the dosage increases. Considering economic costs, the optimal dosage of chalcopyrite inhibitor A1 is between 0.5 and 15 kg / t.

[0095] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any embodiments having substantially the same structure and effect as the technical concept within the scope of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the present application, any other embodiments that can be conceived by those skilled in the art and that combine some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A process for separating copper and molybdenum, characterized in that: The steps include: The copper-molybdenum mixed concentrate is added to the flotation equipment for slurry preparation, and then the chalcopyrite inhibitor, pH regulator, collector and frother are added in sequence, and the reaction is carried out for a preset time; the air filling valve is opened to allow air to flow for flotation; Wherein, the chalcopyrite inhibitor is an amino acid derivative derived from both amino and carboxyl groups; the amino acid comprises one of glycine, alanine, valine, and leucine; the structural formula of the chalcopyrite inhibitor is one of A1-A4; 。 2. The process for separating copper and molybdenum according to claim 1, wherein: The addition amount of the chalcopyrite inhibitor is 0.5-15 kg / t.

3. The process for separating copper and molybdenum according to claim 1, wherein: The pH regulator adjusts the slurry to a pH value of 8-12.

4. The process for separating copper and molybdenum according to claim 1, wherein: The pH regulator is one of NaOH solution and hydrochloric acid solution; the collector is kerosene, with a dosage of 80-120 g / t; and the foaming agent is methyl isobutyl carbinol, with a dosage of 20-30 g / t.

5. The process for separating copper and molybdenum according to claim 1, wherein: During the flotation process, bubbles are scraped every 4-6 seconds and water is added every 25-35 seconds.

6. The process for separating copper and molybdenum according to claim 1, characterized in that: The rotation speed of the flotation equipment is 1000-3000 r / min, and the slurry adjustment time is 1-3 min.

7. The process for separating copper and molybdenum according to claim 1, characterized in that: The frother is added 0.5-1.5 minutes after the collector is added, and the air filling valve is opened 2.5-3.5 minutes after the collector is added to allow air to flow for flotation.

8. The process for separating copper and molybdenum according to claim 1, wherein: During the flotation process, the floating molybdenum concentrate was collected at 1 minute, 3 minutes, 6 minutes and 10 minutes respectively.

9. The process for separating copper and molybdenum according to claim 1, wherein: The recovery rate of molybdenum ore is 90%, and the recovery rate of chalcopyrite is 7%.

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