Environmentally friendly chalcopyrite inhibitor and method for separating copper and molybdenum

Abstract

The present application provides an environmentally friendly chalcopyrite inhibitor and a method for separating copper and molybdenum, belonging to the field of copper-molybdenum separation technology. The environmentally friendly chalcopyrite inhibitor is a sulfur-containing histidine derivative, and its unique aromatic conjugated structure can be converted into a thiol group through tautomerism of the thiocarbonyl group. The S in the thiol group and the N atom in the aromatic ring that contains a lone pair of electrons and does not participate in the conjugation cooperate with each other to directionally chelate the copper ions in the chalcopyrite. The formed chelate has a cyclic structure, which avoids chelation with the molybdenum in the molybdenite and shows excellent selectivity. The environmentally friendly chalcopyrite inhibitor contains both carboxyl and tertiary amine groups. These two types of hydrophilic functional groups with different structures ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit the target mineral in a wider pH window. Based on the specific spatial structure, functional group types and mutual cooperation between different functional groups of the environmentally friendly chalcopyrite inhibitor, it is possible to achieve efficient and selective inhibition of chalcopyrite in copper and molybdenum associated ores in a safe and environmentally friendly manner over a wide pH range.

Description

Technical Field

[0001] The present invention relates to the technical field of copper-molybdenum separation, and in particular to an environmentally friendly chalcopyrite inhibitor and a method for separating copper-molybdenum. Background Art

[0002] At present, traditional chalcopyrite inhibitors mainly include cyanide, sulfide, Knox agent, etc. Although these inhibitors can have a certain inhibitory effect, there are potential environmental and safety problems during use, which are difficult to meet the existing market needs.

[0003] For example, cyanide, as a highly toxic agent, has potential safety uncertainties during production, storage, and transportation. - The complexes formed with impure metal ions have very low dissociation constants, making them difficult to oxidize and prone to long-term accumulation in nature, posing a significant potential hazard to the surrounding environment. Consequently, cyanide is currently banned in many countries. Sulfides, on the other hand, require high concentrations to effectively inhibit sulfide. Research has shown that to achieve separation of mixed molybdenum concentrates, a minimum sulfide inhibitor dosage of 10 kg / t is required. High concentrations of sulfide are prone to decomposition, causing secondary pollution and making wastewater difficult to treat. While Knox Agent has strong inhibitory capabilities, its raw material is highly toxic arsenic, making it hazardous to the human body during preparation and use. Furthermore, the preparation of Knox Agent produces large amounts of H2S gas, which pollutes the environment.

[0004] In addition, when traditional chalcopyrite inhibitors are used in copper-molybdenum separation, their selectivity is often poor, making it difficult to carry out targeted inhibition of chalcopyrite in complex ore systems. At the same time, in the actual flotation process, due to the narrow pH range in which traditional chalcopyrite inhibitors are applicable, there are certain limitations in the application of such inhibitors in copper-molybdenum separation. Summary of the Invention

[0005] In view of the technical problems existing in the background technology, the present application provides an environmentally friendly chalcopyrite inhibitor and a method for separating copper and molybdenum, aiming to solve the technical problems of traditional chalcopyrite inhibitors such as high hazard, poor selectivity and narrow applicable pH range.

[0006] In a first aspect, the embodiments of the present application provide an environmentally friendly chalcopyrite inhibitor, the structural formula of which is as follows:

[0007] .

[0008] The environmentally friendly chalcopyrite inhibitor provided in the embodiment of the present application belongs to a sulfur-containing histidine derivative and is a non-toxic and harmless small molecule organic compound. At the same time, its unique aromatic conjugated structure can be converted into a thiol group through tautomerism of the thiol group, and the S in the thiol group and the N atom in the aromatic ring that contains a lone pair of electrons and does not participate in the conjugation cooperate with each other, which can directionally chelate the copper ions in the chalcopyrite, and the formed chelate presents a cyclic structure, avoiding chelation with molybdenum in molybdenite, showing excellent selectivity. In addition, the environmentally friendly chalcopyrite inhibitor contains two types of hydrophilic functional groups with different structures, namely carboxyl and tertiary amine groups. Among them, the carboxyl group is hydrolyzed to form salts under alkaline conditions, ensuring the hydrophilicity of alkaline conditions, and the tertiary amine group forms a quaternary ammonium salt under acidic conditions, ensuring the hydrophilicity under acidic conditions. These two hydrophilic functional groups of different properties ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit the target mineral in a wider pH window and has a wide range of applications. Therefore, based on the specific spatial structure, functional group types, and mutual cooperation between different functional groups in the molecular structure of the environmentally friendly chalcopyrite inhibitor provided in the embodiments of the present application, it is possible to achieve efficient and selective inhibition of chalcopyrite in copper and molybdenum associated ores in a wide pH range in a safe and environmentally friendly manner.

[0009] In a second aspect, an embodiment of the present application provides a method for separating copper and molybdenum, comprising the following steps:

[0010] The environmentally friendly chalcopyrite inhibitor, pH value regulator, collector and frother are added to the copper-molybdenum mixed concentrate slurry to carry out flotation and collect the floating molybdenum concentrate.

[0011] In the technical solution of the embodiment of the present application, the hydrophilic group of the environmentally friendly chalcopyrite inhibitor can maintain good hydrophilicity in the pH environment formed by the pH regulator, and then fully contact with the chalcopyrite particles in the slurry, and use its specific spatial structure to directionally chelate the copper ions in the chalcopyrite, thereby achieving effective inhibition of chalcopyrite; while inhibiting chalcopyrite, the synergistic effect of the collector and the frother is used to promote the floating of the molybdenum concentrate, thereby achieving copper-molybdenum separation.

[0012] In some embodiments, the environmentally friendly chalcopyrite inhibitor is used in an amount of 0.5-15 kg / t.

[0013] In this embodiment, controlling the amount of the environmentally friendly chalcopyrite inhibitor can help achieve efficient inhibition of chalcopyrite.

[0014] In some embodiments, the pH adjuster adjusts the pH of the slurry to 3-12.

[0015] In this embodiment, since the environmentally friendly chalcopyrite inhibitor contains two types of hydrophilic functional groups with different structures, it can effectively inhibit the target mineral in a wider pH window. Its suitable pH value range is relatively wide. Within the pH range of 3 to 12, the environmentally friendly chalcopyrite inhibitor can stably and efficiently interact with chalcopyrite to achieve effective inhibition of chalcopyrite.

[0016] In some embodiments, the pH adjuster is a NaOH solution or a hydrochloric acid solution; the mass volume fraction of the NaOH solution is 2% to 4%, and the concentration of the hydrochloric acid solution is 0.05 to 0.15 mol / L.

[0017] In this embodiment, by using a NaOH solution or a hydrochloric acid solution of a specific concentration as a pH regulator, the pH value of the slurry can be effectively regulated.

[0018] In some embodiments, the collector is kerosene, and the amount of the collector is 80-120 g / t.

[0019] In this embodiment, by regulating the type and amount of the collector, it is beneficial to give full play to the collecting effect of the collector and efficiently collect the molybdenum concentrate.

[0020] In some embodiments, the foaming agent is methyl isobutyl carbinol, and the amount of the foaming agent is 20-30 g / t.

[0021] In this embodiment, by regulating the type and amount of the foaming agent, it is beneficial to fully exert the effect of the foaming agent and promote the flotation of the molybdenum concentrate.

[0022] In some embodiments, the method for preparing the copper-molybdenum mixed concentrate slurry comprises:

[0023] Grinding the copper-molybdenum mixed concentrate to obtain ore powder;

[0024] The ore powder is mixed with water, stirred and slurried to obtain copper-molybdenum mixed concentrate slurry.

[0025] In this embodiment, the copper-molybdenum mixed concentrate is made into slurry to facilitate flotation.

[0026] In some embodiments, the frother is added 0.5 to 1.5 minutes after the collector is added; and air is introduced for flotation 2.5 to 3.5 minutes after the frother is added.

[0027] In this embodiment, by controlling the addition time of each reagent, the effect of each reagent can be fully exerted, thereby improving the flotation effect.

[0028] In some embodiments, the flotation method includes:

[0029] Scrape the foam every 4-6 seconds and add water every 25-35 seconds;

[0030] The floating molybdenum concentrate was collected when the cumulative flotation time was 1 min, 3 min, 6 min and 10 min respectively.

[0031] In this embodiment, by scraping the foam at a specific time during the flotation process, the thickness and uniformity of the foam can be effectively controlled, and the accumulation of foam on the pulp surface can be avoided, thereby improving the flotation effect; at the same time, by replenishing water at a specific time, it is possible to ensure that the amount of water in the flotation process is sufficient to ensure the smooth progress of the flotation process; on this basis, by collecting the molybdenum concentrate at a specific time, the molybdenum concentrate can be recovered multiple times and efficiently, thereby improving the recovery rate of the molybdenum concentrate.

[0032] 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

[0033] 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.

[0034] Figure 1 Schematic diagram of the mechanism of action of the environmentally friendly chalcopyrite inhibitor in the embodiments of this application;

[0035] Figure 2 Schematic diagram of the process flow for separation of copper and molybdenum in the embodiment of this application. DETAILED DESCRIPTION

[0036] 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.

[0037] 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.

[0038] 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.

[0039] In order to solve the technical problems of traditional chalcopyrite inhibitors such as high hazards, poor selectivity and narrow applicable pH range, the present application provides an environmentally friendly chalcopyrite inhibitor and a method for separating copper and molybdenum. The environmentally friendly chalcopyrite inhibitor utilizes its specific spatial structure, functional group types and the mutual cooperation between different functional groups in the molecular structure to achieve efficient and selective inhibition of chalcopyrite in copper and molybdenum associated ores in a safe and environmentally friendly manner over a wide pH range.

[0040] In a first aspect, the embodiments of the present application provide an environmentally friendly chalcopyrite inhibitor, the structural formula of which is as follows:

[0041] .

[0042] This environmental protection chalcopyrite inhibitor is 2-dimethylamino-3-(2-mercapto-1H-imidazole-5-yl) propionic acid, belongs to sulphur-containing histidine derivatives, is usually used as thioneine quaternization precursor, for the preparation of thioneine. This material is used as environmental protection chalcopyrite inhibitor for the first time in this application, and its mechanism of action schematic diagram is as shown in FIG. Figure 1 As shown. The unique aromatic conjugated structure of this environmentally friendly chalcopyrite inhibitor can be converted into a thiol group through tautomerism of the thiocarbonyl group. The S in the thiol group and the N atom in the aromatic ring that contains a lone pair of electrons and is not involved in the conjugation cooperate with each other to directionally chelate the copper ions in the chalcopyrite. The formed chelate presents a cyclic structure, avoiding chelation with the molybdenum in the molybdenite, showing excellent selectivity. At the same time, the environmentally friendly chalcopyrite inhibitor contains two types of hydrophilic functional groups with different structures, namely carboxyl groups and tertiary amine groups. Among them, the carboxyl group hydrolyzes under alkaline conditions to form salts, ensuring hydrophilicity under alkaline conditions, and the tertiary amine group forms a quaternary ammonium salt under acidic conditions, ensuring hydrophilicity under acidic conditions. These two different hydrophilic functional groups ensure that the environmentally friendly chalcopyrite inhibitor can effectively inhibit the target mineral in a wide pH window and has a wide range of applications. In addition, this substance is a non-toxic and harmless small molecule organic compound with the characteristics of safety and environmental protection. Therefore, the environmentally friendly chalcopyrite inhibitor provided by the present application has the advantages of being safe and environmentally friendly, highly selective, and having a wide applicable pH range. It can achieve efficient and selective inhibition of chalcopyrite in copper and molybdenum associated ores in a safe and environmentally friendly manner over a wide pH range.

[0043] In a second aspect, an embodiment of the present application provides a method for separating copper and molybdenum, comprising the following steps:

[0044] Environmentally friendly chalcopyrite inhibitor, pH regulator, collector and frother are added to the copper-molybdenum mixed concentrate slurry for flotation and the floating molybdenum concentrate is collected.

[0045] Among them, the environmentally friendly chalcopyrite inhibitor added to the slurry can maintain good hydrophilicity under the pH environment formed by the pH regulator, and then fully contact with the chalcopyrite particles in the slurry, and use its specific spatial structure to directionally chelate the copper ions in the chalcopyrite, thereby achieving effective inhibition of chalcopyrite; while inhibiting chalcopyrite, the synergistic effect of the collector and the frother is used to promote the floating of the molybdenum concentrate, thereby realizing the separation of copper and molybdenum.

[0046] Furthermore, in some embodiments, the amount of the environmentally friendly chalcopyrite inhibitor is 0.5-15 kg / t.

[0047] In the technical solution of the embodiment of the present application, by controlling the dosage of the environmentally friendly chalcopyrite inhibitor, it is beneficial to achieve efficient inhibition of chalcopyrite.

[0048] Furthermore, in some embodiments, the pH adjuster adjusts the pH of the slurry to 3-12.

[0049] In the technical solution of the embodiment of the present application, since the environmentally friendly chalcopyrite inhibitor contains two types of hydrophilic functional groups with different structures, it can effectively inhibit the target mineral in a wider pH window. Its suitable pH value range is relatively wide. Within the pH range of 3 to 12, the environmentally friendly chalcopyrite inhibitor can stably and efficiently interact with chalcopyrite to achieve effective inhibition of chalcopyrite.

[0050] Furthermore, in some embodiments, the pH adjuster is a NaOH solution or a hydrochloric acid solution; the mass volume fraction of the NaOH solution is 2% to 4%, and the concentration of the hydrochloric acid solution is 0.05 to 0.15 mol / L.

[0051] In the technical solution of the embodiment of the present application, by using a NaOH solution or a hydrochloric acid solution of a specific concentration as a pH regulator, the pH value of the slurry can be effectively regulated.

[0052] Furthermore, in some embodiments, the collector is kerosene, and the amount used is 80-120 g / t.

[0053] In the technical solution of the embodiment of the present application, by regulating the type and dosage of the collector, it is beneficial to give full play to the collecting effect of the collector and efficiently collect the molybdenum concentrate.

[0054] Furthermore, in some embodiments, the foaming agent is methyl isobutyl carbinol (MIBC), and the amount thereof is 20-30 g / t.

[0055] In the technical solution of the embodiment of the present application, by regulating the type and amount of the foaming agent, it is beneficial to give full play to the role of the foaming agent and promote the flotation of the molybdenum concentrate.

[0056] It should be noted that, in this application, the dosages of the aforementioned environmentally friendly chalcopyrite inhibitors, collectors, and frothers all represent the mass concentration of the respective agents relative to the copper-molybdenum mixed concentrate, i.e., the dosage of the agents required per ton of copper-molybdenum mixed concentrate. For example, a dosage of 0.5-15 kg / t of environmentally friendly chalcopyrite inhibitor means that 0.5-15 kg of environmentally friendly chalcopyrite inhibitor is required per ton of copper-molybdenum mixed concentrate.

[0057] Furthermore, in some embodiments, the method for preparing the copper-molybdenum mixed concentrate slurry includes:

[0058] Grinding the copper-molybdenum mixed concentrate to obtain ore powder;

[0059] The ore powder is mixed with water, stirred and slurried to obtain copper-molybdenum mixed concentrate slurry.

[0060] In the technical solutions of the embodiments of the present application, copper-molybdenum mixed concentrate is prepared into a slurry to facilitate flotation. More specifically, in some embodiments, particles with a particle size of less than 0.074 mm in the ore powder after grinding account for more than 80% of the total mass of the ore powder; the mass concentration of the ore powder in the slurry is preferably 300-400 g / L; the rotation speed during slurry preparation is preferably 1000-3000 r / min, and the slurry preparation time is preferably 1-3 minutes, so that the mineral particles are evenly dispersed in the slurry, facilitating subsequent flotation.

[0061] Furthermore, in some embodiments, the frother is added 0.5 to 1.5 minutes after the collector is added; and air is introduced for flotation 2.5 to 3.5 minutes after the frother is added.

[0062] In the technical solution of the embodiment of the present application, by controlling the addition time of each reagent, the effect of each reagent can be fully exerted, thereby improving the flotation effect.

[0063] Furthermore, in some embodiments, the flotation method includes:

[0064] Scrape the foam every 4-6 seconds and add water every 25-35 seconds;

[0065] The floating molybdenum concentrate was collected when the cumulative flotation time was 1 min, 3 min, 6 min and 10 min respectively.

[0066] In the technical solution of the embodiment of the present application, by scraping the foam at a specific time during the flotation process, the thickness and uniformity of the foam can be effectively controlled, and the accumulation of foam on the pulp surface can be avoided, thereby improving the flotation effect; at the same time, by replenishing water at a specific time, it is possible to ensure that there is sufficient water in the flotation process to ensure that the flotation process proceeds smoothly; on this basis, by collecting the molybdenum concentrate at a specific time, the molybdenum concentrate can be recovered multiple times and efficiently to improve the recovery rate of the molybdenum concentrate.

[0067] 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.

[0068] Example 1

[0069] This embodiment provides a method for separating copper and molybdenum, and its process flow diagram is as follows: Figure 2 As shown, the specific steps include:

[0070] S1. Grind the copper-molybdenum mixed concentrate to obtain ore powder (particles with a particle size of less than 0.074 mm account for 80% of the total mass of the ore powder); mix 1000 g of the ore powder with water to prepare 3 L of ore slurry, place the slurry in a flotation machine, set the impeller speed of the flotation machine to 2000 r / min, and mix the slurry for 2 minutes to obtain a copper-molybdenum mixed ore concentrate slurry.

[0071] S2. Add 10 kg / t of environmentally friendly chalcopyrite inhibitor to the copper-molybdenum mixed concentrate slurry. Immediately adjust the slurry's pH to 8 using 3% w / v NaOH solution. Then, add kerosene (100 g / t) and, 1 minute later, add the frother MIBC (25 g / t).

[0072] S3. After the frother has been active for 3 minutes, open the air valve to allow air in and begin flotation. During flotation, scrape bubbles every 5 seconds and add water every 30 seconds. The floating concentrate is collected after the cumulative flotation time reaches 1 minute, 3 minutes, 6 minutes, and 10 minutes. The concentrates collected at different times are mixed, filtered, and dried at 60°C to obtain the molybdenum concentrate.

[0073] The recovery rates of molybdenite and chalcopyrite can be calculated based on the mass and composition of the copper-molybdenum mixed concentrate used in step S1 and the molybdenum concentrate obtained in step S3. Here, the recovery rate of molybdenite = (the mass of molybdenite in the molybdenum concentrate / the mass of molybdenite in the copper-molybdenum mixed concentrate) × 100%; the recovery rate of chalcopyrite = (the mass of chalcopyrite in the molybdenum concentrate / the mass of chalcopyrite in the copper-molybdenum mixed concentrate) × 100%.

[0074] In this embodiment, the mass fraction of molybdenite in the copper-molybdenum mixed concentrate used in step S1 is 0.85%, and the mass fraction of chalcopyrite is 7.00%, that is, the mass of molybdenite in the copper-molybdenum mixed concentrate is 8.5g, and the mass of chalcopyrite is 70g. The mass of molybdenite in the molybdenum concentrate obtained in step S3 is measured to be 7.5g, and the mass of chalcopyrite is 5.6g. From this, the recovery rate of molybdenite is calculated to be 7.5÷8.5×100%=88%, and the recovery rate of chalcopyrite is calculated to be 5.6÷70×100%=8%.

[0075] In this embodiment, the environmentally friendly chalcopyrite inhibitor used in step S2 is commercially available 2-dimethylamino-3-(2-mercapto-1H-imidazol-5-yl)propionic acid, and its structural formula is as follows:

[0076] .

[0077] Combined with the above recovery rates of molybdenite and chalcopyrite, it can be seen that the environmentally friendly chalcopyrite inhibitor and copper-molybdenum separation method provided in this embodiment effectively reduces the recovery rate of chalcopyrite while improving the recovery rate of molybdenite, and achieves efficient and selective inhibition of chalcopyrite while efficiently recovering molybdenite.

[0078] Comparative Example 1

[0079] This comparative example provides a method for separating copper and molybdenum. Compared with Example 1, the only difference is that no environmentally friendly chalcopyrite inhibitor is added in step S2. The remaining steps are consistent with Example 1 and are not repeated here.

[0080] The recovery rates of molybdenite and chalcopyrite were tested and calculated in the same manner as in Example 1. The results showed that the recovery rate of molybdenite in this comparative example was 42%, and the recovery rate of chalcopyrite was 78%. The recovery rate of molybdenite was significantly lower than that in Example 1, while the recovery rate of chalcopyrite was significantly higher than that in Example 1. This shows that, without the addition of an environmentally friendly chalcopyrite inhibitor, the collector kerosene preferentially captures chalcopyrite, resulting in a large amount of chalcopyrite being recovered, while the molybdenite cannot be effectively recovered.

[0081] Comparative Examples 2 to 5

[0082] Comparative Examples 2 to 5 respectively provide a method for separating copper and molybdenum. Compared with Example 1, the only difference is the type of chalcopyrite inhibitor added in step S2. The remaining steps are consistent with Example 1 and are not repeated here.

[0083] The types of chalcopyrite inhibitors used in Comparative Examples 2 to 5 and the recoveries of molybdenite and chalcopyrite obtained therefrom are shown in Table 1.

[0084] Table 1 Types and recovery rates of chalcopyrite inhibitors used in Comparative Examples 2 to 5

[0085]

[0086] As can be seen from Table 1, although the traditional chalcopyrite inhibitor can have a certain inhibitory effect on chalcopyrite, its effect is not good. The recovery rate of chalcopyrite is still significantly higher than that of Example 1, and the recovery rate of molybdenite is significantly lower than that of Example 1. Therefore, compared with the traditional chalcopyrite inhibitors used in Comparative Examples 2 to 5, the environmentally friendly chalcopyrite inhibitor provided in Example 1 is not only safer, but also can significantly improve the selective inhibition effect on chalcopyrite, thereby achieving effective separation of copper and molybdenum.

[0087] Examples 2 to 10

[0088] Examples 2 to 10 respectively provide a method for separating copper and molybdenum. Compared with Example 1, the only difference is that the slurry is adjusted to different pH values in step S2. The remaining steps are consistent with Example 1 and are not repeated here.

[0089] The pH values of the slurries in Examples 2 to 10 and the recoveries of the molybdenite and chalcopyrite obtained therefrom are shown in Table 2.

[0090] Table 2 pH value and recovery rate data of slurry in Examples 2 to 10

[0091]

[0092] As can be seen from Table 2, the environmentally friendly chalcopyrite inhibitor can achieve good results in the pH range of 3 to 12, with the recovery rate of molybdenite reaching more than 80%, and the recovery rate of chalcopyrite ≤11%. The environmentally friendly chalcopyrite inhibitor provided in this application can be applied to a wide pH range, mainly because the environmentally friendly chalcopyrite inhibitor contains both carboxyl groups and tertiary amine groups. The carboxyl groups hydrolyze under alkaline conditions to form salts, ensuring hydrophilicity under alkaline conditions, and the tertiary amine groups form quaternary ammonium salts under acidic conditions, ensuring hydrophilicity under acidic conditions. These two hydrophilic functional groups of different properties ensure that the environmentally friendly chalcopyrite inhibitor can effectively inhibit chalcopyrite in a wide pH window.

[0093] Examples 11 to 19 and Comparative Examples 6 to 8

[0094] Examples 11 to 19 and Comparative Examples 6 to 8 respectively provide a method for separating copper and molybdenum. Compared with Example 1, the only difference is the amount of environmentally friendly chalcopyrite inhibitor used in step S2. The remaining steps are consistent with Example 1 and are not repeated here.

[0095] The dosage of the environmentally friendly chalcopyrite inhibitor in Examples 11 to 19 and Comparative Examples 6 to 8 and the recovery rates of the resulting molybdenite and chalcopyrite are shown in Table 3.

[0096] Table 3 Dosage and recovery data of environmentally friendly chalcopyrite inhibitor in Examples 11 to 19 and Comparative Examples 6 to 8

[0097]

[0098] As can be seen from Table 3, the dosage of the environmentally friendly chalcopyrite inhibitor can be adjusted between 0.5 and 15 kg / t, all of which can achieve a molybdenite recovery rate of ≥80% and a chalcopyrite recovery rate of ≤12%. When the dosage of the environmentally friendly chalcopyrite inhibitor is less than 0.5 kg / t, the chalcopyrite recovery rate will significantly increase to 20%, affecting the inhibitory effect on chalcopyrite. When the dosage of the environmentally friendly chalcopyrite inhibitor reaches 15 kg / t, the inhibitory effect on chalcopyrite has stabilized. Further increasing the dosage does not improve the effect and instead increases the cost of the agent. Therefore, the dosage range of the environmentally friendly chalcopyrite inhibitor provided in this application is preferably 0.5 to 15 kg / t.

[0099] In summary, the present application provides an environmentally friendly chalcopyrite inhibitor and a method for separating copper and molybdenum, which belongs to the field of copper and molybdenum separation technology. The environmentally friendly chalcopyrite inhibitor is a sulfur-containing histidine derivative. Its unique aromatic conjugated structure can be converted into a thiol group through tautomerism of the thiocarbonyl group. The S in the thiol group and the N atom in the aromatic ring that contains a lone pair of electrons and is not involved in the conjugation cooperate with each other to directionally chelate the copper ions in the chalcopyrite. The formed chelate has a cyclic structure, which avoids chelation with the molybdenum in the molybdenite and shows excellent selectivity. The environmentally friendly chalcopyrite inhibitor contains both carboxyl and tertiary amine groups. These two types of hydrophilic functional groups with different structures ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit the target mineral in a wider pH window. Based on the specific spatial structure, functional group types and mutual cooperation between different functional groups of the environmentally friendly chalcopyrite inhibitor, it is possible to achieve efficient and selective inhibition of chalcopyrite in copper and molybdenum associated ores in a safe and environmentally friendly manner over a wide pH range. Moreover, based on the environmentally friendly chalcopyrite inhibitor and copper-molybdenum separation method provided in the embodiments of the present application, the recovery rate of molybdenite in the finally collected molybdenum concentrate is ≥80%, and the recovery rate of chalcopyrite is ≤12%, which effectively suppresses chalcopyrite while efficiently recovering molybdenite.

[0100] 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 method for separating copper and molybdenum, characterized in that: The steps include: Adding environmentally friendly chalcopyrite inhibitor, pH regulator, collector and frother to the copper-molybdenum mixed concentrate slurry to carry out flotation and collect the floating molybdenum concentrate; The structural formula of the environmentally friendly chalcopyrite inhibitor is as follows: 。 2. The method for separating copper and molybdenum according to claim 1, wherein The usage of the environmentally friendly chalcopyrite inhibitor is 0.5-15 kg / t.

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

4. The method for separating copper and molybdenum according to claim 1, wherein The pH adjuster is a NaOH solution or a hydrochloric acid solution; the mass volume fraction of the NaOH solution is 2% to 4%, and the concentration of the hydrochloric acid solution is 0.05 to 0.15 mol / L.

5. The method for separating copper and molybdenum according to claim 1, wherein The collector is kerosene, and the amount of the collector is 80-120 g / t.

6. The method for separating copper and molybdenum according to claim 1, wherein The foaming agent is methyl isobutyl carbinol, and the amount of the foaming agent is 20-30 g / t.

7. The method for separating copper and molybdenum according to claim 1, wherein The preparation method of the copper-molybdenum mixed concentrate slurry comprises: Grinding the copper-molybdenum mixed concentrate to obtain ore powder; The ore powder is mixed with water, stirred and slurried to obtain copper-molybdenum mixed concentrate slurry.

8. The method for separating copper and molybdenum according to claim 1, wherein The frother is added 0.5 to 1.5 minutes after the collector is added; and air is introduced for flotation 2.5 to 3.5 minutes after the frother is added.

9. The method for separating copper and molybdenum according to claim 1, wherein The flotation method includes: Scrape the foam every 4-6 seconds and add water every 25-35 seconds; The floating molybdenum concentrate was collected when the cumulative flotation time was 1 min, 3 min, 6 min and 10 min respectively.

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