Environment-friendly chalcopyrite inhibitor and copper-molybdenum separation method

Abstract

The invention provides an environment-friendly chalcopyrite inhibitor and a copper-molybdenum separation method, and belongs to the technical field of copper-molybdenum separation. The environment-friendly chalcopyrite inhibitor is a sulfur-containing histidine derivative, a unique aromatic conjugated structure of the environment-friendly chalcopyrite inhibitor can be converted into sulfydryl through thiocarbonyl tautomerization, S in the sulfydryl and N atoms which contain lone pair electrons and do not participate in conjugation in an aromatic ring cooperate with each other, copper ions in chalcopyrite can be directionally chelated, a formed chelate is of an annular structure, and the chalcopyrite inhibitor can be used for inhibiting copper ions in chalcopyrite. Chelation with molybdenum in molybdenite is avoided, and excellent selectivity is shown. The environment-friendly chalcopyrite inhibitor contains carboxyl and tertiary amino at the same time, and it is guaranteed that the environment-friendly chalcopyrite inhibitor can efficiently inhibit target minerals in a wide pH window through the two hydrophilic functional groups of different structures. Based on the specific space structure of the environment-friendly chalcopyrite inhibitor, the types of functional groups and mutual cooperation of different functional groups, efficient selective inhibition of chalcopyrite in copper and molybdenum associated ores can be achieved safely and environmentally in a wide pH range.

Description

Technical Field

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

[0002] At present, traditional chalcopyrite inhibitors mainly include cyanides, sulfides, Knox agents, etc. Although these inhibitors can achieve certain inhibition effects, there are potential environmental protection and safety problems during use, making it difficult to meet the existing market needs.

[0003] For example, cyanides, as highly toxic agents, have potential safety uncertainties during production, storage, and transportation. And the dissociation constant of the complex formed by CN - and impurity metal ions is very low, it is difficult to oxidize, and it is easy to accumulate in nature for a long time, thus causing great potential harm to the surrounding environment. Therefore, cyanides are currently prohibited in many countries. Sulfides can only achieve good inhibition effects at higher concentrations. Research shows that in order to separate molybdenum bulk concentrate, the minimum dosage of sulfide inhibitor needs to reach 10 kg / t. And high-concentration sulfides are easy to decompose, which will cause secondary pollution and the wastewater is difficult to treat. Although Knox agents have strong inhibition ability, their preparation raw material is highly toxic arsenic trioxide, which is harmful to the human body during the preparation and use process. In addition, a large amount of H 2 S gas is generated during the preparation process of Knox agents, resulting in environmental pollution.

[0004] Moreover, when traditional chalcopyrite inhibitors are applied to copper-molybdenum separation, their selectivity is often poor, and it is difficult to selectively inhibit chalcopyrite in complex ore systems; at the same time, in the actual flotation process, due to the narrow pH range suitable for traditional chalcopyrite inhibitors, there are certain limitations when this inhibitor is applied to copper-molybdenum separation. Summary of the Invention

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

[0006] In the first aspect, an embodiment of the present application provides an environmentally friendly chalcopyrite inhibitor, and its structural formula is as follows: .

[0007] The environmentally friendly chalcopyrite inhibitor provided by the embodiments of the present application belongs to sulfur-containing histidine derivatives and is a non-toxic and harmless small molecule organic compound. At the same time, its unique aromatic conjugate structure can be converted into a mercapto group through thiocarbonyl tautomerism. The S in the mercapto group and the N atom with lone pair electrons not participating in conjugation in the aromatic ring cooperate with each other, can chelate copper ions in chalcopyrite directionally, and the formed chelate presents a cyclic structure, avoiding chelation with molybdenum in molybdenite, showing excellent selectivity. Moreover, 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 to form salts under alkaline conditions, ensuring hydrophilicity under alkaline conditions, and the tertiary amine group forms quaternary ammonium salts under acidic conditions, ensuring hydrophilicity under acidic conditions. These two hydrophilic functional groups with different properties ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit the target mineral in a relatively wide pH window and has a wide application range. Therefore, based on the specific spatial structure, types of functional groups, and the mutual cooperation between different functional groups in the molecular structure of the environmentally friendly chalcopyrite inhibitor provided by the embodiments of the present application, it can safely and environmentally friendly achieve efficient selective inhibition of chalcopyrite in copper-molybdenum associated ores in a relatively wide pH range.

[0008] In a second aspect, the embodiments of the present application provide a method for separating copper and molybdenum, including the following steps: Add the environmentally friendly chalcopyrite inhibitor, pH value regulator, collector, and foaming agent to the copper-molybdenum mixed concentrate pulp, carry out flotation, and collect the floating molybdenum concentrate.

[0009] In the technical solution of the embodiments of the present application, the hydrophilic groups of the environmentally friendly chalcopyrite inhibitor can maintain good hydrophilicity in the pH value environment formed by the pH value regulator, and then fully contact with chalcopyrite particles in the pulp, and use its specific spatial structure to chelate copper ions in chalcopyrite directionally, achieving effective inhibition of chalcopyrite; while inhibiting chalcopyrite, the synergistic effect of the collector and the foaming agent is used to promote the floating of molybdenum concentrate, thereby realizing the separation of copper and molybdenum.

[0010] In some embodiments, the dosage of the environmentally friendly chalcopyrite inhibitor is 0.5 - 15 kg / t.

[0011] In this embodiment, by controlling the dosage of the environmentally friendly chalcopyrite inhibitor, it is beneficial to achieve efficient inhibition of chalcopyrite.

[0012] In some embodiments, the pH value regulator adjusts the pH value of the pulp to 3 - 12.

[0013] In this embodiment, since the environmentally friendly chalcopyrite inhibitor contains two types of hydrophilic functional groups with different structures, it can efficiently inhibit the target mineral in a wide pH window, and its suitable pH value range is relatively wide. In the range of pH value from 3 to 12, the environmentally friendly chalcopyrite inhibitor can stably and efficiently act with chalcopyrite to achieve effective inhibition of chalcopyrite.

[0014] In some embodiments, the pH regulator is a NaOH solution or a hydrochloric acid solution; the mass-volume fraction of the NaOH solution is 2% - 4%, and the concentration of the hydrochloric acid solution is 0.05 - 0.15 mol / L.

[0015] In this embodiment, by using a NaOH solution or a hydrochloric acid solution with a specific concentration as the pH regulator, it is convenient to effectively regulate the pH value of the pulp.

[0016] In some embodiments, the collector is kerosene, and the dosage of the collector is 80 - 120 g / t.

[0017] In this embodiment, 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 molybdenum concentrate.

[0018] In some embodiments, the frother is methyl isobutyl carbinol, and the dosage of the frother is 20 - 30 g / t.

[0019] In this embodiment, by regulating the type and dosage of the frother, it is beneficial to give full play to the role of the frother and promote the floating of molybdenum concentrate.

[0020] In some embodiments, the method for preparing the copper-molybdenum bulk concentrate pulp includes: Grinding the copper-molybdenum bulk concentrate to obtain ore powder; Mixing the ore powder with water, stirring and adjusting the pulp to obtain the copper-molybdenum bulk concentrate pulp.

[0021] In this embodiment, by making the copper-molybdenum bulk concentrate into pulp, it is convenient to carry out flotation on it.

[0022] In some embodiments, the frother is added 0.5 - 1.5 min after adding the collector; air is introduced for flotation 2.5 - 3.5 min after adding the frother.

[0023] In this embodiment, by controlling the addition time of each reagent, the functions of each reagent can be fully exerted, thereby improving the flotation effect.

[0024] In some embodiments, the flotation method includes: Skimming the foam every 4 - 6 s, and replenishing water every 25 - 35 s; Collect the floating molybdenum concentrate at cumulative flotation times of 1 min, 3 min, 6 min, and 10 min respectively.

[0025] In this embodiment, by skimming the foam at specific times during the flotation process, the thickness and uniformity of the foam can be effectively controlled, preventing the foam from accumulating on the pulp surface, thereby improving the flotation effect. At the same time, by replenishing water at specific times, the sufficient water volume during the flotation process can be ensured to guarantee the smooth progress of the flotation process. On this basis, by collecting the molybdenum concentrate at specific times, multiple and efficient recovery of the molybdenum concentrate can be achieved to improve the recovery rate of the molybdenum concentrate.

[0026] The above description is only an overview of the technical solution of this application. In order to understand the technical means of this application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features, and advantages of this application more obvious and understandable, the specific embodiments of this application are specifically given below. Brief Description of the Drawings

[0027] In order to more clearly illustrate the technical solution of this application, the drawings used in this application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0028] Figure 1 It is a schematic diagram of the action mechanism of the environmentally friendly chalcopyrite inhibitor in the embodiment of this application; Figure 2 It is a schematic diagram of the process flow of copper-molybdenum separation in the embodiment of this application. Detailed Embodiments

[0029] The embodiments of the technical solution of this application will be described in detail below with reference to the drawings. The following embodiments are only used to illustrate the technical solution of this application more clearly, so they are only examples and cannot be used to limit the protection scope of this application.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field 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 drawings are intended to cover non-exclusive inclusion.

[0031] Reference to "embodiment" in this document means that the specific features, structures, or characteristics described in connection with the embodiment may be included in at least one embodiment of the present application. The phrase appears in various places in the specification and does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art explicitly and implicitly understand that the embodiments described herein may be combined with other embodiments.

[0032] To solve the technical problems of traditional chalcopyrite inhibitors, such as high harm, poor selectivity, and a narrow applicable pH range, the present application provides an environmentally friendly chalcopyrite inhibitor and a method for copper-molybdenum separation. By utilizing the specific spatial structure, functional group types, and the mutual cooperation between different functional groups in the molecular structure of the environmentally friendly chalcopyrite inhibitor, efficient and selective inhibition of chalcopyrite in copper-molybdenum associated ores can be achieved safely and environmentally friendly within a wide pH range.

[0033] In a first aspect, an embodiment of the present application provides an environmentally friendly chalcopyrite inhibitor, and its structural formula is as follows: 。

[0034] This environmentally friendly chalcopyrite inhibitor is 2-dimethylamino-3-(2-mercapto-1H-imidazol-5-yl)propanoic acid, which belongs to sulfur-containing histidine derivatives and is usually used as a quaternization precursor of ergothioneine for the preparation of ergothioneine. In the present application, this substance is used as an environmentally friendly chalcopyrite inhibitor for the first time, and the schematic diagram of its action mechanism is as Figure 1 shown. The unique aromatic conjugate structure of this environmentally friendly chalcopyrite inhibitor can be converted into a mercapto group through thionyl-carbonyl tautomerism. The S in the mercapto group and the N atom with lone pairs of electrons not participating in conjugation in the aromatic ring cooperate with each other, which can chelate copper ions in chalcopyrite directionally, and the formed chelate presents a cyclic structure, avoiding chelation with molybdenum in molybdenite, showing excellent selectivity. At the same time, this environmentally friendly chalcopyrite inhibitor contains two types of hydrophilic functional groups with different structures, namely carboxyl group and tertiary amine group. Among them, the carboxyl group hydrolyzes to form salts under alkaline conditions, ensuring hydrophilicity under alkaline conditions, and the tertiary amine group forms quaternary ammonium salts under acidic conditions, ensuring hydrophilicity under acidic conditions. These two hydrophilic functional groups with different properties ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit the target mineral within a wide pH window, with a wide applicable range. Moreover, this substance belongs to non-toxic and harmless small molecule organic compounds, having the characteristics of safety and environmental protection. Therefore, the environmentally friendly chalcopyrite inhibitor provided by the present application has the advantages of safety and environmental protection, strong selectivity, and a relatively wide applicable pH value range, and can achieve efficient and selective inhibition of chalcopyrite in copper-molybdenum associated ores safely and environmentally friendly within a wide pH range.

[0035] In a second aspect, an embodiment of the present application provides a method for copper-molybdenum separation, including the following steps: Add an environmentally friendly chalcopyrite inhibitor, a pH regulator, a collector, and a foaming agent to the copper-molybdenum bulk concentrate pulp, carry out flotation, and collect the floating molybdenum concentrate.

[0036] Among them, the environmentally friendly chalcopyrite inhibitor added to the pulp can maintain good hydrophilicity in the pH environment formed by the pH regulator, and then fully contact with the chalcopyrite particles in the pulp, and use its specific spatial structure to chelate the copper ions in chalcopyrite directionally, so as to effectively inhibit chalcopyrite; while inhibiting chalcopyrite, use the synergistic effect of the collector and the foaming agent to promote the floating of molybdenum concentrate, so as to achieve the separation of copper and molybdenum.

[0037] Further, in some embodiments, the dosage of the environmentally friendly chalcopyrite inhibitor is 0.5~15 kg / t.

[0038] 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.

[0039] Further, in some embodiments, the pH regulator adjusts the pH value of the pulp to 3~12.

[0040] In the technical solution of the embodiment of the present application, since the environmentally friendly chalcopyrite inhibitor contains two different types of hydrophilic functional groups at the same time, it can efficiently inhibit the target mineral in a wide pH window, and its suitable pH value range is relatively wide. In the range of pH value from 3 to 12, the environmentally friendly chalcopyrite inhibitor can stably and efficiently act with chalcopyrite to achieve effective inhibition of chalcopyrite.

[0041] Further, in some embodiments, the pH regulator is a NaOH solution or a hydrochloric acid solution; the mass-volume fraction of the NaOH solution is 2%~4%, and the concentration of the hydrochloric acid solution is 0.05~0.15 mol / L.

[0042] In the technical solution of the embodiment of the present application, by using a NaOH solution or a hydrochloric acid solution with a specific concentration as the pH regulator, it is convenient to effectively control the pH value of the pulp.

[0043] Further, in some embodiments, the collector is kerosene, and its dosage is 80~120 g / t.

[0044] 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 molybdenum concentrate.

[0045] Further, in some embodiments, the foaming agent is methyl isobutyl carbinol (MIBC), and its dosage is 20~30 g / t.

[0046] In the technical solution of the embodiment of the present application, by regulating the type and dosage of the foaming agent, it is beneficial to give full play to the role of the foaming agent and promote the flotation of molybdenum concentrate.

[0047] It should be noted that in the present application, the dosages of the above-mentioned environmentally friendly chalcopyrite inhibitor, collector, and foaming agent all represent the mass concentration of the corresponding reagent relative to the copper-molybdenum bulk concentrate, that is, the dosage of the reagent required per ton of copper-molybdenum bulk concentrate. For example, if the dosage of the environmentally friendly chalcopyrite inhibitor is 0.5 - 15 kg / t, it means that 0.5 - 15 kg of the environmentally friendly chalcopyrite inhibitor needs to be added per ton of copper-molybdenum bulk concentrate.

[0048] Furthermore, in some embodiments, the method for preparing the copper-molybdenum bulk concentrate pulp includes: Grinding the copper-molybdenum bulk concentrate to obtain mineral powder; Mixing the mineral powder with water, stirring and adjusting the pulp to obtain the copper-molybdenum bulk concentrate pulp.

[0049] In the technical solution of the embodiment of the present application, by making the copper-molybdenum bulk concentrate into pulp, it is convenient to carry out flotation on it. More specifically, in some embodiments, the particles with a particle size less than 0.074 mm in the mineral powder after grinding treatment account for more than 80% of the total mass of the mineral powder; the mass concentration of the mineral powder in the pulp is preferably 300 - 400 g / L; the rotation speed during pulp adjustment is preferably 1000 - 3000 r / min, and the pulp adjustment time is preferably 1 - 3 min, so as to make the mineral particles evenly dispersed in the pulp and facilitate the subsequent flotation.

[0050] Furthermore, in some embodiments, the foaming agent is added 0.5 - 1.5 min after adding the collector; air is introduced for flotation 2.5 - 3.5 min after adding the foaming agent.

[0051] In the technical solution of the embodiment of the present application, by controlling the addition time of each reagent, the functions of each reagent can be fully exerted, thereby improving the flotation effect.

[0052] Furthermore, in some embodiments, the flotation method includes: Scraping the foam every 4 - 6 s and replenishing water every 25 - 35 s; Collecting the floating molybdenum concentrate at cumulative flotation times of 1 min, 3 min, 6 min, and 10 min respectively.

[0053] In the technical solution of the embodiment of the present application, by skimming foam at specific times during the flotation process, the thickness and uniformity of the foam can be effectively controlled, preventing the foam from accumulating on the pulp surface, thereby improving the flotation effect. At the same time, by replenishing water at specific times, the sufficient water volume during the flotation process can be ensured to guarantee the smooth progress of the flotation process. On this basis, by collecting molybdenum concentrate at specific times, multiple and efficient recovery of molybdenum concentrate can be achieved to improve the recovery rate of molybdenum concentrate.

[0054] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain the present application and should not be construed as a limitation of the present application. For those technologies or conditions not specified in the embodiments, they shall be carried out according to the technologies or conditions described in the literature in the field or according to the product instructions. For the reagents or instruments whose manufacturers are not specified, they are all conventional products that can be obtained through commercial purchase.

[0055] Example 1 This embodiment provides a method for copper-molybdenum separation. The schematic process flow diagram is as Figure 2 shown, and specifically includes the following steps: S1. Grind the copper-molybdenum mixed concentrate to obtain ore powder (the particles with a particle size less than 0.074 mm in the ore powder 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 pulp, put the pulp into a flotation machine, set the impeller speed of the flotation machine to 2000 r / min, and adjust the pulp for 2 min to obtain the copper-molybdenum mixed concentrate pulp.

[0056] S2. Add an environmentally friendly chalcopyrite inhibitor (dosage: 10 kg / t) to the copper-molybdenum mixed concentrate pulp, and then immediately adjust the pH value of the pulp to 8 using a NaOH solution with a mass-volume fraction of 3% w / v; then add kerosene (dosage: 100 g / t), and add the foaming agent MIBC (dosage: 25 g / t) 1 min later.

[0057] S3. After the foaming agent acts for 3 min, open the air inlet valve to introduce air and start flotation. During flotation, skim the foam every 5 s, replenish water every 30 s, and collect the floating concentrate at cumulative flotation times of 1 min, 3 min, 6 min, and 10 min respectively. After mixing and filtering the concentrates collected at different times, dry them at 60 °C, and the obtained product is used as molybdenum concentrate.

[0058] According to the masses and compositions of the copper-molybdenum bulk concentrate used in step S1 and the molybdenum concentrate obtained in step S3, the recovery rates of molybdenite and chalcopyrite can be calculated. Among them, the recovery rate of molybdenite = (the mass of molybdenite in the molybdenum concentrate ÷ the mass of molybdenite in the copper-molybdenum bulk concentrate) × 100%; the recovery rate of chalcopyrite = (the mass of chalcopyrite in the molybdenum concentrate ÷ the mass of chalcopyrite in the copper-molybdenum bulk concentrate) × 100%.

[0059] In this embodiment, the mass fraction of molybdenite in the copper-molybdenum bulk 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 bulk concentrate is 8.5 g, and the mass of chalcopyrite is 70 g. It is measured that the mass of molybdenite in the molybdenum concentrate obtained in step S3 is 7.5 g, and the mass of chalcopyrite is 5.6 g. From this, the recovery rate of molybdenite is calculated as 7.5 ÷ 8.5 × 100% = 88%, and the recovery rate of chalcopyrite is 5.6 ÷ 70 × 100% = 8%.

[0060] 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: .

[0061] Combined with the recovery rates of molybdenite and chalcopyrite above, it can be seen that the environmentally friendly chalcopyrite inhibitor and the copper-molybdenum separation method provided in this embodiment effectively reduce the recovery rate of chalcopyrite while increasing the recovery rate of molybdenite, and achieve efficient selective inhibition of chalcopyrite while efficiently recovering molybdenite.

[0062] Comparative Example 1 This comparative example provides a copper-molybdenum separation method. Compared with Example 1, the difference is only that the environmentally friendly chalcopyrite inhibitor is not added in step S2, and the remaining steps are the same as those in Example 1, which will not be elaborated here.

[0063] The recovery rates of molybdenite and chalcopyrite are tested and calculated in the same manner as in Example 1. The results show that: the recovery rate of molybdenite in this comparative example is 42%, and the recovery rate of chalcopyrite is 78%. The recovery rate of molybdenite is significantly lower than that in Example 1, while the recovery rate of chalcopyrite is significantly higher than that in Example 1. From this, it can be seen that without adding the environmentally friendly chalcopyrite inhibitor, the collector kerosene will preferentially collect chalcopyrite, resulting in a large amount of chalcopyrite being recovered, while molybdenite cannot be effectively recovered.

[0064] Comparative Examples 2 - 5 Comparative Examples 2 - 5 respectively provide a copper-molybdenum separation method. Compared with Example 1, the difference is only that the types of chalcopyrite inhibitors added in step S2 are different, and the remaining steps are the same as those in Example 1, which will not be elaborated here.

[0065] The types of chalcopyrite inhibitors used in Comparative Examples 2 to 5 and the recovery rates of molybdenite and chalcopyrite obtained are shown in Table 1.

[0066] Table 1 Types and recovery rate data of chalcopyrite inhibitors used in Comparative Examples 2 to 5 As can be seen from Table 1, although the traditional chalcopyrite inhibitors can have a certain inhibitory effect on chalcopyrite, their effects are 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, the environmentally friendly chalcopyrite inhibitor provided in Example 1 not only has higher safety compared with the traditional chalcopyrite inhibitors used in Comparative Examples 2 to 5, but also can significantly improve the selective inhibitory effect on chalcopyrite, realizing the effective separation of copper and molybdenum.

[0067] Examples 2 to 10 Examples 2 to 10 respectively provide a method for separating copper and molybdenum. Compared with Example 1, the difference is only that the pulp is adjusted to different pH values in step S2, and the remaining steps are the same as those in Example 1, which will not be elaborated here.

[0068] The pulp pH values in Examples 2 to 10 and the recovery rates of molybdenite and chalcopyrite obtained are shown in Table 2.

[0069] Table 2 Pulp pH values and recovery rate data in Examples 2 to 10 As can be seen from Table 2, the environmentally friendly chalcopyrite inhibitor can have good effects in the pH range of 3 to 12, enabling the recovery rate of molybdenite to reach over 80%, and the recovery rate of chalcopyrite ≤ 11%. The environmentally friendly chalcopyrite inhibitor provided in this application can be applicable to a relatively wide pH value range. The main reason is that the environmentally friendly chalcopyrite inhibitor contains both carboxyl and tertiary amine groups at the same time. The carboxyl hydrolyzes to form salts under alkaline conditions, ensuring the hydrophilicity under alkaline conditions, and the tertiary amine group forms quaternary ammonium salts under acidic conditions, ensuring the hydrophilicity under acidic conditions. These two hydrophilic functional groups with different properties ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit chalcopyrite in a relatively wide pH value window.

[0070] Examples 11 to 19 and Comparative Examples 6 to 8 Examples 11 to 19 and Comparative Examples 6 to 8 respectively provide a method for separating copper and molybdenum. Compared with Example 1, the difference is only that the dosage of the environmentally friendly chalcopyrite inhibitor is different in step S2, and the remaining steps are the same as those in Example 1, which will not be elaborated here.

[0071] The dosages of the environmentally friendly chalcopyrite inhibitors in Examples 11 to 19 and Comparative Examples 6 to 8, and the recovery rates of molybdenite and chalcopyrite obtained are shown in Table 3.

[0072] Table 3 Dosages of the environmentally friendly chalcopyrite inhibitors and recovery rate data in Examples 11 to 19 and Comparative Examples 6 to 8 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, and the recovery rate of molybdenite can be ≥80%, and the recovery rate of chalcopyrite can be ≤12%. When the dosage of the environmentally friendly chalcopyrite inhibitor is lower than 0.5 kg / t, the recovery rate of chalcopyrite will increase significantly to 20%, which affects the inhibitory effect on chalcopyrite; when the dosage of the environmentally friendly chalcopyrite inhibitor reaches 15 kg / t, the inhibitory effect on chalcopyrite has tended to be stable, and increasing its dosage further will not improve the effect, but will increase the reagent cost. Therefore, the preferred dosage range of the environmentally friendly chalcopyrite inhibitor provided in this application is 0.5 to 15 kg / t.

[0073] In summary, this application provides an environmentally friendly chalcopyrite inhibitor and a method for separating copper and molybdenum, belonging to the technical field of copper-molybdenum separation. The environmentally friendly chalcopyrite inhibitor is a sulfur-containing histidine derivative, and its unique aromatic conjugate structure can be transformed into a mercapto group through thione-enol tautomerism. The S in the mercapto group and the N atom with lone pair electrons not participating in conjugation in the aromatic ring cooperate with each other, and can chelate the copper ions in chalcopyrite directionally. The formed chelate has a cyclic structure, avoiding chelation with molybdenum in molybdenite, and showing excellent selectivity. The environmentally friendly chalcopyrite inhibitor contains both carboxyl groups and tertiary amine groups at the same time. These two types of hydrophilic functional groups with different structures ensure that the environmentally friendly chalcopyrite inhibitor can efficiently inhibit the target minerals in a wide pH window. Based on the specific spatial structure, types of functional groups and the mutual cooperation between different functional groups of the environmentally friendly chalcopyrite inhibitor, it can safely and environmentally achieve efficient selective inhibition of chalcopyrite in copper-molybdenum associated ores in a wide pH range. And, based on the environmentally friendly chalcopyrite inhibitor and the method for separating copper and molybdenum provided in the examples of this application, the recovery rate of molybdenite in the finally collected molybdenum concentrate is ≥80%, and the recovery rate of chalcopyrite is ≤12%. While efficiently recovering molybdenite, effective inhibition of chalcopyrite is achieved.

[0074] It should be noted that this application is not limited to the above embodiments. The above embodiments are only examples, and embodiments with the same structure and the same effect as the technical idea within the technical solution scope of this application are all included in the technical scope of this application. In addition, within the scope of not departing from the gist of this application, various deformations that those skilled in the art can think of for the embodiments, and other ways constructed by combining some constituent elements in the embodiments are also included in the scope of this application.

Claims

1. An environmentally friendly chalcopyrite inhibitor, characterized in that: Its structural formula is as follows: 。 2. A method for separating copper and molybdenum, characterized in that: The steps include: The environmentally friendly chalcopyrite inhibitor, pH regulator, collector and frother as described in claim 1 are added to the copper-molybdenum mixed concentrate slurry to carry out flotation and collect the floating molybdenum concentrate.

3. The method for separating copper and molybdenum according to claim 2, characterized in that: The usage of the environmentally friendly chalcopyrite inhibitor is 0.5-15 kg / t.

4. The method for separating copper and molybdenum according to claim 2, characterized in that: The pH regulator adjusts the pH value of the slurry to 3-12.

5. The method for separating copper and molybdenum according to claim 2, characterized in that: 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.

6. The method for separating copper and molybdenum according to claim 2, characterized in that: The collector is kerosene, and the amount of the collector is 80-120 g / t.

7. The method for separating copper and molybdenum according to claim 2, characterized in that: The foaming agent is methyl isobutyl carbinol, and the dosage of the foaming agent is 20-30 g / t.

8. The method for separating copper and molybdenum according to claim 2, characterized in that: The method for preparing 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.

9. The method for separating copper and molybdenum according to claim 2, characterized in that: 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.

10. The method for separating copper and molybdenum according to claim 2, characterized in that: 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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