Chalcopyrite inhibiting agent and application

Abstract

The invention provides a chalcopyrite inhibiting agent and application, and belongs to the field of copper-molybdenum separation.The chalcopyrite inhibiting agent is an amino acid derivative derived from amino and carboxyl at the same time; the amino acid comprises one of glycine, alanine, valine and leucine. According to the application, active amino groups and carboxyl groups of amino acids which are simple and easy to obtain are derived, a hydrophilic cyclic aliphatic oxygen heterocyclic ring and a solid-philic dithiocarbonyl group are introduced, and the hydrophilic cyclic aliphatic oxygen heterocyclic ring can realize dissolution of the chalcopyrite inhibition medicament in a water phase; selective chelation of the chalcopyrite inhibiting agent and copper ions in the chalcopyrite in the mineral to be separated can be achieved through the solidity dithiocarbonyl group; meanwhile, the hydrophilic annular aliphatic oxygen heterocycle forms a layer of hydrophilic film on the surface of the chalcopyrite, effective inhibition of the chalcopyrite is further achieved, and the purpose of copper-molybdenum separation is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of copper-molybdenum separation, and particularly relates to a chalcopyrite depressant and its application. Background Art

[0002] With the development of China's economy, the demand for copper-molybdenum resources is also increasing. Copper and molybdenum mineral resources mostly show characteristics such as "poor resource endowment, fine dissemination particle size, many associated components, similar flotability, and great difficulty in beneficiation and smelting", resulting in difficulties in copper-molybdenum separation. The high copper content in molybdenum concentrate not only reduces the quality of molybdenum concentrate but also causes losses of copper resources.

[0003] Depressant is one of the core elements to ensure the beneficiation production index. Currently, the traditional chalcopyrite depressants used in copper-molybdenum separation mainly include sodium sulfide, sodium hydrosulfide, sodium cyanide, etc. Sodium sulfide and sodium hydrosulfide have large dosages and high reagent costs; sodium cyanide is highly toxic and the subsequent environmental protection treatment cost is high, making it difficult to meet the increasingly strict environmental protection requirements; at the same time, it is difficult for traditional chalcopyrite depressants to achieve the directional inhibition of chalcopyrite in complex ore systems. Summary of the Invention

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

[0005] In the first aspect, an embodiment of the present application provides a chalcopyrite depressant, which is an amino acid derivative with both amino and carboxyl groups derivatized; the amino acid includes one of glycine, alanine, valine, and leucine; the structural formula of the chalcopyrite depressant is one of A1 - A4; .

[0006] In the technical solution of the embodiment of the present application, by derivatizing the active amino and carboxyl groups of simple and easily available amino acids, a hydrophilic heterocycle and a copper-fixing dithiocarbonyl group are introduced. The hydrophilic heterocycle can achieve the dissolution of the chalcopyrite depressant in the aqueous phase; the copper-fixing dithiocarbonyl group can achieve the selective chelation of the chalcopyrite depressant with copper ions in chalcopyrite in the ore to be selected; at the same time, the hydrophilic heterocycle forms a hydrophilic film on the surface of chalcopyrite, further achieving the effective inhibition of chalcopyrite and achieving the purpose of copper-molybdenum separation.

[0007] In the second aspect, an embodiment of the present application provides a process method for copper-molybdenum separation, including the following steps: Add the copper-molybdenum bulk concentrate into the flotation equipment, and then sequentially add the chalcopyrite depressant, pH regulator, collector, and frother, and react for a preset time; open the air inlet valve to introduce air for flotation.

[0008] In the technical solution of the embodiment of the present application, first, the copper-molybdenum mixed concentrate is added into the flotation equipment to form pulp; then, a chalcopyrite inhibitor, a pH regulator, a collector, and a foaming agent are successively added to the pulp. The pH regulator adjusts the pulp to an appropriate pH condition, and the hydrophilic group and the solid-binding group of the chalcopyrite inhibitor cooperate with each other to effectively inhibit chalcopyrite; after the collector collects molybdenum ore, the foaming agent and the collector cooperate with each other to form a foam layer required for flotation on the pulp surface, realizing the floating of molybdenum ore, thereby realizing the separation of copper and molybdenum.

[0009] In some embodiments, the addition amount of the chalcopyrite inhibitor is 0.5 - 15 kg / t.

[0010] In this embodiment, by reasonably controlling the addition amount of the chalcopyrite inhibitor, the efficient inhibition of chalcopyrite is realized.

[0011] In some embodiments, the pH regulator adjusts the pulp to a pH value of 8 - 12.

[0012] In this embodiment, by reasonably controlling the pH value of the pulp, the chalcopyrite inhibitor stably exists in the pulp and acts on chalcopyrite, realizing the efficient inhibition of chalcopyrite.

[0013] In some embodiments, the pH regulator is one of a NaOH solution and a hydrochloric acid solution; the collector is kerosene, and the dosage is 80 - 120 g / t; the foaming agent is methyl isobutyl carbinol, and the dosage is 20 - 30 g / t.

[0014] In this embodiment, 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 foaming agent, the flotation of molybdenum ore is successfully realized.

[0015] In some embodiments, during the flotation process, the foam is scraped every 4 - 6 s, and water is replenished every 25 - 35 s.

[0016] In this embodiment, the foam is scraped every 4 - 6 s to evenly scrape out the flotation foam, effectively controlling the thickness and uniformity of the foam, thereby avoiding the accumulation of foam on the pulp surface and improving the flotation effect; water is replenished every 25 - 35 s, making the water volume in the flotation equipment sufficient, providing favorable conditions for the smooth flotation of molybdenum ore.

[0017] In some embodiments, the rotation speed of the flotation equipment is 1000 - 3000 r / min, and the pulp conditioning time is 1 - 3 min.

[0018] In this embodiment, by reasonably controlling the rotation speed of the flotation equipment and the pulp conditioning time, the minerals to be selected are evenly dispersed in the pulp, providing favorable conditions for the effective inhibition of chalcopyrite and the flotation of molybdenum ore.

[0019] In some embodiments, the frother is added 0.5 - 1.5 min after the collector is added, and the air valve is opened to introduce air for flotation 2.5 - 3.5 min later.

[0020] In this embodiment, by reasonably controlling the addition time of different reagents, different reagents can fully play their roles, further realizing the effective inhibition of chalcopyrite and the efficient flotation of molybdenite.

[0021] In some embodiments, during the flotation process, the floating molybdenum concentrate is collected at 1 min, 3 min, 6 min, and 10 min respectively.

[0022] In this embodiment, the molybdenite obtained by flotation is collected at specific times, realizing the multiple and efficient recovery of molybdenite and improving the recovery rate of molybdenite.

[0023] In some embodiments, the recovery rate of molybdenite is as high as 90%, and the recovery rate of chalcopyrite is as low as 7%.

[0024] In this embodiment, by adding the chalcopyrite inhibitor with a specific structure in the present application to the flotation process, the efficient recovery of molybdenite is realized, and at the same time, the recovery rate of chalcopyrite is relatively low, indicating that the chalcopyrite inhibitor in the present application has a good inhibitory effect on chalcopyrite.

[0025] The above description is only an overview of the technical solution of the present application. In order to be able to understand the technical means of the present 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 the present application more obvious and understandable, the specific embodiments of the present application are given below. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solution of the present application, the drawings used in the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0027] Figure 1 It is the mechanism diagram of the chalcopyrite inhibitor in the embodiment of the present application; Figure 2 It is the process flow diagram of copper-molybdenum separation in the embodiment of the present application; Figure 3 It is the preparation flow diagram of the chalcopyrite inhibitor A1 in Example 1; Figure 4 It is the nuclear magnetic resonance hydrogen spectrum diagram of the chalcopyrite inhibitor A1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] The embodiments of the technical solution of the present application will be described in detail below with reference to the accompanying drawings. The following embodiments are only used to illustrate the technical solution of the present application more clearly, so they are only examples and cannot be used to limit the protection scope of the present application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill 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 accompanying drawings are intended to cover non-exclusive inclusion.

[0030] Reference to "embodiment" herein means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of this 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 will explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.

[0031] Copper and molybdenum mineral resources mostly exhibit characteristics such as "many associated components and similar floatabilities", which makes the separation of copper and molybdenum difficult. Currently, the traditional chalcopyrite inhibitor used for copper-molybdenum separation has strong toxicity and high subsequent environmental protection treatment costs; it is difficult to achieve the directional inhibition of chalcopyrite in complex ore systems, that is, the inhibition effect is poor.

[0032] To solve the technical problems of strong toxicity and poor inhibition effect of traditional chalcopyrite inhibitors, this application provides a chalcopyrite inhibitor, its preparation method and application. Among them, through the regulation of the specific molecular skeleton spatial structure of the chalcopyrite inhibitor, the design of the types of functional groups, and the mutual cooperation between the two types of functional groups, the efficient selective inhibition of chalcopyrite in copper-molybdenum associated ores is achieved, and the purpose of copper-molybdenum separation is achieved.

[0033] In a first aspect, an embodiment of this application provides a chalcopyrite inhibitor, which is an amino acid derivative derived from both amino and carboxyl groups; the amino acid includes one of glycine, alanine, valine, and leucine; the structural formula of the chalcopyrite inhibitor is one of A1 - A4; .

[0034] In the technical solution of the embodiment of this application, as Figure 1 shown, by derivatizing the active amino and carboxyl groups of simple and easily available amino acids, a functionalized heterocycle with a special structure (that is, the functionalized functional group B in Figure 1 ) and a dithiocarbonyl group (that is, Figure 1The functionalized functional groups A) in it. The polar groups with two different molecular structures in the molecular skeleton of the chalcopyrite inhibitor play different roles. Specifically: First, the hydroxyl group and the cyclic aliphatic oxacycle act as hydrophilic groups to achieve the dissolution of the chalcopyrite inhibitor in the aqueous phase; Second, the dithiocarbonyl group acts as a solid-phase affinity group to achieve the interfacial chemical adsorption of the chalcopyrite inhibitor and chalcopyrite in the ore to be selected. In this process, the lone pair electrons on the sulfur - and nitrogen in the dithiocarbonyl group selectively chelate with the copper ions in chalcopyrite to achieve a strong bond between chalcopyrite and the chalcopyrite inhibitor; At the same time, the hydroxyl group and the cyclic aliphatic oxacycle form a hydrophilic film on the surface of chalcopyrite, making chalcopyrite stably exist in the pulp, realizing the effective inhibition of chalcopyrite. Moreover, the steric effect of the cyclic aliphatic oxacycle makes different groups in the chalcopyrite inhibitor in specific positions, that is, the cyclic aliphatic oxacycle endows the molecular structure of the chalcopyrite inhibitor with a special spatial position, satisfying the mutual cooperation of the two functionalized functional groups, thereby achieving the directional chelation of copper ions and finally realizing the separation of chalcopyrite and molybdenum ore (such as molybdenite). That is, the present application realizes the efficient selective inhibition of chalcopyrite in copper-molybdenum associated ores and achieves the purpose of copper-molybdenum separation through the regulation of the specific molecular skeleton spatial structure of the chalcopyrite inhibitor, the design of the types of functional groups, and the mutual cooperation between the two types of functional groups. In addition, the chalcopyrite inhibitor is an amino acid derivative, and the amino acid raw materials are widely sourced, non-toxic, and easily degradable, avoiding problems such as the difficult degradation and high toxicity of traditional chalcopyrite inhibitors.

[0035] In a second aspect, the embodiments of the present application provide a process method for copper-molybdenum separation, including the following steps: Add the copper-molybdenum mixed concentrate into the flotation equipment, and then successively add the chalcopyrite inhibitor, pH regulator, collector, and frother, and react for a preset time; Open the air inlet valve to introduce air for flotation.

[0036] In the technical solution of the embodiments of the present application, first, the copper-molybdenum mixed concentrate is added into the flotation equipment, and the copper-molybdenum mixed concentrate and the water in the flotation equipment form a pulp; Then, the chalcopyrite inhibitor, pH regulator, collector, and frother are successively added to the pulp. The pH regulator adjusts the pulp to an appropriate pH condition. The hydrophilic groups of the chalcopyrite inhibitor achieve the dissolution of the reagent in the aqueous phase, and at the same time, the solid-phase affinity groups achieve the selective chelation of the reagent and chalcopyrite in the ore, and the hydrophilic groups form a hydrophilic film on the surface of chalcopyrite, making chalcopyrite stably exist in the pulp, realizing the effective inhibition of chalcopyrite; After the collector recovers molybdenum ore, the frother and the collector cooperate with each other to form a foam layer required for flotation on the pulp surface, realizing the floating of molybdenum ore, thereby obtaining molybdenum ore and achieving copper-molybdenum separation.

[0037] In some embodiments, the addition amount of the chalcopyrite inhibitor is 0.5 - 15 kg / t. Specifically, 0.5 - 15 kg of the chalcopyrite inhibitor is added to each ton of the copper-molybdenum bulk concentrate.

[0038] In the technical solution of the embodiments of the present application, by reasonably controlling the addition amount of the chalcopyrite inhibitor, it is avoided that the amount of the chalcopyrite inhibitor is too small to play an inhibitory role, and at the same time, it is avoided that the amount of the chalcopyrite inhibitor is too large, resulting in waste and increasing the subsequent treatment difficulty.

[0039] In some embodiments, the pH regulator adjusts the pulp to a pH value of 8 - 12.

[0040] In the technical solution of the embodiments of the present application, by reasonably controlling the pH value of the pulp, the chalcopyrite inhibitor stably exists in the pulp and acts on chalcopyrite, realizing the efficient inhibition of chalcopyrite.

[0041] In some embodiments, the pH regulator is one of a NaOH solution and a hydrochloric acid solution; the collector is kerosene, and the dosage is 80 - 120 g / t; the frother is methyl isobutyl carbinol (MIBC), and the dosage is 20 - 30 g / t. Specifically, the concentration of the NaOH solution is 500 g / L; the hydrochloric acid solution is prepared by mixing hydrochloric acid and water at a volume ratio of 1:1; 80 - 120 g of kerosene and 20 - 30 g of MIBC are added to each ton of the copper-molybdenum bulk concentrate.

[0042] In the technical solution of the embodiments of the present application, by reasonably setting the type and concentration of the pH regulator, selecting a suitable pH regulator according to the type of the minerals to be selected, and adjusting the pulp to a suitable acidity and alkalinity, the inhibitory effect of the chalcopyrite inhibitor on chalcopyrite can be effectively exerted. By reasonably controlling the type and addition amount of the collector, the recovery of molybdenum ore is smoothly realized. By reasonably controlling the type and addition amount of the frother, and utilizing the mutual synergy of the collector and the frother, the flotation of molybdenum ore is smoothly realized.

[0043] In some embodiments, during the flotation process, the foam is scraped every 4 - 6 s, and water is replenished every 25 - 35 s.

[0044] In the technical solution of the embodiments of the present application, the foam is scraped every 4 - 6 s, and the flotation foam is evenly scraped out, effectively controlling the thickness and uniformity of the foam, thereby avoiding the accumulation of foam on the pulp surface and improving the flotation effect; water is replenished every 25 - 35 s, making the water volume in the flotation equipment sufficient, providing favorable conditions for the smooth flotation of molybdenum ore.

[0045] In some embodiments, the rotation speed of the flotation equipment is 1000 - 3000 r / min, and the pulp conditioning time is 1 - 3 min.

[0046] In the technical solution of the embodiment of the present application, by reasonably controlling the rotation speed of the flotation equipment and the pulp conditioning time, the minerals to be selected are evenly dispersed in the pulp, providing favorable conditions for the effective inhibition of chalcopyrite and the flotation of molybdenite.

[0047] In some embodiments, the frother is added 0.5 - 1.5 min after adding the collector, and the air inlet valve is opened to introduce air for flotation 2.5 - 3.5 min later.

[0048] In the technical solution of the embodiment of the present application, by reasonably controlling the addition time of different reagents, different reagents can fully play their roles, further realizing the effective inhibition of chalcopyrite and the efficient flotation of molybdenite.

[0049] In some embodiments, during the flotation process, the floating molybdenum concentrate is collected at 1 min, 3 min, 6 min, and 10 min respectively.

[0050] In the technical solution of the embodiment of the present application, the floating molybdenum concentrate is collected at 1 min, 3 min, 6 min, and 10 min respectively, and the flotation - obtained molybdenite is collected regularly, realizing the multiple and efficient recovery of molybdenite and improving the recovery rate of molybdenite.

[0051] In some embodiments, the recovery rate of molybdenite is as high as 90%, and the recovery rate of chalcopyrite is as low as 7%. Specifically, the recovery rate of molybdenite = the total mass of molybdenite in the floating molybdenum concentrate / the total mass of molybdenite in the copper - molybdenum mixed concentrate, and the recovery rate of chalcopyrite = the total mass of chalcopyrite in the floating molybdenum concentrate / the total mass of chalcopyrite in the copper - molybdenum mixed concentrate. The higher the recovery rate of molybdenite and the lower the recovery rate of chalcopyrite, the lower the copper content in the floating molybdenum concentrate, indicating that the chalcopyrite inhibitor has a better inhibitory effect on chalcopyrite.

[0052] In the technical solution of the embodiment of the present application, by adding a chalcopyrite inhibitor with a specific structure in the present application to the flotation process, the efficient recovery of molybdenite is realized, and at the same time, the recovery rate of chalcopyrite is relatively low, indicating that the chalcopyrite inhibitor in the present application has a good inhibitory effect on chalcopyrite.

[0053] 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 to the present application. For those without specific technologies or conditions indicated in the embodiments, they are carried out according to the technologies or conditions described in the literature in the field or according to the product specifications. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0054] Example 1 A process method for copper - molybdenum separation, as Figure 2 shown, includes the following steps: S1. Grind the copper-molybdenum bulk concentrate so that the portion with a particle size less than 0.074 mm in the ore powder accounts for 80% of the total mass of the ore powder. Prepare 1000 g of the copper-molybdenum bulk concentrate into 3 L of slurry, put the slurry into an XFG-3 flotation machine, adjust the water level in the flotation machine to the appropriate position, set the impeller speed of the flotation machine to 2000 r / min, and condition the pulp for 2 min to obtain the slurry. Specifically, the types and contents of minerals in the copper-molybdenum bulk concentrate are shown in Table 1.

[0055] S2. Add 10 kg / t of chalcopyrite inhibitor A1 to the slurry, immediately adjust the pH value of the pulp to 8 with NaOH solution, add 100 g / t of kerosene after 3 min, and add 25 g / t of MIBC after 1 min.

[0056] S3. After the frother MIBC acts for 3 min, open the air inlet valve to introduce air and start flotation. Skim the foam every 5 s and replenish water every 30 s, and repeat. Collect the floating molybdenum concentrate at cumulative flotation times of 1 min, 3 min, 6 min, and 10 min respectively to obtain 4 kinds of molybdenum concentrates. Mix the 4 kinds of molybdenum concentrates, filter, dry them in an oven at 60 °C, then weigh them, detect the contents of molybdenite and chalcopyrite in the flotation molybdenum concentrate, and calculate the recovery rates of molybdenite and chalcopyrite.

[0057] Recovery rate of molybdenite = total mass of molybdenite in the flotation molybdenum concentrate / total mass of molybdenite in the copper-molybdenum bulk concentrate, Recovery rate of chalcopyrite = total mass of chalcopyrite in the flotation molybdenum concentrate / total mass of chalcopyrite in the copper-molybdenum bulk concentrate.

[0058] Among them, as Figure 3 shown, the preparation method of the chalcopyrite inhibitor A1 includes the following steps: (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), stir for 3 h under reflux at 100 °C. After the reaction is completed, adjust the pH value of the reaction solution to neutral with 0.5 M sodium hydroxide solution. Extract with ethyl acetate repeatedly, collect the organic phase, and rotary evaporate under vacuum to remove ethyl acetate to obtain glycine isosorbide ester, with a yield of 27%-30%.

[0059] (2). Mix 0.05 mol of glycine isosorbide ester, 0.04 mol of carbon disulfide, and 0.08 mol of sodium hydroxide, stir at 40 °C for 2 h. After the reaction is completed, add water to dissolve by ultrasonic treatment, filter, collect the aqueous phase, and distill under reduced pressure to obtain the chalcopyrite inhibitor A1, with a yield of 82%-87%. As Figure 4 shown, it is the 1H NMR (D 2(O, 400 MHz) spectrum, 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).

[0060] The preparation method of chalcopyrite inhibitors A2 - A4 is similar to that of chalcopyrite inhibitor A1, except that glycine is replaced by alanine, valine, and leucine respectively, which will not be elaborated here.

[0061] Table 1 Measurement results of mineral contents in copper - molybdenum bulk concentrate Examples 2 - 4 and Comparative Examples 1 - 11 A process method for copper - molybdenum separation. Compared with Example 1, the difference lies in that in step S2, the types of chalcopyrite - inhibiting agents are different, and the rest is roughly the same as in Example 1, which will not be elaborated here.

[0062] The copper - molybdenum separation effects of the chalcopyrite - inhibiting agents used in Examples 1 - 4 and Comparative Examples 1 - 11 are shown in Table 2.

[0063] Table 2 Copper - molybdenum separation effects of Examples 1 - 4 and Comparative Examples 1 - 11 As can be seen from Table 2, the recovery rates of molybdenite using the chalcopyrite - inhibiting agents in Examples 1 - 4 are all higher than 80%, while the recovery rates of chalcopyrite are only 9% - 13%. This shows that the chalcopyrite - inhibiting agents used in Examples 1 - 4 can achieve selective and efficient inhibition of chalcopyrite, thereby achieving the purpose of copper - molybdenum separation. This phenomenon can be attributed to the mutual cooperation of the hydrophilic hydroxyl groups, cyclic aliphatic oxacycles, and copper - fixing dithiocarbonyl groups in the chalcopyrite - inhibiting agents A1 - A4. In addition, through Examples 1 - 4, it can be found that as the steric hindrance of the amino acid side chains in the chalcopyrite - inhibiting agents A1 - A4 increases, the recovery rate of chalcopyrite increases, indicating that the inhibitory effect of the chalcopyrite - inhibiting agent on chalcopyrite weakens. This may be because the increase in the steric hindrance of the side - chain groups reduces the stability of the copper chelate and the inhibitory effect on copper.

[0064] When no chalcopyrite inhibitor is introduced (Comparative Example 1), the collector kerosene preferentially collects chalcopyrite at this time, and a large amount of molybdenite will be collected additionally, making it difficult to achieve the separation of copper and molybdenum. When traditional sodium sulfide, sodium cyanide, thiosulfate, and ferrous cyanide are used as chalcopyrite inhibitors (Comparative Examples 2 - 5), the recovery rates of chalcopyrite and molybdenite in the flotation molybdenum concentrate are basically the same, indicating that copper and molybdenum in the flotation molybdenum concentrate basically coexist, and it is impossible to efficiently inhibit chalcopyrite and achieve the separation of copper and molybdenum.

[0065] When only the amino group in the amino acid is derivatized, that is, there is no heterocyclic group in the chalcopyrite inhibitor (Comparative Examples 6 - 9), the recovery rate of molybdenite in the flotation molybdenum concentrate is lower than 70%, and the recovery rate of chalcopyrite is relatively high, indicating that Comparative Examples 6 - 9 cannot achieve the separation of copper and molybdenum. It can be seen that the lack of an aliphatic cyclic structure cannot achieve the selective chelation of chalcopyrite.

[0066] When only the carboxyl group in the amino acid is derivatized, that is, there is no dithiocarbonyl group in the chalcopyrite inhibitor (Comparative Example 10), the recovery rate of molybdenite in the flotation molybdenum concentrate is 90%, and the recovery rate of chalcopyrite is as high as 91%, indicating that Comparative Example 10 cannot achieve the separation of copper and molybdenum. It can be seen that the lack of a dithiocarbonyl group cannot achieve the selective chelation of chalcopyrite. When only the heterocyclic structure is replaced with other aliphatic cyclic fragments (Comparative Example 11), the recovery rate of molybdenite in the flotation molybdenum concentrate is only 35%, and the recovery rate of chalcopyrite is as high as 62%, indicating that Comparative Example 11 cannot achieve the separation of copper and molybdenum. It can be seen that the lack of an aliphatic cyclic structure with a hydrophilic effect cannot achieve the selective chelation of chalcopyrite. Comparative Examples 6 - 11 illustrate that the chalcopyrite inhibitor of the present application efficiently inhibits chalcopyrite through the mutual cooperation of a specific heterocyclic structure, amino acid type, and dithiocarbonyl group, thereby achieving the purpose of copper-molybdenum separation.

[0067] Examples 5 - 8 and Comparative Examples 12 - 13 A process method for copper-molybdenum separation, compared with Example 1, the difference lies in that in step S2, the pH value of the pulp is different, and the others are substantially the same as in Example 1, which will not be elaborated here.

[0068] The copper-molybdenum separation effects of Examples 5 - 8 and Comparative Examples 12 - 13 are shown in Table 3.

[0069] Table 3 Copper-molybdenum separation effects of Examples 5 - 8 and Comparative Examples 12 - 13 As can be seen from Table 3, the chalcopyrite inhibitor A1 in Example 1 has a recovery rate of molybdenite greater than 85% in the range of pulp pH values from 8 to 12, with a relatively high recovery rate. At the same time, the recovery rate of chalcopyrite is ≤10%, that is, the selective separation of copper and molybdenum can be achieved, indicating that the chalcopyrite inhibitor has a relatively wide application window in an alkaline environment. When the pulp pH value is 7, effective separation of copper and molybdenum cannot be achieved. This may be because the carboxyl group and heterocyclic structure in the chalcopyrite inhibitor molecule exist in a protonated form at this time, and the activation site is not activated, so it cannot undergo a chelation reaction with copper ions. When the pulp pH ≥ 13, the content of chalcopyrite in the molybdenum concentrate obtained by flotation is relatively high, indicating that the copper-molybdenum separation effect is poor. This may be because the concentration of OH - in the pulp is too high, and the copper ions and iron ions on the surface of some chalcopyrite are respectively converted into forms such as copper hydroxide, cuprous hydroxide, iron hydroxide, and ferrous hydroxide. It is difficult for the chalcopyrite inhibitor to undergo a chelation reaction with these several alkaline substances and cannot inhibit copper hydroxide or cuprous hydroxide, resulting in some copper being floated with molybdenum, leading to a deterioration of the copper-molybdenum separation effect.

[0070] Examples 9 - 13 and Comparative Examples 14 - 16 A process method for separating copper and molybdenum with a chalcopyrite inhibitor. Compared with Example 1, the difference lies in that in step S2, the dosage of the chalcopyrite inhibitor A1 is different, and the others are roughly the same as in Example 1, which will not be elaborated here.

[0071] The copper-molybdenum separation effects of Examples 9 - 13 and Comparative Examples 14 - 16 are shown in Table 4.

[0072] Table 4 Copper-molybdenum separation effects of Examples 9 - 13 and Comparative Examples 14 - 16 As can be seen from Table 4, the chalcopyrite inhibitor A1 can achieve efficient inhibition of chalcopyrite under low dosage conditions to achieve the purpose of copper-molybdenum separation. When the dosage of the chalcopyrite inhibitor A1 is less than 0.5 kg / t, due to the insufficient dosage of the chalcopyrite inhibitor A1, a good inhibition effect cannot be achieved, resulting in a relatively high recovery rate of chalcopyrite. When the dosage of the chalcopyrite inhibitor A1 is higher than 15 kg / t, with the further increase in the dosage of the chalcopyrite inhibitor A1, the inhibition effect of chalcopyrite is basically stable. Considering the economic cost, the optimal dosage of the chalcopyrite inhibitor A1 is 0.5 - 15 kg / t.

[0073] It should be noted that this application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and embodiments with the same structure and the same function and effect as the technical idea within the scope of the technical solution 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 modifications that can be conceived by those skilled in the art to the embodiments, and other ways constructed by combining some of the constituent elements in the embodiments are also included in the scope of this application.

Claims

1. A chalcopyrite inhibitor, characterized in that: 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 structural formula of the chalcopyrite inhibitor is one of A1-A4; 。 2. 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 performed for a preset time; the inflation valve is opened to allow air to be introduced for flotation.

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

4. The process for separating copper and molybdenum according to claim 2, characterized in that: The pH regulator adjusts the slurry to a pH value of 8-12.

5. The process for separating copper and molybdenum according to claim 2, characterized in that: The pH regulator is one of a NaOH solution and a hydrochloric acid solution; the collector is kerosene, and the dosage is 80-120 g / t; the foaming agent is methyl isobutyl carbinol, and the dosage is 20-30 g / t.

6. The process for separating copper and molybdenum according to claim 2, characterized in that: During the flotation process, the bubbles are scraped off every 4-6 seconds and water is added every 25-35 seconds.

7. The process for separating copper and molybdenum according to claim 2, characterized in that: The rotation speed of the flotation equipment is 1000-3000r / min, and the pulping time is 1-3min.

8. The process for separating copper and molybdenum according to claim 2, 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 be introduced for flotation.

9. The process for separating copper and molybdenum according to claim 2, characterized in that: During the flotation process, the floating molybdenum concentrate was collected at 1 minute, 3 minutes, 6 minutes and 10 minutes respectively.

10. The process for separating copper and molybdenum according to claim 2, characterized in that: The recovery rate of molybdenum ore is 90%, and the recovery rate of chalcopyrite is 7%.

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