A method for the flotation separation of a copper-molybdenum bulk concentrate

Abstract

The application provides a flotation separation method of copper-molybdenum mixed concentrate, relates to the technical field of non-ferrous metal dressing and metallurgy, and solves the problems of large amount of existing inhibitor for enlarging the floatability difference of molybdenite and chalcopyrite and serious environmental pollution. The method comprises the following steps: inserting a cathode and an anode into an electrolytic cell respectively, adding a salt solution into the electrolytic cell, adding a copper-molybdenum mixed concentrate slurry into the electrolytic cell while stirring, wherein the anode material is one of Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3 or Ti / SnO2-Sb; the salt solution is one or more of sodium nitrate or potassium nitrate; after stirring, the stirring is continuously maintained, a constant current source is turned on, an electric current is applied to the electrolytic cell, and the constant current pretreatment is maintained for 15-35 min to obtain a mixed slurry; and the mixed slurry is transferred to a flotation system for flotation operation to obtain molybdenite and chalcopyrite. The method can adjust the hydrophilicity and hydrophobicity of molybdenite and chalcopyrite, and then separate the two.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of non-ferrous metal beneficiation and metallurgy, and particularly relates to a flotation separation method of copper-molybdenum mixed concentrate. BACKGROUND

[0002] Molybdenum and alloys are widely used in metallurgy, agriculture, electricity, chemical industry, environmental protection, aerospace and military fields due to excellent physical and chemical properties. In recent years, molybdenum has been listed as a key metal by many countries. The industrial production of molybdenum mainly comes from molybdenite, and it is of great significance to efficiently recover molybdenite from molybdenum ore resources.

[0003] Molybdenum ore resources mainly include porphyry copper-molybdenum ore, in which copper and molybdenum mainly exist in the form of chalcopyrite and molybdenite. Molybdenite and chalcopyrite are associated and have good floatability and are close to each other, so it is difficult to separate them by flotation. Efficient separation of copper and molybdenum is the key to obtaining molybdenite concentrate. In the current copper-molybdenum flotation separation process, an inhibitor "copper-inhibiting and molybdenum-floating" needs to be added to expand the floatability difference between molybdenite and chalcopyrite. Common inhibitors include sulfides such as sodium sulfide, sodium hydrosulfide and ammonium sulfide, cyanides such as sodium cyanide, potassium cyanide, sodium ferricyanide and sodium ferrocyanide, and Knox, etc. These inhibitors have problems such as large dosage, toxicity, and serious environmental pollution.

[0004] In recent years, oxidizing agents have also been used for pretreatment to expand the floatability difference between molybdenite and chalcopyrite. Common oxidizing agents include peroxides, hypochlorite, bleaching powder and ozone, etc. However, they all have the disadvantages of large dosage, easy production of by-products, high cost, and difficult industrial application. SUMMARY

[0005] In view of the above analysis, the present application aims to provide a flotation separation method of copper-molybdenum mixed concentrate, which can at least solve one of the following technical problems: (1) the existing inhibitors for expanding the floatability difference between molybdenite and chalcopyrite have the problems of large dosage, toxicity and serious environmental pollution; (2) the use of oxidizing agents has the problems of large dosage, easy production of by-products, easy introduction of difficult ions and high cost; (3) copper-molybdenum mixed concentrate cannot be simultaneously subjected to drug removal and oxidation pretreatment.

[0006] The main purpose of the present application is achieved by the following technical solutions:

[0007] The present application provides a flotation separation method of copper-molybdenum mixed concentrate, which comprises the following steps:

[0008] Step 1: inserting the cathode and anode into the electrolytic cell respectively, adding a salt solution into the electrolytic cell, and adding the slurry of the copper-molybdenum mixed concentrate into the electrolytic cell while stirring; wherein the anode material is one of Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3 or Ti / SnO2-Sb; and the salt solution is one or more of sodium nitrate or potassium nitrate;

[0009] Step 2: After stirring evenly, continue stirring, turn on the constant current source, apply current to the electrolytic cell, and perform constant current pretreatment for 15 to 35 minutes to obtain an electrocatalytic oxidation pretreated mixed ore pulp;

[0010] Step 3: Transfer the electrocatalytic oxidation pre-treated mixed ore pulp to a flotation system for flotation operation to obtain chalcopyrite and molybdenite.

[0011] Furthermore, the cathode material is one of iron sheet, stainless steel sheet, copper sheet or graphite sheet.

[0012] Furthermore, in step 1, the concentration of the salt solution is 0.02 to 0.15 mol / L.

[0013] Furthermore, in step 1, the slurry concentration of the copper-molybdenum mixed concentrate is 1.0% to 10.0wt%.

[0014] Furthermore, in step 2, the current is 0.4 to 1.0A.

[0015] Furthermore, in step three, the flotation reagents added in the flotation operation include a regulator, a collector and a frother.

[0016] Furthermore, the adjusting agent is dilute sulfuric acid, the collecting agent is emulsified kerosene, and the foaming agent is methyl isobutyl carbinol.

[0017] Furthermore, in step three, the pH of the slurry during the flotation operation is controlled to be 9.0-10.0.

[0018] Furthermore, in step three, the flotation operation includes roughing.

[0019] Furthermore, in step three, the flotation operation also includes concentration and / or scavenging.

[0020] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0021] a) In the method for flotation separation of the copper-molybdenum mixed concentrate of the present application, the slurry of the copper-molybdenum mixed concentrate is added into an electrolytic cell for electro-catalytic oxidation pretreatment, and then flotation is performed, green and strong oxidizing active free radicals such as hydroxyl radicals and superoxide radicals are generated by electro-catalysis, and then the different oxidation abilities and paths of chalcopyrite and molybdenite are used to make the surfaces of chalcopyrite and molybdenite have different hydrophilic and hydrophobic properties, thereby increasing the difference in floatability, that is, the adjustment of the hydrophilic and hydrophobic properties of chalcopyrite and molybdenite can be realized, and then the two can be separated in flotation, without using toxic and harmful chalcopyrite depressants such as sodium sulfide, sodium hydrosulfide and sodium cyanide, thereby reducing the harm to workshop operators and the pollution to the ecological environment.

[0022] b) In the present application, by using anode materials such as Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3 and Ti / SnO2-Sb, and sodium nitrate or potassium nitrate salt solution, combined with current control and reaction time control, the hydrophilic and hydrophobic properties of chalcopyrite and molybdenite can be reasonably adjusted, and then the two can be separated in flotation.

[0023] c) In the method of the present application, the amount of sodium nitrate or potassium nitrate salt solution used is small, the cost is low, and by-products are not easy to produce.

[0024] d) In the method of the present application, the hydroxyl radicals and superoxide radicals generated can not only perform drug removal treatment on the copper-molybdenum mixed concentrate, but also electro-catalytically oxidize chalcopyrite and molybdenite to increase the difference in floatability, and then realize selective flotation separation of the two.

[0025] e) In the method of the present application, the copper-molybdenum mixed concentrate is pretreated and then subjected to flotation, and no chalcopyrite depressant needs to be added in the flotation process, and by-products are not easy to produce; due to the good effect of electro-catalytic oxidation pretreatment, the difference in floatability of chalcopyrite and molybdenite after pretreatment is large, compared with the flotation of the copper-molybdenum mixed concentrate without pretreatment, under the same flotation recovery rate conditions, the flotation operation can be reduced by 1-2 stages.

[0026] f) The electro-catalytic oxidation pretreatment-flotation separation method for the copper-molybdenum mixed concentrate of the present application has a short process, simple operation and easy automatic control.

[0027] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent from the description, or can be learned by practice of the present application. The objects and other advantages of the present application can be achieved and obtained by the structure particularly pointed out in the written description. BRIEF DESCRIPTION OF DRAWINGS

[0028] The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the technical solutions of the application, and do not constitute a limitation on the technical solutions of the application.

[0029] Figure 1 is a process flow diagram of embodiment 1 of the application;

[0030] Figure 2 is a process flow diagram of embodiment 2 and embodiment 3 of the application; DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, but not all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the application. The values, fractions or ratios involved therein are mass values, mass fractions or mass ratios, if not otherwise specified.

[0032] The application provides a method for electro-catalytic oxidation pretreatment-flotation separation of copper-molybdenum mixed concentrate, comprising the following steps:

[0033] Step 1: a cathode and an anode are respectively inserted into an electrolytic cell, and a salt solution is added into the electrolytic cell, and a copper-molybdenum mixed concentrate slurry is added into the electrolytic cell while stirring; the anode material can be one of Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3 or Ti / SnO2-Sb; the salt solution can be one or more of sodium nitrate or potassium nitrate;

[0034] Step 2: after uniform stirring, the stirring is continuously maintained, a constant current source is turned on, an electric current is applied to the electrolytic cell, and the constant current pretreatment is performed for 15-35 min to obtain an electro-catalytic oxidation pretreatment mixed slurry;

[0035] Step 3: the electro-catalytic oxidation pretreatment mixed slurry is transferred to a flotation system for flotation operation to obtain chalcopyrite and molybdenite.

[0036] Specifically, in the step one, the anode material can be one of Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3, Ti / SnO2-Sb, etc., and the cathode material can be one of iron sheet, stainless steel sheet, copper sheet or graphite sheet, etc. These anode materials are composed of transition metals and have a reduced state, which can catalyze the hydrogen peroxide generated in the electrolyte system to generate hydroxyl radicals. In the step two, the electrocatalytic generation of hydroxyl radicals and superoxide radicals and other green and strong oxidizing active radical groups can be ensured, and then the different oxidation ability and path of the active radical groups to chalcopyrite and molybdenite make the surfaces of chalcopyrite and molybdenite have different hydrophilic and hydrophobic properties, thereby increasing the difference in floatability; and the copper-molybdenum concentrate is generally obtained by flotation operation, and the surface of the copper-molybdenum concentrate obtained by flotation operation generally remains flotation reagents such as xanthate, and the hydroxyl radicals and superoxide radicals and other green and strong oxidizing active radical groups can also oxidize and degrade the flotation reagents of xanthate remaining on the surface of the copper-molybdenum concentrate.

[0037] Specifically, in the step one, considering that monovalent salt is active and alkaline conditions will not produce precipitation; the electrode potential of nitrate is higher than that of water, and the property is stable and will not be electrolyzed; nitrate will not react with metal ions to form a precipitate; therefore, the salt solution can be one or several of sodium nitrate and potassium nitrate.

[0038] Considering that the concentration of the electrolyte salt solution is too low, the solution resistance is large, under the same current condition, the cell voltage is large, and the energy consumption of the electrocatalytic oxidation process is high; the salt solution concentration is high, the solution resistance is small, under the same current condition, the cell voltage is low, and it is insufficient to catalytically generate hydroxyl radicals near the anode. Therefore, in the step one, the concentration of the salt solution is controlled to be 0.02-0.15 mol / L.

[0039] Specifically, in the step one, the concentration of the copper-molybdenum concentrate slurry is too large, the solution resistance is small, under the same current condition, the cell voltage is low, and it is insufficient to catalytically generate hydroxyl radicals near the anode; the concentration of the slurry is too low, the solution resistance is large, under the same current condition, the cell voltage is large, and the energy consumption of the electrocatalytic oxidation process is high. Therefore, the concentration of the copper-molybdenum concentrate slurry is controlled to be 1.0%-10.0wt%.

[0040] Specifically, in the above step two, the electro-catalytic water generates green and strong oxidizing active free radicals such as hydroxyl radicals and superoxide radicals, which can oxidize chalcopyrite into metal oxides such as iron hydroxide, copper oxide and iron oxide to cover on the surface of chalcopyrite, so as to reduce the floatability of chalcopyrite; under the same conditions, the hydroxyl radicals and superoxide radicals can oxidize molybdenite into molybdate and sulfate ions, and the trace amounts of the two ions generated enter the solution, and the hydrophobic surface of molybdenite is continuously exposed, so that the floatability remains unchanged. Therefore, through the treatment of step two, the chalcopyrite and molybdenite surfaces have different hydrophilicity and hydrophobicity, thereby increasing the floatability difference between chalcopyrite and molybdenite, and then through the flotation operation, the molybdenite and chalcopyrite are selectively separated from the copper-molybdenum mixed concentrate.

[0041] Specifically, in the above step two, on the one hand, the anode material is selected, and on the other hand, the current size is controlled; in the electro-catalytic oxidation process, the hydroxyl ions generated by the anode lose electrons to generate oxygen, and under alkaline conditions, the oxygen reacts with water molecules and electrons to generate peroxyl radical ions, the peroxyl radical ions react with water and electrons to generate hydrogen peroxide, and the hydrogen peroxide generates hydroxyl radicals under the catalysis of the reduced metal. The related electrochemical reactions include:

[0042] Hydroxyl radical reaction:

[0043] H2O→H + +OH -

[0044] 4OH - -4e→O2+2H2O

[0045] O2+H2O+2e→HO2 - +OH -

[0046] HO2 - +H2O→H2O2+OH -

[0047] M (电极催化剂-还原态) +H2O2→M (电极催化剂-氧化态) +HO·+OH -

[0048] Other superoxide radical functional group reactions:

[0049] 2·OH→H2O2

[0050] H2O2-e - →HO2·+H + ;

[0051] H2O2+·OH→HO2·+H2O

[0052] Specifically, in the step two, the current is too large, the cell voltage is also large, and the energy consumption is high; the current is small, the cell voltage is small, and it is not enough to generate hydroxyl radicals near the anode; the time is long, on the one hand, the energy consumption is high, on the other hand, a large amount of molybdenite will enter the solution in the form of molybdate ions, resulting in the loss of molybdenite; the time is short, the oxidation degree of chalcopyrite surface is low, and the efficient flotation separation of chalcopyrite and molybdenite cannot be realized. Therefore, the current is controlled to be 0.4-1.0 A, and the pretreatment time is 15-35 min.

[0053] Specifically, in the step three, the flotation reagents added in the flotation operation include the regulator, the collector and the frother, and the chalcopyrite depressant does not need to be added.

[0054] Specifically, in the step three, the regulator is dilute sulfuric acid, the collector is emulsified kerosene, and the frother is methyl isobutyl carbinol.

[0055] Specifically, in the step three, the pulp pH of the flotation operation is controlled to be 9.0-10.0, in this pH range, the methyl isobutyl alcohol has good foaming performance; and the flotation recovery rate of molybdenite is high under this condition.

[0056] Specifically, in the step three, due to the good effect of electro-catalytic oxidation pretreatment, the floatability difference between chalcopyrite and molybdenite after pretreatment is large, compared with the flotation of the copper-molybdenum mixed concentrate without pretreatment, under the condition of the same flotation recovery rate, the flotation operation can reduce 1-2 stages.

[0057] Specifically, in the step three, the flotation operation includes roughing.

[0058] Specifically, in the step three, the flotation operation further includes cleaning and or scavenging.

[0059] Specifically, the method further includes:

[0060] Step four, the flotation products are dried, weighed, and analyzed.

[0061] Compared with the prior art, in the method for electro-catalytic oxidation pretreatment-flotation separation of the copper-molybdenum mixed concentrate, by using the anode materials of Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3, Ti / SnO2-Sb, and the sodium nitrate or potassium nitrate salt solution, the hydrophobicity and hydrophilicity of molybdenite and chalcopyrite can be adjusted, and the toxic and harmful chalcopyrite depressants such as sodium sulfide, sodium hydrosulfide and sodium cyanide do not need to be used, thereby reducing the harm to the workshop operators and the pollution to the ecological environment.

[0062] In the method, the amount of sodium nitrate or potassium nitrate salt solution is small, the cost is low, and the by-products are not easy to produce.

[0063] The hydroxyl radicals and superoxide radicals generated in the method of the present application can not only perform the reagent removal treatment on the copper-molybdenum mixed concentrate, but also can perform the electro-catalytic oxidation pretreatment on the chalcopyrite and molybdenite to increase the floatability difference, and then realize the selective flotation separation of the chalcopyrite and molybdenite.

[0064] The method of the present application has the advantages of short process, simple operation and easy automatic control.

[0065] The present application also provides an electro-catalytic oxidation pretreatment-flotation separation device for copper-molybdenum mixed concentrate, which comprises a plurality of closed electrolytic cells connected in series, a stirring tank and a flotation machine group. The copper-molybdenum mixed concentrate is pretreated in the electrolytic cell first, then put into the stirring tank to be stirred uniformly with part of the flotation reagents, and then put into the flotation machine group for flotation separation.

[0066] The embodiments of the present application are laboratory tests. The laboratory tests are discontinuous processes, the electro-catalytic oxidation pretreatment is completed in a small electrolytic cell, and the flotation process is completed through the simulation of closed-circuit test in a small hanging tank flotation machine. The following embodiments are all laboratory tests.

[0067] Embodiment 1

[0068] The present embodiment provides a method of electro-catalytic oxidation pretreatment-flotation separation for copper-molybdenum mixed concentrate. The copper-molybdenum mixed concentrate in the present embodiment is an artificial mixed concentrate, which is prepared by mixing chalcopyrite and molybdenite in a mass ratio of 3:1. The fineness of the mixed concentrate is 86.94% of -0.074mm, and the grades of copper and molybdenum in the copper-molybdenum mixed concentrate are 24.15% and 13.93%, respectively.

[0069] Step one: respectively insert the cathode graphite sheet and the anode Ti / SnO2-Sb plate into the electrolytic cell, add 0.05mol / L potassium nitrate solution into the electrolytic cell, and add the copper-molybdenum mixed concentrate slurry into the electrolytic cell while stirring, and control the slurry concentration to be 8.33%;

[0070] Step two: after stirring uniformly, continue to maintain stirring, open the constant current source, apply a current of 0.7A to the electrolytic cell, and perform constant current treatment for 20min to obtain the pretreated mixed slurry;

[0071] Step three: transfer the mixed slurry to the flotation tank for flotation operation, adjust the pH of the slurry to 9.0 by using dilute sulfuric acid, and then add 60g / t kerosene and 30g / t methyl isobutyl carbinol in sequence to perform a flotation test to obtain molybdenum concentrate and copper concentrate;

[0072] Step four: dry, weigh and analyze the molybdenum concentrate and copper concentrate.

[0073] In this embodiment, the grade of molybdenum in the molybdenum concentrate obtained in step four is 53.21%, the grade of copper is 1.136%, the recovery rate of molybdenum is 89.53%; the grade of copper in the copper concentrate is 31.19%, the grade of molybdenum is 1.90%, and the recovery rate of copper is 98.89%.

[0074] Embodiment 2

[0075] The embodiment provides a method for electro-catalytic oxidation pretreatment-flotation separation of copper-molybdenum mixed concentrate.

[0076] In this embodiment, a copper-molybdenum mixed concentrate is produced by mixed flotation of a certain black-white tungsten associated molybdenum-copper-sulfide ore in northern Guangdong. The components of the copper-molybdenum mixed concentrate mainly include molybdenite, chalcopyrite, pyrite and gangue minerals; the gangue minerals mainly include quartz, muscovite, apatite, chlorite, biotite, calcite, hornblende, etc., the copper grade is 21.36%, and the molybdenum grade is 3.19%.

[0077] Step one: respectively insert the cathode copper sheet and the anode Pt-WO3 plate into the electrolytic cell, and add 0.1 mol / L sodium nitrate solution into the electrolytic cell, while stirring, add the copper-molybdenum mixed concentrate into the electrolytic cell, and control the pulp concentration to be 3.5%;

[0078] Step two: after uniform stirring, continue to maintain stirring, open the constant current source, apply a current of 0.4 A to the electrolytic cell, and constant current treatment for 35 min to obtain the pretreated mixed slurry;

[0079] Step three: transfer the mixed slurry to the flotation tank for flotation operation, adjust the pH of the slurry to 9.0 by using dilute sulfuric acid, then add 90 g / t kerosene and 40 g / t methyl isobutyl carbinol respectively, then perform once roughing, and the roughing concentrate is subjected to twice cleaning, and no reagent is added in cleaning; the roughing tailings are subjected to twice scavenging, and only 40 g / t emulsified kerosene and 40 g / t methyl isobutyl carbinol are added in scavenging I and scavenging II, and the middlings are recycled to return to the closed-circuit test, and finally the molybdenum concentrate and the copper concentrate are obtained;

[0080] Step four: dry, weigh and analyze the molybdenum concentrate and the copper concentrate.

[0081] In this embodiment, the grade of molybdenum in the molybdenum concentrate obtained in step four is 47.25%, the grade of copper is 0.21%, the recovery rate of molybdenum is 91.98%; the grade of copper in the copper concentrate is 22.46%, the grade of molybdenum is 0.27%, and the recovery rate of copper is 98.62%.

[0082] Embodiment 3

[0083] The embodiment provides a method for electro-catalytic oxidation pretreatment-flotation separation of copper-molybdenum mixed concentrate.

[0084] This example uses a copper-molybdenum mixed concentrate produced by mixed flotation of a large-scale porphyry copper-molybdenum ore. The concentrate primarily consists of pyrite, chalcocite, chalcopyrite, bornite, molybdenite, sphalerite, and gangue minerals. The gangue minerals primarily include quartz, with minor amounts of muscovite, feldspar, and kaolin. The concentrate has a copper grade of 27.54% and a molybdenum grade of 2.96%.

[0085] Step 1: Insert the cathode stainless steel sheet and the anode Ti / IrO2-Ta2O5 plate into the electrolytic cell respectively, add 0.15 mol / L sodium nitrate solution into them, add copper-molybdenum mixed concentrate into the electrolytic cell while stirring, and control the pulp concentration to 10%;

[0086] Step 2: After stirring evenly, continue stirring, turn on the constant current source, apply a current of 1.0A to the electrolytic cell, and treat at the constant current for 15 minutes to obtain the pretreated mixed slurry;

[0087] Step 3: The mixed pulp is transferred to the flotation tank for flotation operation. Dilute sulfuric acid is used to adjust the pulp pH to 9.0, and then 90g / t kerosene and 40g / t methyl isobutyl carbinol are added respectively. Finally, a roughing operation is carried out. The roughing concentrate is then subjected to a secondary cleaning operation without adding reagents. The roughing tailings are subjected to a secondary scavenging operation. Only 40g / t emulsified kerosene and 40g / t methyl isobutyl carbinol are added to scavenging I and scavenging II. The middlings are recycled for closed-circuit testing to finally obtain molybdenum concentrate and copper concentrate.

[0088] Step 4: Dry, weigh and analyze the molybdenum concentrate and copper concentrate.

[0089] In this embodiment, the molybdenum grade of the molybdenum concentrate obtained in step 4 is 45.33%, the copper grade is 0.19%, and the molybdenum recovery rate is 92.65%; the copper grade of the copper concentrate is 29.15%, the molybdenum grade is 0.23%, and the copper recovery rate is 99.44%.

[0090] Comparative Example 1

[0091] This comparative example provides a method for flotation separation of copper-molybdenum mixed concentrate.

[0092] The copper-molybdenum mixed concentrate in this comparative example is an artificial mixed concentrate, prepared with pure chalcopyrite and molybdenite in a mass ratio of 3:1. The mixed concentrate has a fineness of -0.074mm, accounting for 86.94%, and the copper and molybdenum grades in the copper-molybdenum mixed concentrate are 24.15% and 13.93%, respectively.

[0093] Step 1: Add the artificially mixed copper-molybdenum concentrate into the flotation tank, add water to adjust the pulp, and control the pulp concentration to 8.33%;

[0094] Step two: open the floatation machine, first add dilute sodium hydroxide solution to the floatation tank, adjust the pH of the ore pulp to 9.0, stir for 3 min, then add 30 kg / t of sodium sulfide, keep stirring for 3 min;

[0095] Step three: add 30 kg / t of sodium sulfide to the floatation tank, keep stirring for 3 min;

[0096] Step four: finally, add 60 g / t of emulsified kerosene and 30 g / t of methyl isobutyl carbinol to the floatation tank at intervals of 3 min, respectively, stir for 3 min, then start the floatation operation, to obtain molybdenum concentrate and copper concentrate;

[0097] Step five: dry, weigh and analyze the molybdenum concentrate and copper concentrate.

[0098] In this embodiment, the grade of molybdenum in the molybdenum concentrate obtained in step four is 48.79%, the grade of copper is 3.11%, the recovery rate of molybdenum is 70.05%; the grade of copper in the copper concentrate is 29.22%, the grade of molybdenum is 2.65%, and the recovery rate of copper is 96.80%.

[0099] Compared with Example 1, Comparative Example 1 added 30 kg / t of sodium sulfide as a depressant for chalcopyrite, the grade of molybdenum in the molybdenum concentrate decreased by 4.42%, the recovery rate of molybdenum decreased by 19.48%; the grade of copper in the copper concentrate decreased by 1.97%, and the recovery rate of copper decreased by 2.09%. The separation effect of molybdenite and chalcopyrite is not as good as that of Example 1.

[0100] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features, as long as they are within the spirit and principles of the present application. Any modification, equivalent replacement, improvement, etc. made within the scope of the present application should be included in the protection scope of the present application.

Claims

1. A method for the flotation separation of copper-molybdenum bulk concentrates, characterized in that, It comprises the following steps: Step one, the cathode and anode are inserted into the electrolytic cell, and the salt solution is added into the electrolytic cell, and the copper-molybdenum mixed concentrate slurry is added into the electrolytic cell while stirring; wherein the anode material is one of Pt-WO3, Ti-SnO2-PbO2, Ti / IrO2-Ta2O5, Ti / SnO2-Sb2O3 or Ti / SnO2-Sb; the salt solution is one or several of sodium nitrate or potassium nitrate; Step two, after stirring evenly, continue to maintain stirring, open the constant current source, apply current to the electrolytic cell, and constant current pretreatment for 15-35 min to obtain an electro-catalytic oxidation pretreatment mixed slurry; Step three, the electro-catalytic oxidation pretreatment mixed slurry is transferred to the flotation system for flotation operation to obtain chalcopyrite and molybdenite; In step one, the concentration of the salt solution is 0.02-0.15 mol / L; the concentration of the copper-molybdenum mixed concentrate slurry is 1.0%-10.0wt%. In step two, the current size is 0.4-1.0A, and the electrochemical reactions involved include: Hydroxyl radical reaction: H2O → H + + OH - 4 OH - - 4e→ O2+ 2H2O O2 + H2O + 2e→ HO2 - + OH - HO2 - + H2O→H2O2+OH - M (电极催化剂-还原态) + H2O2→ M (电极催化剂-氧化态) + HO·+OH - Other superoxide radical functional group reactions: 2·OH→H2O2 H2O2-e - → HO2· + H + ; H2O2+·OH→HO2·+H2O.

2. The floatation separation method according to claim 1, characterized in that, The cathode material is one of iron sheet, stainless steel sheet, copper sheet or graphite sheet.

3. The floatation separation method according to claim 1, characterized by, In step one, the concentration of the salt solution is 0.05-0.15 mol / L.

4. The floatation separation method according to claim 1, characterized by, In step one, the concentration of the copper-molybdenum mixed concentrate slurry is 3.5%-10.0wt%.

5. The floatation separation method according to claim 1, characterized by, In step three, the flotation reagents added in the flotation operation include adjusting agent, collector and foaming agent.

6. The floatation separation method according to claim 5, characterized in that, The adjusting agent is dilute sulfuric acid, the collector is emulsified kerosene, and the foaming agent is methyl isobutyl carbinol.

7. The floatation separation method according to claim 6, characterized in that, In step three, the pH of the slurry in the flotation operation is controlled to be 9.0-10.

0.

8. The floatation separation method according to any one of claims 1 to 7, characterized in that, In step three, the flotation operation includes roughing.

9. The floatation separation method according to claim 8, characterized in that, In step three, the flotation operation also includes cleaning and / or scavenging.

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