A beneficiation method for gradation separation of copper-molybdenum mixed concentrate

Abstract

The invention discloses a beneficiation method for the tiered separation of copper-molybdenum mixed concentrates. The method comprises the following steps: subjecting the copper-molybdenum mixed concentrate slurry to drug removal treatment under weakly acidic conditions to achieve preliminary separation of the copper-molybdenum mixed concentrate, removing some low-grade copper middlings, and obtaining a higher-grade copper-molybdenum mixed concentrate; then, selectively enriching non-magnetic molybdenite to further separation, and producing a higher-molybdenum-grade mixed concentrate. This method achieves the purpose of reduction in the next sorting process, greatly reduces the amount of inhibitor used when entering the next molybdenum flotation and copper suppression process, further reduces the COD value of wastewater obtained after beneficiation, and can reduce the cost of wastewater treatment in the later stage.

Description

Technical Field

[0001] The present invention belongs to the technical field of copper-molybdenum ore dressing and separation, and in particular relates to a ore dressing method for the tiered separation of copper-molybdenum mixed concentrates. Background Art

[0002] Porphyry copper deposits are associated with abundant low-grade molybdenum resources. Molybdenite is the main carrier mineral of molybdenum. Molybdenum is usually enriched in copper concentrate by mixed flotation process to obtain copper-molybdenum mixed concentrate, and then the copper-molybdenum mixed concentrate is separated. Molybdenum concentrate and copper concentrate are usually produced by the method of suppressing copper sulfide minerals to flotate molybdenite.

[0003] Sodium sulfide or sodium hydrosulfide is usually added as an effective copper inhibitor when separating copper and molybdenum from mixed copper and molybdenum concentrate to obtain molybdenum crude concentrate and copper concentrate. The main problems in the use of sodium sulfide or sodium hydrosulfide are as follows: sodium sulfide or sodium hydrosulfide is easily oxidized by oxygen dissolved in water, resulting in a large amount of reagents. 2- When it enters the solution, it will inhibit the floating of copper in the copper-molybdenum mixed float process, and at the same time a large amount of OH will be generated in the aqueous solution. - , strong alkalinity will also deteriorate the beneficiation indicators of molybdenum; the use of a large amount of flotation agents, their strong reducing properties will cause the COD content in the alkaline water of copper concentrate and molybdenum concentrate to be high, which can reach 2000-4000 mg / L, which has a great impact on the environment and high treatment costs, bringing great technical difficulties to industrial water treatment. Summary of the Invention

[0004] In order to overcome the technical problems of high difficulty in separating copper and molybdenum from copper-molybdenum mixed concentrate, large dosage of sodium sulfide used, and high COD content of alkaline aqueous solution, the present invention provides a beneficiation method for tiered separation of copper-molybdenum mixed concentrate.

[0005] In order to solve the above technical problems, the technical solutions proposed by the present invention are as follows:

[0006] The present invention provides a beneficiation method for the cascade separation of copper-molybdenum mixed concentrates, comprising the following steps:

[0007] S1. Add the acidic solution to the copper-molybdenum mixed concentrate slurry, adjust the pH to 6-6.9, add the de-agent, stir evenly and then perform flotation to obtain mineralized foam A.

[0008] S2. Performing strong magnetic separation on the mineralized foam A obtained in step S1 to obtain non-magnetic pulp C.

[0009] S3. Concentrate the non-magnetic slurry C obtained in step S2 to obtain overflow water and underflow.

[0010] S4, the underflow obtained in step S3 is subjected to molybdenum flotation and copper suppression treatment to obtain molybdenum concentrate and copper concentrate.

[0011] The present invention first removes the drug from the copper-molybdenum mixed concentrate, and then performs flotation to obtain mineralized foam A and pulp B, thereby achieving the preliminary separation of the copper-molybdenum mixed concentrate, wherein the mineralized foam A is a higher-grade copper-molybdenum mixed concentrate, and the pulp B is a low-grade copper middling, and then the mineralized foam A is subjected to strong magnetic separation to obtain non-magnetic pulp C and magnetic pulp D, thereby achieving the separation of the copper-molybdenum mixed concentrate again, wherein the non-magnetic pulp C is a higher-grade molybdenum mixed concentrate, and the magnetic pulp D is a low-molybdenum copper concentrate, and finally the non-magnetic pulp C is concentrated and subjected to floating molybdenum and copper suppression treatment to obtain molybdenum concentrate and copper concentrate. The amount of non-magnetic pulp C obtained in the present invention is greatly reduced compared to the copper-molybdenum mixed concentrate. At this time, when an inhibitor is added to perform floating molybdenum and copper suppression treatment, the amount of the inhibitor used can be greatly reduced, further avoiding the problems of poor beneficiation indicators and high COD values ​​in the wastewater subsequently generated.

[0012] In the present invention, the copper-molybdenum mixed concentrate (pH is about 11) is neutralized with an acidic solution to neutralize the alkalinity of the copper-molybdenum mixed concentrate, and a subsequent separation process is carried out under weakly acidic conditions (pH is 6 to 6.9), which is conducive to the role of the deagent and can reduce the content of COD in the subsequent output wastewater. The effect of adding a deagent is to oxidize and decompose the collector in the copper-molybdenum mixed concentrate and the collector on the surface of the copper sulfide mineral, destroy the molecular structure of the residual agent, complete the deagent, increase the floatability difference between the naturally hydrophobic molybdenite and chalcopyrite in the copper-molybdenum mixed concentrate, and then obtain a higher-grade copper-molybdenum mixed concentrate, achieve the purpose of preliminary sorting, and then further separate according to the magnetic difference of the two main minerals in the copper-molybdenum mixed concentrate, chalcopyrite and molybdenite, to obtain a higher-grade molybdenum mixed concentrate and a low-molybdenum copper concentrate. The higher-grade molybdenum mixed concentrate obtained is mainly non-magnetic molybdenite, which is prepared for the next step of floating molybdenum to suppress copper, achieves the purpose of the next step of sorting reduction, and reduces the use of inhibitors.

[0013] As an optional embodiment, in the mineral processing method provided by the present invention, in step S1, the solid matter content in the copper-molybdenum mixed concentrate slurry is 15-20%, the copper grade is 22-25%, the molybdenum grade is 0.3-1.0%, and the pH value is 11-13.

[0014] The copper-molybdenum mixed concentrate slurry in the present invention is a copper-molybdenum mixed concentrate slurry obtained by enriching molybdenum in copper concentrate through a mixed flotation process of copper ore.

[0015] As an optional embodiment, in the mineral processing method provided by the present invention, in step S1, the acid solution is acidic wastewater obtained after copper precipitation in the mine, and the pH value of the acidic wastewater is 2.0-3.0; the acidic wastewater obtained after copper precipitation in the mine is acidic wastewater containing iron ions generated during the copper mining and dressing process, and the acidic wastewater is acidic wastewater after copper ions are extracted.

[0016] The acidic wastewater obtained after copper precipitation in the mine of the present invention is acidic wastewater containing iron ions produced in the mining and waste rock field during the copper mining and dressing process due to the action of air, water and microorganisms. This type of wastewater has a large water volume, a low pH value and contains a high concentration of sulfate. Such wastewater must be discharged with lime to adjust the pH value to meet the standard, which will increase production costs. If it is directly discharged, it will cause huge damage to the environment. If it accumulates in abandoned mines for a long time, it will cause heavy metal ions to penetrate deep into the soil and pollute surrounding water sources. Once heavy metal ions are taken up by organisms through water sources, they will accumulate in the human body and cause various diseases. The acidic wastewater obtained after copper precipitation in the mine of the present invention is acidic wastewater from which copper ions have been extracted. Other ions do not affect flotation. Therefore, the present invention provides a suitable method for treating acidic wastewater generated after copper precipitation in the mine, which solves the problem of treating acidic wastewater in some mines. At the same time, it can also be applied to the copper-molybdenum mixed concentrate slurry obtained after the copper mine adopts the mixed flotation process, realizing on-site application.

[0017] As an optional embodiment, in the mineral processing method provided by the present invention, in step S1, the de-agent includes ferrous sulfate and hydrogen peroxide.

[0018] In the present invention, ferrous sulfate and hydrogen peroxide are selected as the de-acidification agents, which are used to remove the 2+ Under the catalytic action of ions, hydrogen peroxide can generate two very active hydroxyl free radicals, which oxidize the collector in the ore pulp and the collector on the surface of the copper sulfide mineral, destroying the structural molecules of the agent and making it ineffective, thereby achieving the purpose of removing residual agents.

[0019] At the same time, when the acidic wastewater obtained after copper precipitation in mines is used as an acidic solution to adjust pH, the hydrogen peroxide and Fe 3+ Ion reaction produces Fe 2+ ions, Fe 2+ The ions act as catalysts to promote the de-drugation process of hydrogen peroxide.

[0020] As an optional embodiment, in the mineral processing method provided by the present invention, the de-agent further includes an auxiliary agent, and the auxiliary agent is potassium permanganate or activated carbon.

[0021] In this invention, in addition to ferrous sulfate and hydrogen peroxide as flotation agents, permanganate or activated carbon is added to oxidize and adsorb the agent molecules, further disrupting their structure. This facilitates the removal of flotation agents from the surfaces of sulfide minerals in the mixed concentrate and from the slurry phase, restoring the natural floatability of the sulfide minerals. The natural floatability difference between molybdenite and copper sulfide ores is then utilized to achieve preliminary separation of the copper-molybdenum mixed concentrate.

[0022] As an optional embodiment, in the mineral processing method provided by the present invention, the mass ratio of ferrous sulfate to hydrogen peroxide is (0.1-1): (1-10).

[0023] As an optional embodiment, in the mineral processing method provided by the present invention, the mass ratio of ferrous sulfate, hydrogen peroxide and potassium permanganate is (0.1-1): (1-10): (0.1-1).

[0024] As an optional embodiment, in the mineral processing method provided by the present invention, the mass ratio of ferrous sulfate, hydrogen peroxide and activated carbon is (0.1-1): (1-10): (0.1-1).

[0025] As an optional embodiment, in the mineral processing method provided by the present invention, in step S1, 300 to 3000 g of de-agent is added to each ton of dry ore of the copper-molybdenum mixed concentrate, and the de-agent time is 10 to 30 minutes.

[0026] As an optional embodiment, in the mineral processing method provided by the present invention, in step S2, the magnetic field strength of the strong magnetic separation is 0.85 to 1.75 Tesla, and the flow rate of the mineralized foam A in the magnetic separator is 1.0 to 6.0 cm / s.

[0027] As an optional embodiment, in the mineral processing method provided by the present invention, in step S4, during the molybdenum flotation and copper suppression treatment, 5 to 10 kg of inhibitor is added to the dry ore amount of each ton of copper-molybdenum mixed concentrate.

[0028] In the present invention, after the two separation steps of drug removal flotation and high-intensity magnetic separation, the non-magnetic slurry C, i.e., the higher-grade molybdenum mixed concentrate, is obtained. At this time, when the non-magnetic slurry C is subjected to molybdenum flotation and copper suppression treatment, the amount of copper suppression agent can be greatly reduced due to the reduction in amount after drug removal and magnetic separation. Only 5 to 20 kg of inhibitor can be added to each ton of higher-grade molybdenum mixed concentrate.

[0029] As an optional embodiment, in the mineral processing method provided by the present invention, slurry B is also produced in step S1, and the slurry B is returned to step S1 to continue to prepare the copper-molybdenum mixed concentrate.

[0030] In the present invention, in the weakly acidic slurry system, after the drug removal, the collector on the mineral surface loses its effect, and some ore slimes and poor intergrowths originally attached to the mineral surface have poor floatability. After preliminary drug removal and flotation, they are used as slurry B, that is, low-grade copper middlings are returned to the copper-molybdenum mixed selection process, which can ensure that the copper and molybdenum metals are not lost, and the purpose of separating the ore slimes and poor intergrowths and other minerals after preliminary separation is achieved, thereby achieving the purpose of improving the grade of the copper-molybdenum mixed concentrate.

[0031] As an optional embodiment, in the mineral processing method provided by the present invention, magnetic pulp D is also produced in step S2, and the magnetic pulp D is mixed with the copper concentrate obtained in step S4 as the final copper concentrate.

[0032] As an optional embodiment, in the mineral processing method provided by the present invention, the overflow water obtained in step S3 is recovered for backwater in front of the plant. In the present invention, the traditional backwater of domestic mineral processing plants refers to the overflow water concentrated in front of the plant by flotation tailings or the centralized backwater of the tailings pond.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The present invention first neutralizes the acid solution with the copper-molybdenum mixed concentrate pulp, adjusts the pulp pH value to be weakly acidic, and then removes the copper-molybdenum mixed concentrate to increase the floatability difference between molybdenite and chalcopyrite, thereby achieving preliminary separation of the copper-molybdenum mixed concentrate, removing some low-grade copper middlings, and obtaining a higher-grade copper-molybdenum mixed concentrate. Then, based on the difference in relative magnetic susceptibility between molybdenite and chalcopyrite, the non-magnetic molybdenite is selectively enriched to achieve further separation and produce a higher-grade molybdenum mixed concentrate, thereby achieving the purpose of reducing the amount in the next sorting process. When entering the next step of floating molybdenum and suppressing copper, the amount of inhibitor used is greatly reduced, and the COD value of the wastewater obtained after mineral processing is further reduced, which can reduce the cost of wastewater treatment in the later stage.

[0035] (2) The present invention makes full use of the natural hydrophobicity and non-magnetic characteristics of molybdenite to carry out a tiered separation method, which has the characteristics of strong targeting, high selectivity, high recovery rate and low cost. It requires the copper-molybdenum mixed concentrate to be selected to have a low grade and has strong applicability. DETAILED DESCRIPTION

[0036] In order to facilitate understanding of the present invention, the present invention will be described more comprehensively and meticulously below in combination with the specification and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0037] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0038] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0039] Example 1

[0040] A beneficiation method for the cascade separation of copper-molybdenum mixed concentrates comprises the following steps:

[0041] (1) The acidic wastewater (pH=3.00) obtained after copper precipitation in the mine was mixed with copper-molybdenum mixed concentrate (fineness -0.019mm accounting for 57.9%, pulp concentration of 19.5%, copper grade 22.54%, molybdenum grade 0.442%, pH=11.87) in a ratio of 8:100. The pH after mixing was 6.5. Then, according to the amount of copper-molybdenum mixed concentrate, 500g / t of ferrous sulfate and 300g / t of hydrogen peroxide were added. 0%)) 1500g / t, stirring and slurrying for 15min for flotation to obtain a high-grade copper-molybdenum mixed concentrate with a yield of 87.75%, a molybdenum grade of 0.489% and a recovery rate of 97.11%. The bottom product is used as a low-grade copper middling (with a yield of 12.25%, a copper grade of 7.10% and a molybdenum grade of 0.104%). The low-grade copper middling is returned to the copper-molybdenum mixed selection process to continue to prepare a copper-molybdenum mixed concentrate.

[0042] (2) A CRIMM-500 double-box reciprocating permanent magnet high gradient magnetic separator was used to obtain a high-grade copper-molybdenum mixed concentrate. Under the conditions of a magnetic field intensity of 0.6 Tesla and a slurry flow rate of 4 cm / s, a high-molybdenum-grade mixed concentrate and a low-molybdenum copper concentrate with a yield of 62.23%, a molybdenum grade of 0.624% and a recovery rate of 87.82% were obtained. Among them, the low-molybdenum copper concentrate is a low-molybdenum high-grade copper concentrate with a yield of 25.52%, a molybdenum grade of 0.161%, a loss rate of 9.29% and a copper grade of 26.49%.

[0043] (3) The 18% high-molybdenum grade mixed concentrate obtained by strong magnetic separation was concentrated to 55%. The underflow was then subjected to copper suppression and molybdenum flotation separation using 8 kg / t of sodium sulfide and 150 g / t of kerosene as a suppressant. A molybdenum concentrate with a yield of 6.87%, a molybdenum grade of 5.25%, and a recovery of 81.65% was obtained. The bottom product was copper concentrate (copper grade of 23.70%, molybdenum grade of 0.044%, and molybdenum loss rate of 6.17%). The average COD content of the generated beneficiation wastewater was determined to be 572.57 mg / L.

[0044] (4) The low-molybdenum high-grade copper concentrate obtained in (2) is mixed with the copper concentrate obtained in (3) to form a copper concentrate.

[0045] Example 2

[0046] A beneficiation method for the cascade separation of copper-molybdenum mixed concentrates comprises the following steps:

[0047] (1) The acidic wastewater (pH = 3.00) obtained after copper precipitation in the mine was mixed with copper-molybdenum mixed concentrate (fineness -0.019mm, accounting for 60.1%, pulp concentration of 22.5%, copper grade 20.34%, molybdenum grade 0.466%, pH = 11.90) in a ratio of 7:100. The pH after mixing was 6.25. Then, according to the dry ore amount of copper-molybdenum mixed concentrate, 400g / t of ferrous sulfate and 180g / t of hydrogen peroxide (30%) were added. 00g / t, 300g / t potassium permanganate, stirring and slurrying for 10min for flotation, to obtain a high-grade copper-molybdenum mixed concentrate with a yield of 88.60%, a molybdenum grade of 0.512% and a recovery rate of 97.38%. The bottom product is used as a low-grade copper middling (with a yield of 11.40%, a copper grade of 7.10% and a molybdenum grade of 0.107%). The low-grade copper middling is returned to the copper-molybdenum mixed selection process to continue to prepare a copper-molybdenum mixed concentrate.

[0048] (2) A CRIMM-500 double-box reciprocating permanent magnet high gradient magnetic separator was used to obtain a high-grade copper-molybdenum mixed concentrate. Under the conditions of a magnetic field intensity of 1.0 Tesla and a slurry flow rate of 5 cm / s, a high-molybdenum-grade mixed concentrate and a low-molybdenum copper concentrate with a yield of 63.5%, a molybdenum grade of 0.649% and a recovery rate of 88.46% were obtained. Among them, the low-molybdenum copper concentrate was a low-molybdenum high-grade copper concentrate with a yield of 25.10%, a molybdenum grade of 0.166%, a loss rate of 8.92% and a copper grade of 26.12%.

[0049] (3) The 11% high-molybdenum grade mixed concentrate obtained by strong magnetic separation was concentrated to 56%. The underflow was then subjected to copper suppression and molybdenum flotation separation. Sodium sulfide was used as a suppressant at a dosage of 7 kg / t and kerosene at a dosage of 180 g / t. A molybdenum concentrate with a yield of 6.59%, a molybdenum grade of 5.75%, and a recovery rate of 81.36% was obtained. The bottom product was copper concentrate (copper grade of 23.05%, molybdenum grade of 0.058%, and molybdenum loss rate of 7.10%). The average COD content of the generated mineral processing wastewater was determined to be 525.02 mg / L.

[0050] (4) The low-molybdenum high-grade copper concentrate obtained in (2) is mixed with the copper concentrate obtained in (3) to form a copper concentrate.

[0051] Example 3

[0052] A beneficiation method for the cascade separation of copper-molybdenum mixed concentrates comprises the following steps:

[0053] (1) The acidic wastewater (pH = 3.05) obtained after copper precipitation in the mine was mixed with copper-molybdenum mixed concentrate (fineness -0.019mm accounting for 57.9%, slurry concentration of 21.5%, copper grade 25.47%, molybdenum grade 0.474%, pH = 12.05) in a ratio of 8:100. The pH after mixing was 6.10. Then, according to the amount of copper-molybdenum mixed concentrate, 300g / t of ferrous sulfate and 120g / t of hydrogen peroxide (30%) were added. 00g / t, activated carbon 500g / t, stirring and slurrying for 15min for flotation, to obtain a high-grade copper-molybdenum mixed concentrate with a yield of 82.02%, a molybdenum grade of 0.559% and a recovery rate of 96.66%. The bottom product was used as a low-grade copper middling (with a yield of 17.98%, a copper grade of 12.84% and a molybdenum grade of 0.088%). The low-grade copper middling was returned to the copper-molybdenum mixed selection process to continue to prepare a copper-molybdenum mixed concentrate.

[0054] (2) A CRIMM-500 double-box reciprocating permanent magnet high gradient magnetic separator was used to obtain a high-grade copper-molybdenum mixed concentrate. Under the conditions of a magnetic field strength of 1.5 T and a slurry flow rate of 6 cm / s, a high-molybdenum-grade mixed concentrate and a low-molybdenum copper concentrate with a yield of 60.23%, a molybdenum grade of 0.713% and a recovery rate of 90.59% were obtained. Among them, the low-molybdenum copper concentrate is a low-molybdenum high-grade copper concentrate with a yield of 21.79%, a molybdenum grade of 0.132%, a loss rate of 6.07% and a copper grade of 27.45%.

[0055] (3) The 18% high-molybdenum grade mixed concentrate obtained by strong magnetic separation was concentrated to 58%. The underflow was then subjected to a copper suppression and molybdenum flotation separation operation. Sodium sulfide was used as a suppressant at a dosage of 7 kg / t and kerosene at a dosage of 200 g / t. A molybdenum concentrate with a yield of 4.62%, a molybdenum grade of 8.25%, and a recovery rate of 80.53% was obtained. The bottom product was copper concentrate (copper grade of 28.27%, molybdenum grade of 0.085%, and molybdenum loss rate of 10.06%). The average COD content of the generated mineral processing wastewater was determined to be 450.25 mg / L.

[0056] (4) The low-molybdenum high-grade copper concentrate obtained in (2) is mixed with the copper concentrate obtained in (3) to form a copper concentrate.

[0057] Comparative Example 1

[0058] The conventional copper-molybdenum mixed flotation-copper suppression flotation molybdenum separation process was adopted, and the copper grade of the selected slurry was 22.56% and the molybdenum grade was 0.459%. The original ore slurry was also concentrated to 55% for copper suppression flotation molybdenum separation test. When the sodium sulfide dosage was 18kg / t and the kerosene dosage was 200g / t, a crude molybdenum concentrate with a yield of 26.94%, a molybdenum grade of 1.38% and a recovery rate of 80.92% was obtained. The average COD content of the generated mineral processing wastewater was determined to be 1877.9mg / l.

[0059] Comparative Example 2

[0060] The cyclone classification pretreatment-copper suppression and molybdenum floating separation process was adopted. The copper grade of the selected slurry was 22.63% and the molybdenum grade was 0.452%. After the cyclone classification pretreatment, the sedimentation yield was 90.5%, the molybdenum grade was 0.444%, and the recovery rate was 90.5%. The sedimentation concentration was concentrated from 38% to 55% for the copper suppression and molybdenum floating separation test. When the sodium sulfide dosage was 10kg / t and the kerosene dosage was 200g / t, the crude molybdenum concentrate with a yield of 8.51%, a molybdenum grade of 4.31%, and a recovery rate of 81.06% was obtained. The average COD content of the generated mineral processing wastewater was determined to be 1045mg / l.

[0061] Comparative Example 3

[0062] (1) The acidic wastewater (pH = 3.00) obtained after copper precipitation in the mine and the copper-molybdenum mixed concentrate (fineness -0.019mm accounting for 57.9%, slurry concentration of 19.5%, copper grade 22.54%, molybdenum grade 0.442%, pH = 11.87) were mixed in a ratio of 8:100, and the pH after mixing was 6.5. Subsequently, 1500g / t of hydrogen peroxide (30%) was added according to the amount of dry ore of the copper-molybdenum mixed concentrate, and the slurry was stirred and mixed for 15 minutes for flotation to obtain a high-grade copper-molybdenum mixed concentrate with a yield of 77.99%, a molybdenum grade content of 0.533%, and a recovery rate of 94.09%. The bottom product was used as a low-grade copper middling (yield of 22.01%, copper grade of 14.40%, and molybdenum grade of 0.119%). The low-grade copper middling was returned to the copper-molybdenum mixed selection process to continue to prepare a copper-molybdenum mixed concentrate.

[0063] (2) A CRIMM-500 double-box reciprocating permanent magnet high gradient magnetic separator was used to obtain a high-grade copper-molybdenum mixed concentrate. Under the conditions of a magnetic field intensity of 0.6 Tesla and a slurry flow rate of 4 cm / s, a high-molybdenum-grade mixed concentrate and a low-molybdenum copper concentrate with a yield of 53.34%, a molybdenum grade of 0.704% and a recovery rate of 84.95% were obtained. Among them, the low-molybdenum copper concentrate had a yield of 24.65%, a molybdenum grade of 0.164%, a loss rate of 9.14% and a copper grade of 26.79%.

[0064] (3) The 10% high-molybdenum grade mixed concentrate obtained by strong magnetic separation was concentrated to 55%. The underflow was then subjected to a copper suppression and molybdenum flotation separation operation. Sodium sulfide was used as a suppressant at a dosage of 8 kg / t and kerosene at a dosage of 150 g / t. A molybdenum concentrate with a yield of 5.87%, a molybdenum grade of 5.75%, and a recovery rate of 76.45% was obtained. The bottom product was copper concentrate (copper grade of 23.70%, molybdenum grade of 0.079%, and molybdenum loss rate of 8.50%). The average COD content of the generated mineral processing wastewater was determined to be 592.57 mg / L.

[0065] (4) The low-molybdenum high-grade copper concentrate obtained in (2) is mixed with the copper concentrate obtained in (3) to form a copper concentrate.

[0066] The difference from Example 1 is that in step (1), only 1500 g / t of hydrogen peroxide (30%) is added, and ferrous sulfate is not added. The remaining steps are the same as in Example 1.

[0067] Comparative Example 4

[0068] (1) The copper-molybdenum mixed concentrate (fineness -0.019mm, accounting for 57.9%, pulp concentration of 19.5%, copper grade of 22.54%, molybdenum grade of 0.442%, pH = 11.87) is directly added to the copper-molybdenum mixed concentrate according to the dry ore amount of the copper-molybdenum mixed concentrate, and the slurry is stirred for 15 minutes for flotation to obtain a high-grade copper-molybdenum mixed concentrate with a yield of 77.64%, a molybdenum grade of 0.488%, and a recovery rate of 90.45%. The bottom product is used as a low-grade copper middling (yield of 22.36%, a copper grade of 15.41%, and a molybdenum grade of 0.179%). The low-grade copper middling is returned to the copper-molybdenum mixed selection process to continue to prepare a copper-molybdenum mixed concentrate.

[0069] (2) A CRIMM-500 double-box reciprocating permanent magnet high gradient magnetic separator was used to obtain a high-grade copper-molybdenum mixed concentrate. Under the conditions of a magnetic field intensity of 0.6 Tesla and a slurry flow rate of 4 cm / s, a high-molybdenum-grade mixed concentrate and a low-molybdenum copper concentrate with a yield of 57.62%, a molybdenum grade of 0.585% and a recovery rate of 80.45% were obtained. Among them, the low-molybdenum copper concentrate had a yield of 20.04%, a molybdenum grade of 0.209%, a loss rate of 10.0% and a copper grade of 26.69%.

[0070] (3) The 9% high-molybdenum grade mixed concentrate obtained by strong magnetic separation was concentrated to 55%. The underflow was then subjected to a copper suppression and molybdenum flotation separation operation. Sodium sulfide was used as a suppressant at a dosage of 8 kg / t and kerosene at a dosage of 150 g / t. A molybdenum concentrate with a yield of 5.63%, a molybdenum grade of 5.45%, and a recovery rate of 73.21% was obtained. The bottom product was copper concentrate (copper grade of 23.50%, molybdenum grade of 0.058%, and molybdenum loss rate of 7.24%). The average COD content of the generated mineral processing wastewater was determined to be 652.1 mg / L.

[0071] (4) The low-molybdenum high-grade copper concentrate obtained in (2) is mixed with the copper concentrate obtained in (3) to form a copper concentrate.

[0072] The difference from Example 1 is that in step (1), the acidic wastewater (pH = 3.00) obtained after copper precipitation in the mine is not added, and 500 g / t of ferrous sulfate and 1500 g / t of hydrogen peroxide (30%) are directly added to the copper-molybdenum mixed concentrate, and the slurry is stirred and adjusted for 15 minutes for flotation. The remaining steps are the same as in Example 1.

[0073] Comparative Example 5

[0074] (1) The copper-molybdenum mixed concentrate (fineness -0.019mm accounting for 57.9%, pulp concentration of 19.5%, copper grade 22.54%, molybdenum grade 0.442%, pH = 11.87) was subjected to high-intensity magnetic separation using a CRIMM-500 model. Under the conditions of a magnetic field intensity of 0.6 Tesla and a pulp flow rate of 4 cm / s, a high-molybdenum-grade mixed concentrate and a low-molybdenum copper concentrate with a yield of 75.24%, a molybdenum grade of 0.503%, and a recovery rate of 90.55% were obtained. Among them, the low-molybdenum copper concentrate was a low-molybdenum copper concentrate with a yield of 24.76%, a molybdenum grade of 0.159%, a loss rate of 9.45%, and a copper grade of 23.91%.

[0075] (2) The 9% high-molybdenum grade mixed concentrate obtained by strong magnetic separation was concentrated to 55%. The underflow was then subjected to copper suppression and molybdenum flotation separation. Sodium sulfide was used as a suppressant at a dosage of 12 kg / t and kerosene at a dosage of 250 g / t. A molybdenum concentrate with a yield of 10.02%, a molybdenum grade of 3.40%, and a recovery rate of 81.49% was obtained. The bottom product was copper concentrate (copper grade of 22.90%, molybdenum grade of 0.058%, and molybdenum loss rate of 9.06%). The average COD content of the generated mineral processing wastewater was determined to be 858.2 mg / L.

[0076] (3) The low-molybdenum copper concentrate obtained in (2) is mixed with the copper concentrate obtained in (3) to form a copper concentrate.

[0077] The difference from Example 1 is that the step of preliminary analysis after drug removal is not performed, and strong magnetic separation and molybdenum flotation to suppress copper are directly performed.

[0078] Comparative Example 6

[0079] (1) The copper-molybdenum mixed concentrate (fineness -0.019mm, accounting for 57.9%, pulp concentration of 19.5%, copper grade of 22.54%, molybdenum grade of 0.442%, pH = 11.87) was subjected to strong magnetic separation using a CRIMM-500 double-box reciprocating permanent magnet high gradient magnetic separator. Under the conditions of a magnetic field intensity of 0.6 Tesla and a pulp flow rate of 4 cm / s, a high-molybdenum-grade mixed concentrate with a yield of 70.91%, a molybdenum grade of 0.620%, and a recovery rate of 90.43% and a low-molybdenum copper concentrate were obtained. Among them, the low-molybdenum copper concentrate had a yield of 29.09%, a molybdenum grade of 0.160%, a loss rate of 9.57%, and a copper grade of 27.45%.

[0080] (2) The 10% high-molybdenum grade mixed concentrate is concentrated to 25%, and then the acidic wastewater (pH = 3.00) obtained after copper precipitation in the mine is mixed with the high-molybdenum grade mixed concentrate (slurry concentration of 19.5%, copper grade 27.45%, molybdenum grade 0.620%, pH = 10.90) in a ratio of 3:100. The pH after mixing is 6.10, and then 400g / t of ferrous sulfate and hydrogen peroxide are added. (30%) 1500g / t, stirring and slurrying for 15min for flotation, to obtain a high-grade copper-molybdenum mixed concentrate with a yield of 63.90%, a molybdenum grade of 0.660% and a recovery rate of 86.81%. The bottom product was used as a low-grade copper middling (with a yield of 7.01%, a copper grade of 14.10% and a molybdenum grade of 0.251%). The low-grade copper middling was returned to the copper-molybdenum mixed selection process to continue to prepare a copper-molybdenum mixed concentrate.

[0081] (3) The higher-grade copper-molybdenum mixed concentrate in (2) was subjected to copper suppression and molybdenum flotation separation. Sodium sulfide was used as a suppressant at a dosage of 10 kg / t and kerosene at a dosage of 250 g / t. A molybdenum concentrate with a yield of 8.34%, a molybdenum grade of 4.50%, and a recovery rate of 77.26% was obtained. The bottom product was copper concentrate (copper grade of 27.65%, molybdenum grade of 0.084%, and molybdenum loss rate of 9.55%). The average COD content of the generated mineral processing wastewater was determined to be 695.0 mg / L.

[0082] (4) The low-molybdenum copper concentrate obtained in (1) is mixed with the copper concentrate obtained in (3) to obtain copper concentrate.

[0083] The difference from Example 1 is that the method first uses strong magnetic separation and then performs dedoping and molybdenum flotation to suppress copper.

[0084] The test indicators of each separation process in Examples 1-3 and Comparative Examples 1-6 are shown in Table 1 below. The enrichment ratio in this application is the ratio of molybdenum in the concentrate grade to the original ore grade.

[0085] Table 1: Comparison table of test indicators of various sorting processes

[0086] Process Name Rough concentrate yield% Molybdenum grade% Molybdenum recovery rate % Enrichment ratio COD value (mg / L) Example 1 6.87 5.25 81.65 11.88 572.57 Example 2 6.59 5.75 81.36 12.34 525.02 Example 3 4.62 8.25 80.53 17.41 450.25 Comparative Example 1 26.94 1.38 80.92 3.05 1877.9 Comparative Example 2 8.06 4.31 76.95 9.75 1045 Comparative Example 3 5.87 5.75 76.45 9.76 592.57 Comparative Example 4 5.63 5.45 73.21 13.01 652.1 Comparative Example 5 10.02 3.40 81.49 12.33 858.2 Comparative Example 6 8.34 4.50 77.26 6.76 695.0

[0087] The above is a further detailed description of the present invention in conjunction with specific preferred embodiments, and the specific implementation of the present invention should not be considered to be limited to these descriptions. For those skilled in the art to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, and all of these should be considered to fall within the scope of protection of the present invention.

Claims

1. A beneficiation method for the graded separation of copper-molybdenum mixed concentrates, characterized in that: The following steps are involved: S1. Add an acidic solution to a copper-molybdenum mixed concentrate pulp, adjust the pH to 6-6.9, add a de-agent, stir evenly, and then perform flotation to obtain a mineralized foam A; the acidic solution is acidic wastewater obtained after copper precipitation in a mine, and the pH value of the acidic wastewater is 2.0-3.0; the acidic wastewater obtained after copper precipitation in the mine is acidic wastewater containing iron ions generated during copper mining and dressing, and the acidic wastewater is acidic wastewater after copper ions are extracted; the de-agent includes ferrous sulfate and hydrogen peroxide, and the de-agent also includes an auxiliary agent, which is potassium permanganate or activated carbon; S2, performing strong magnetic separation on the mineralized foam A obtained in step S1 to obtain non-magnetic pulp C; S3, concentrating the non-magnetic slurry C obtained in step S2 to obtain overflow water and underflow; S4, the underflow obtained in step S3 is subjected to molybdenum flotation and copper suppression treatment to obtain molybdenum concentrate and copper concentrate.

2. The ore dressing method for the tiered separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: In step S1, the copper-molybdenum mixed concentrate slurry has a solid matter content of 15-20%, a copper grade of 22-25%, a molybdenum grade of 0.3-1.0%, and a pH value of 11-13; the copper-molybdenum mixed concentrate slurry is a copper-molybdenum mixed concentrate slurry obtained by enriching molybdenum in copper concentrate using a mixed flotation process of copper ore.

3. The ore dressing method for the gradation separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: In step S1, the mass ratio of ferrous sulfate to hydrogen peroxide is (0.1-1): (1-10).

4. The ore dressing method for the cascade separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: The mass ratio of the ferrous sulfate, hydrogen peroxide and potassium permanganate is (0.1-1): (1-10): (0.1-1), and the mass ratio of the ferrous sulfate, hydrogen peroxide and activated carbon is (0.1-1): (1-10): (0.1-1).

5. The ore dressing method for the cascade separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: In step S1, 300 to 3000 g of a de-acidifying agent is added to each ton of dry ore of the copper-molybdenum mixed concentrate, and the de-acidifying time is 10 to 30 minutes.

6. The ore dressing method for the cascade separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: In step S2, the magnetic field strength of the strong magnetic separation is 0.85 to 1.75 Tesla, and the flow rate of the mineralized foam A in the magnetic separator is 1.0 to 6.0 cm / s.

7. The ore dressing method for the cascade separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: Magnetic slurry D is also produced in step S2, and the magnetic slurry D is mixed with the copper concentrate obtained in step S4 to form the final copper concentrate.

8. The ore dressing method for the cascade separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: In step S4, during the molybdenum flotation and copper suppression treatment, 5 to 10 kg of inhibitor is added to the dry ore amount of each ton of copper-molybdenum mixed concentrate.

9. The ore dressing method for the cascade separation of copper-molybdenum mixed concentrate according to claim 1, characterized in that: In step S1, slurry B is also produced, and the slurry B is returned to step S1 to continue to prepare the copper-molybdenum mixed concentrate.