Beneficiation method for copper-zinc polymetallic ore containing pyrrhotite and collecting agent

Abstract

The invention discloses a beneficiation method for copper-zinc polymetallic ore containing pyrrhotite and a collecting agent, and belongs to the field of beneficiation. The collecting agent comprises 70%-85% of dithiophosphoric acid and / or dithiophosphate; 15% to 25% of mercaptobenzothiazole salt; and 1-5% of a cosolvent. The collecting agent is suitable for copper and zinc flotation of copper-zinc polymetallic ore at the same time. The beneficiation method for the copper-zinc polymetallic ore containing the pyrrhotite comprises the technological methods of ore grinding, copper flotation, magnetic separation and regrinding to remove the pyrrhotite and zinc flotation, and the same collecting agent is adopted for copper flotation and zinc flotation. According to the method, the pyrrhotite is physically removed before zinc flotation, the defect that the pyrrhotite is activated and floats upwards in the zinc flotation operation is fundamentally overcome, and the quality of the zinc concentrate is ensured. Meanwhile, copper flotation and zinc flotation adopt the same collecting agent and have the advantages of being convenient to operate, small in influence of flotation return water on indexes and the like, and the technological process is low in beneficiation reagent cost and high in recovery rate.

Description

Technical Field

[0001] This application belongs to the field of mineral processing, and specifically relates to a method for beneficiating copper-zinc polymetallic ores containing pyrrhotite. Background Technology

[0002] Copper-zinc polymetallic ores containing pyrrhotite are an important type of mineral resource, but their efficient separation has always been a challenge in the mineral processing field. Current technologies typically employ a "preferential flotation of copper, followed by zinc flotation" process. In the zinc flotation operation, copper sulfate is generally added to activate the zinc minerals. However, the added copper sulfate also activates pyrrhotite, and the activated pyrrhotite is difficult to suppress with conventional depressants. This results in a large amount of pyrrhotite entering the zinc concentrate, severely reducing the quality of the zinc concentrate and causing it to fail to meet standards, significantly impacting its economic benefits. Furthermore, traditional preferential flotation processes often use different types of collectors for the copper and zinc flotation operations. For example, selective collectors such as Z-200 (ethyl thiocyanate) and No. 25 black reagent (sodium xylenol dithiophosphate) are used for copper flotation, while butyl xanthate collectors are used for zinc flotation. This multi-reagent system results in complex composition of flotation reflux water. When the reflux water is recycled, it will significantly interfere with flotation indicators, increase the difficulty of process stability control, cause unstable product quality, and consequently reduce metal recovery rate.

[0003] For example, patent publication number CN114632620A discloses a beneficiation method for recovering copper, zinc, and sulfur from zinc-copper-sulfur ores. This method effectively reduces the content of pyrrhotite in the raw ore by performing magnetic separation before flotation, thus eliminating the interference of pyrrhotite on the separation of copper and zinc in the flotation. However, this copper flotation operation uses Feringe collector, while zinc flotation uses butyl xanthate collector. The use of two different types of collectors in the entire system leads to an impact on the flotation parameters when the flotation reflux water from the different types of collectors is used.

[0004] For example, the non-patent literature "Research on Beneficiation Technology of a Pyrite Copper-Lead-Zinc Mine in Qinghai" (Zhu Enling, Zhang Yu, Chen Changcai, et al. Research on Beneficiation Technology of a Pyrite Copper-Lead-Zinc Mine in Qinghai [J]. Hunan Nonferrous Metals, 2015, 31(4):7.) adopts a process flow of copper-lead-zinc ore beneficiation: copper-lead mixed flotation—copper-lead separation—magnetic separation—magnetic tailings preferentially float zinc—flotation of zinc tailings and then sulfur flotation. However, in this study, No. 25 black powder was used as the collector in the copper-lead mixed flotation operation, and butyl xanthate was used as the collector in the zinc beneficiation operation. Two different types of collectors were used in the whole system. The flotation backwater of the two different types of collectors affected the flotation index, and the zinc loss rate in the magnetic concentrate was relatively high.

[0005] For example, in the non-patent literature "Experimental Study on Beneficiation Process of High Pyrrhotite Type Copper-Lead-Zinc Polymetallic Ore" (Chen Xiaobo, Xu Peiqiang, Sun Wenxiang, et al. Experimental Study on Beneficiation Process of High Pyrrhotite Type Copper-Lead-Zinc Polymetallic Ore [J]. Gold, 2020, 41(8):6.), this study uses a magnetic separation-copper-lead-sulfur mixed flotation-tailings zinc beneficiation process for mineral processing. Similarly, this beneficiation operation uses two types of collectors: butyl xanthate as the collector in the copper-lead mixed flotation operation and ZC as the collector in the zinc flotation operation. This causes the flotation backwater of the collector to affect the flotation index. In addition, the recovery rates of copper, lead and zinc obtained by this beneficiation are relatively low.

[0006] For example, in the non-patent literature "Study on the Separation Test of Copper-Lead-Zinc Ore in a High-Magnetic Pyrrhotite Mine" (Zhang Tianjun. Study on the Separation Test of Copper-Lead-Zinc Ore in a High-Magnetic Pyrrhotite Mine [J]. Sichuan Nonferrous Metals, 2016(2):5.), the mineral processing test was carried out using a process flow of pre-magnetic desulfurization-preferential copper flotation-copper-sulfur separation-copper tailings flotation for lead-lead tailings activation flotation for zinc. BP and ethyl xanthate were used as collectors for copper flotation, ethyl thiocyanate was used as a collector for lead flotation, and ethyl thiocyanate was used as a collector for zinc flotation. The variety of collectors led to the influence of the flotation reflux water on the flotation indicators. In addition, the copper loss rate in the magnetic concentrate was relatively high.

[0007] In summary, the existing technical solutions still have the following problems: (1) In the existing beneficiation process of copper-zinc polymetallic ores containing pyrrhotite, two different types of collectors are used in the copper and zinc flotation operations, which causes problems with the flotation indicators caused by the collector's flotation backwater; (2) In the existing beneficiation process of copper-zinc polymetallic ores containing pyrrhotite, there are problems with low recovery rate and poor concentrate quality. Therefore, it is urgent to develop a new beneficiation method and reagent that can effectively remove pyrrhotite, simplify the reagent system, and improve the copper-zinc recovery rate and concentrate quality. Summary of the Invention

[0008] To address the aforementioned issues, one of the main objectives of this application is to provide a collector for copper and zinc flotation in copper-zinc polymetallic ores. By using the same dedicated collector for both copper and zinc flotation, the reagent system is greatly simplified, the problem of mutual interference of flotation backwater caused by the use of multiple different types of collectors is avoided, and the stability and operability of the process are improved.

[0009] The second main objective of this application is to provide a beneficiation method for copper-zinc polymetallic ores containing pyrrhotite, in order to solve the problems in the prior art such as poor concentrate quality due to pyrrhotite interference, large interference from recycled water due to the use of multiple collectors, and low recovery rate of valuable metals.

[0010] In a first aspect, the present invention provides a method for beneficiating copper-zinc polymetallic ores containing pyrrhotite, wherein the collector comprises, by mass percentage: Dithiophosphate and / or dithiophosphate: 70%~85%; Mercaptobenzothiazole salt: 15%~25%; Cosolvent: 1~5%.

[0011] Furthermore, the dithiophosphate is selected from one or more of ammonium dithiophosphate, sodium dithiophosphate, or potassium dithiophosphate.

[0012] Furthermore, the mercaptobenzothiazole salt is selected from one or more of mercaptobenzothiazole sodium or mercaptobenzothiazole ammonium.

[0013] Furthermore, the co-solvent is selected from one or more of polyethylene glycol ether, polyoxyethylene ether, or ethylene glycol ethyl ether.

[0014] A second aspect of the present invention provides a method for beneficiating copper-zinc polymetallic ores containing pyrrhotite, comprising the following steps: Step S1, Slurry preparation: The raw ore is ground to prepare slurry; Step S2, copper flotation: Add modifier and collector to the slurry to carry out copper flotation to obtain copper concentrate and copper flotation tailings; Step S3, magnetic separation: The copper flotation tailings are subjected to magnetic separation to remove pyrrhotite, resulting in magnetic concentrate and magnetic tailings; Step S4, Zinc flotation: Add modifier, collector, activator and frother to the magnetic separation tailings to carry out zinc flotation to obtain zinc concentrate; The collectors used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are the collectors described above in this invention.

[0015] Furthermore, in step S2, the modifier used in the copper flotation operation includes one or more of humate, zinc sulfate, and sodium sulfite.

[0016] Furthermore, in step S4, the conditioning agent in the zinc flotation operation includes one or more of humic acid salts and lime; the activator includes copper sulfate; and the foaming agent includes one or more of polyethylene glycol, No. 2 oil, and methyl isobutyl methanol.

[0017] Furthermore, in step S2, the copper flotation operation includes one stage of roughing, two stages of scavenging, and two stages of cleaning; The first roughing stage includes: adding a modifier and a collector to the copper flotation roughing stage for a first roughing stage. The modifier added in the first roughing stage includes humate, zinc sulfate, and sodium sulfite. The amount of modifier used in the first roughing stage is 2100~4400 g / t. The amount of collector used in the first roughing stage is 40~80 g / t. The two-stage scavenging process includes: adding a modifier and a collector to the slurry obtained after roughing and performing two-stage scavenging; the modifiers added in both the first and second stages of the two-stage scavenging process include zinc sulfate and sodium sulfite; the dosage of the modifier in the first stage is 400~800 g / t; the dosage of the modifier in the second stage is 200~400 g / t; the dosage of the collector in the first stage is 20~40 g / t; and the dosage of the collector in the second stage is 10~20 g / t. The two-stage refining process includes: adding a modifier to the rough concentrate obtained after roughing and performing two-stage refining; the modifiers added to the first and second stages of the two-stage refining process both include zinc sulfate and sodium sulfite, with the modifier dosage for the first stage being 200~400g / t and the modifier dosage for the second stage being 100~200g / t.

[0018] Further, in step S3, the magnetic separation includes: Step S31, First stage magnetic separation: The copper flotation tailings are subjected to a first stage magnetic separation, the intensity of which is 3000~5000 Oe; Step S32, Grinding: The rough concentrate after the first stage of magnetic separation is ground again to a fineness of -0.038mm, accounting for 80-95%; Step S33, Second stage magnetic separation: The slurry after re-grinding is subjected to a second stage magnetic separation. The intensity of the second stage magnetic separation is 3000~5000 Oe, to obtain magnetic concentrate and magnetic tailings.

[0019] Furthermore, in step S4, the zinc flotation operation includes one stage of roughing, two stages of scavenging, and four stages of cleaning; The first-stage roughing process includes: adding a modifier, a collector, an activator, and a frother to the zinc flotation roughing stage for a first-stage roughing process. The dosage of the modifier in the first-stage roughing process is 1100~2300 g / t; the dosage of the collector in the first-stage roughing process is 40~80 g / t; the dosage of the frother in the first-stage roughing process is 20~40 g / t; and the dosage of the activator in the first-stage roughing process is 100~300 g / t. The two-stage scavenging process includes: adding activator, collector, and frother to the slurry obtained after zinc roughing for two-stage scavenging; the dosage of activator in the first stage of the two-stage scavenging is 50-100 g / t, the dosage of collector is 20-40 g / t, and the dosage of frother is 10-20 g / t; the dosage of activator in the second stage of the two-stage scavenging is 20-50 g / t, the dosage of collector is 10-20 g / t, and the dosage of frother is 5-10 g / t. The four-stage beneficiation process includes: adding a modifier to the rough concentrate obtained after zinc roughing and then performing four-stage beneficiation; wherein the modifier dosage for the first stage beneficiation is 600~1300g / t, the modifier dosage for the second stage beneficiation is 300~650g / t, the modifier dosage for the third stage beneficiation is 145~325g / t, and the modifier dosage for the fourth stage beneficiation is 70~160g / t.

[0020] Compared with the prior art, this application has the following beneficial effects: (1) The collector provided by the present invention has good selectivity and collection ability for copper and zinc minerals, while having weak sulfur collection ability. It is suitable for copper and zinc flotation of copper-zinc polymetallic ores, greatly simplifies the reagent system, avoids the problem of mutual interference of flotation reflux water caused by the use of multiple different types of collectors, and has the advantage of little impact of flotation reflux water on indicators, and can realize efficient recovery of copper and zinc ore.

[0021] (2) The copper-zinc polymetallic ore beneficiation method containing pyrrhotite provided by this invention adopts a beneficiation process of "prioritizing copper-removing pyrrhotite-re-re-beneficiating zinc", including grinding, copper flotation, magnetic separation and regrinding to remove pyrrhotite, and zinc flotation. The same collector is used for both copper and zinc flotation. This beneficiation method physically removes pyrrhotite before zinc flotation, fundamentally eliminating the drawback of pyrrhotite being activated and floating during zinc flotation, thus ensuring the quality of the zinc concentrate. Furthermore, using the same collector for both copper and zinc flotation offers advantages such as convenient operation and minimal impact of flotation reclaimed water on indicators. In addition, this process has low reagent costs and high recovery rates, bringing considerable economic benefits to enterprises through cost reduction and efficiency improvement.

[0022] (3) The mineral processing method and collector of the present invention are applicable to polymetallic mines such as copper-zinc mines, copper-lead-zinc mines, and copper polymetallic mines, and have the advantage of wide application range.

[0023] Other features and effects of this application will be set forth in the following description and will be apparent in part from the description or may be learned by practicing this application. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 The mineral processing flow chart and reagent dosage of Embodiment 1 of the present invention are shown; Figure 2 The mineral processing flow and reagent dosage of Comparative Example 1 of the present invention are shown. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0027] To achieve the above objectives, a first aspect of the present invention provides a collector for copper and zinc flotation of copper-zinc polymetallic ores, wherein the collector comprises, by mass percentage: dithiophosphate and / or dithiophosphate: 70%~85%; mercaptobenzothiazole salt: 15%~25%; and co-solvent: 1~5%.

[0028] In some preferred embodiments of the present invention, the dithiophosphate includes, but is not limited to, one or more of ammonium dithiophosphate, sodium dithiophosphate, or potassium dithiophosphate. The mercaptobenzothiazole salt includes, but is not limited to, one or more of sodium mercaptobenzothiazole or ammonium mercaptobenzothiazole. The cosolvent includes, but is not limited to, one or more of polyethylene glycol ether, polyoxyethylene ether, or ethylene glycol ethyl ether.

[0029] To further improve the selectivity and collecting effect of the collector on copper and zinc minerals, in a preferred embodiment of the present invention, the collector comprises, by mass percentage: dithiophosphate and / or dithiophosphate: 75%~82%; mercaptobenzothiazole salt: 17%~22%; and co-solvent: 3~5%.

[0030] To achieve the above objectives, a second aspect of the present invention provides a method for beneficiating copper-zinc polymetallic ores containing pyrrhotite, comprising the following steps: Step S1, Slurry preparation: The raw ore is ground to prepare slurry; Step S2, copper flotation: Add modifier and collector to the slurry to carry out copper flotation to obtain copper concentrate and copper flotation tailings; Step S3, magnetic separation: The copper flotation tailings are subjected to magnetic separation to remove pyrrhotite, resulting in magnetic concentrate and magnetic tailings; Step S4, Zinc flotation: Add modifier, collector, activator and frother to the magnetic separation tailings to carry out zinc flotation to obtain zinc concentrate; The collectors used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are the collectors described above in this invention.

[0031] In a preferred embodiment of the present invention, in step S2, the modifier in the copper flotation operation includes one or more of humate, zinc sulfate, and sodium sulfite.

[0032] In some preferred embodiments of the present invention, in step S4, the conditioning agent in the zinc flotation operation includes one or more of humic acid salts and lime; the activator includes copper sulfate; and the foaming agent includes one or more of polyethylene glycol, No. 2 oil, and MIBC (methyl isobutyl methanol).

[0033] In a preferred embodiment of the present invention, in step S1, the grinding fineness of the grinding process is -0.074 mm, accounting for 70% to 85%, and the slurry concentration is 25% to 35%.

[0034] In order to further improve the copper recovery rate and grade, in a preferred embodiment of the present invention, the copper flotation operation in step S2 includes a roughing stage, two scavenging stages, and two cleaning stages.

[0035] In some embodiments of the present invention, the first-stage roughing includes: adding a modifier and a collector to the copper flotation roughing stage for a first-stage roughing, wherein the modifier added in the first-stage roughing includes humate, zinc sulfate, and sodium sulfite, and the amount of modifier used in the first-stage roughing is 2100~4400 g / t; further, the amount of sodium humate used is 100~400 g / t, the amount of zinc sulfate used is 1000~2000 g / t, the amount of sodium sulfite used is 1000~2000 g / t, and the amount of collector used in the first-stage roughing is 40~80 g / t; further, the time of the first-stage roughing is 3~6 min.

[0036] In some embodiments of the present invention, the two-stage scavenging includes: adding a modifier and a collector to the slurry obtained after roughing and performing two-stage scavenging; the modifier added in both the first and second stages of the two-stage scavenging includes zinc sulfate and sodium sulfite; the amount of modifier used in the first stage of scavenging is 400-800 g / t, further, the amount of zinc sulfate is 200-400 g / t and the amount of sodium sulfite is 200-400 g / t; the amount of modifier used in the second stage of scavenging is 200-400 g / t, further, the amount of zinc sulfate is 200-400 g / t and the amount of sodium sulfite is 200-400 g / t; the amount of collector used in the first stage of scavenging is 20-40 g / t; the amount of collector used in the second stage of scavenging is 10-20 g / t; further, the time for the first stage of scavenging is 3-6 min, and the time for the second stage of scavenging is 2-5 min.

[0037] To further improve the copper recovery rate in copper flotation, a middlings return step is also included in the two-stage scavenging operation: the middlings remaining from the first stage scavenging are returned to the copper roughing operation to participate in the reaction, and the middlings remaining from the second stage scavenging are returned to the first stage scavenging operation to participate in the reaction.

[0038] In some embodiments of the present invention, the two-stage refining includes: adding a modifier to the rough concentrate obtained after roughing for two-stage refining; the modifier added to the first and second stages of the two-stage refining both include zinc sulfate and sodium sulfite, and the amount of modifier used in the first stage of refining is 200~400 g / t; further, the amount of zinc sulfate used in the first stage of refining is 100~200 g / t and the amount of sodium sulfite used is 100~200 g / t, and the amount of modifier used in the second stage of refining is 100~200 g / t; further, the amount of zinc sulfate used in the second stage of refining is 50~100 g / t and the amount of sodium sulfite used is 50~100 g / t.

[0039] To further improve the copper recovery rate in the copper beneficiation process, a middlings return step is included in the two-stage beneficiation process: the middlings remaining from the first stage beneficiation are returned to the copper roughing process to participate in the reaction, and the middlings remaining from the second stage beneficiation are returned to the first stage beneficiation process to participate in the reaction.

[0040] In a preferred embodiment of the present invention, in step S3, the magnetic separation includes: Step S31, First stage magnetic separation: The copper flotation tailings are subjected to a first stage magnetic separation, the intensity of which is 3000~5000 Oe; Step S32, Grinding: The rough concentrate after the first stage of magnetic separation is ground again to a fineness of -0.038mm, accounting for 80-95%; Step S33, Second stage magnetic separation: The slurry after re-grinding is subjected to a second stage magnetic separation. The intensity of the second stage magnetic separation is 3000~5000 Oe, to obtain magnetic concentrate and magnetic tailings.

[0041] This invention effectively removes pyrrhotite by employing a two-stage magnetic separation before zinc flotation, fundamentally eliminating the drawback of pyrrhotite being activated and floating during zinc flotation, thus ensuring the quality of the zinc concentrate. Furthermore, the two-stage magnetic separation process includes grinding. Since pyrrhotite and zinc minerals are closely intercalated, without grinding, some zinc-containing minerals would be lost in the magnetic concentrate. After re-grinding, the zinc content in the magnetic concentrate is lower, improving zinc recovery.

[0042] To further improve the zinc recovery rate and grade, in a preferred embodiment of the present invention, the zinc flotation operation includes a roughing stage, a scavenging stage, and a cleaning stage.

[0043] In some embodiments of the present invention, the first-stage roughing includes: adding a modifier, a collector, an activator, and a frother to the zinc flotation roughing stage for a first-stage roughing, wherein the amount of modifier used in the first-stage roughing is 1100~2300 g / t; further, the added modifier is humate or calcium oxide, wherein the amount of sodium humate is 100~300 g / t, the amount of lime is 1000~2000 g / t, and the amount of copper sulfate used as the activator is 100~300 g / t; the amount of collector used in the first-stage roughing is 40~80 g / t; the amount of frother used in the first-stage roughing is 20~40 g / t; and the amount of activator used in the first-stage roughing is 100~300 g / t; further, the time of the first-stage roughing is 3~6 min.

[0044] In some embodiments of the present invention, the two-stage scavenging includes: adding an activator, a collector, and a frother to the slurry obtained after zinc roughing for two-stage scavenging; the first stage of the two-stage scavenging uses 50-100 g / t of activator, 20-40 g / t of collector, and 10-20 g / t of frother; the second stage of the two-stage scavenging uses 20-50 g / t of activator, 10-20 g / t of collector, and 5-10 g / t of frother; further, the first stage of scavenging lasts for 2-4 minutes, and the second stage of scavenging lasts for 2-4 minutes.

[0045] To further improve the zinc recovery rate in zinc flotation, a middlings return step is also included in the two-stage scavenging operation: the middlings remaining from the first stage scavenging are returned to the zinc roughing operation to participate in the reaction, and the middlings remaining from the second stage scavenging are returned to the first stage scavenging operation to participate in the reaction.

[0046] The four-stage refining process includes: adding a modifier to the rough concentrate obtained after zinc roughing for four-stage refining; wherein, the modifier dosage for the first stage of refining is 600~1300 g / t, and further, the dosage of sodium humate for the first stage of refining is 100~300 g / t and the dosage of lime is 500~1000 g / t; the modifier dosage for the second stage of refining is 300~650 g / t, and further, the dosage of sodium humate for the second stage of refining is 50~15 g / t. The dosage of the first stage is 0 g / t, and the dosage of lime is 250~500 g / t; the dosage of the third stage of the selected modifier is 145~325 g / t, and further, the dosage of sodium humate in the third stage of the selected modifier is 25~75 g / t, and the dosage of lime is 120~250 g / t; the dosage of the fourth stage of the selected modifier is 70~160 g / t, and further, the dosage of sodium humate in the fourth stage of the selected modifier is 10~40 g / t, and the dosage of lime is 60~120 g / t.

[0047] To further improve the zinc recovery rate in zinc flotation, the four-stage cleaning process also includes a middlings return step: the remaining middlings from the four-stage cleaning process are returned to the previous process to participate in the reaction.

[0048] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0049] Example 1 A beneficiation method for a copper-zinc polymetallic ore containing pyrrhotite, wherein the ore contains 0.45% chalcopyrite, 4.75% sphalerite, 1.76% pyrrhotite, 0.16% copper, and 2.90% zinc, includes the following steps, see [link to details]. Figure 1 (EF1113 in the figure is the collector code of the present invention): Step S1, slurry preparation: The raw ore is ground to a fineness of -0.074 mm, accounting for 85%, and the slurry concentration is 30%.

[0050] Step S2, Copper Flotation: The above slurry is mixed with a modifier and a collector and subjected to a first-stage roughing, two-stage scavenging, and two-stage cleaning stages to obtain copper concentrate and copper flotation tailings. The first roughing stage includes: adding conditioning agents and collectors to the copper flotation roughing stage for a first roughing stage. The conditioning agents added are humate, zinc sulfate, and sodium sulfite. The dosage of sodium humate is 200 g / t, the dosage of zinc sulfate is 1000 g / t, the dosage of sodium sulfite is 1000 g / t, the dosage of collector is 50 g / t, and the flotation time is 4 min.

[0051] The two-stage scavenging process includes: adding modifiers and collectors to the pulp obtained after roughing and performing two-stage scavenging. In the first stage, 200 g / t of zinc sulfate, 200 g / t of sodium sulfite, and 25 g / t of collector are added, and the flotation time is 3 min. In the second stage, 100 g / t of zinc sulfate, 100 g / t of sodium sulfite, and 10 g / t of collector are added, and the flotation time is 2 min.

[0052] The two-stage cleaning process includes: adding modifiers to the rough concentrate obtained after roughing and performing two-stage cleaning. In the first stage of cleaning, the amount of zinc sulfate added is 100 g / t and the amount of sodium sulfite added is 100 g / t. In the second stage of cleaning, the amount of zinc sulfate added is 50 g / t and the amount of sodium sulfite added is 50 g / t. The middlings are returned sequentially: the middlings remaining from the first stage of scavenging are returned to the copper roughing operation to participate in the reaction; the middlings remaining from the second stage of scavenging are returned to the first stage of scavenging to participate in the reaction; the middlings remaining from the first stage of cleaning are returned to the copper roughing operation to participate in the reaction; and the middlings remaining from the second stage of cleaning are returned to the first stage of cleaning to participate in the reaction.

[0053] Step S3, subjecting the copper flotation tailings to magnetic separation, the magnetic separation comprising: Step S31, First stage magnetic separation: The copper flotation tailings are subjected to a first stage magnetic separation, and the intensity of the first stage magnetic separation is 3500 Oe; Step S32, Grinding: The rough concentrate after the first stage of magnetic separation is ground again to a fineness of -0.038mm, accounting for 95%. Step S33, Second stage magnetic separation: The slurry after re-grinding is subjected to a second stage magnetic separation. The intensity of the second stage magnetic separation is 3000 Oe, resulting in magnetic concentrate and magnetic tailings.

[0054] Step S4, Zinc Flotation: The above magnetic separation tailings are treated with modifiers, collectors, activators, and frothers, followed by a first-stage roughing, a second-stage scavenging, and a fourth-stage cleaning process to obtain zinc concentrate and tailings. The first roughing stage includes: adding conditioning agent, collector, activator and frother to the zinc flotation roughing stage for first-stage roughing. The added conditioning agent is humate and calcium oxide. The dosage of sodium humate is 100 g / t and the dosage of lime is 1000 g / t. The dosage of copper sulfate activator is 200 g / t, the dosage of collector is 60 g / t, the dosage of frother (No. 2 oil) is 20 g / t, and the flotation time is 4 min.

[0055] The two-stage scavenging process includes adding an activator, a collector, and a frother to the zinc roughing pulp for two-stage scavenging. In the first stage, the activator is added at a rate of 100 g / t of copper sulfate, the collector at a rate of 30 g / t, and the frother at a rate of 10 g / t, with a flotation time of 3 min. In the second stage, the activator is added at a rate of 40 g / t of copper sulfate, the collector at a rate of 10 g / t, and the frother (No. 2 oil) at a rate of 5 g / t, with a flotation time of 3 min.

[0056] The four-stage beneficiation process involves adding a modifier to the rough concentrate from the two-stage scavenging process and then performing four-stage beneficiation to obtain zinc concentrate and tailings. The dosage of sodium humate added in the first stage is 200 g / t and lime is 600 g / t; the dosage of sodium humate added in the second stage is 100 g / t and lime is 300 g / t; the dosage of sodium humate added in the third stage is 50 g / t and lime is 200 g / t; and the dosage of sodium humate added in the fourth stage is 30 g / t and lime is 100 g / t.

[0057] Mid-ore return: The mid-ore remaining from the first stage of scavenging is returned to the zinc roughing operation to participate in the reaction; the mid-ore remaining from the second stage of scavenging is returned to the first stage of scavenging to participate in the reaction; the mid-ore remaining from the fourth stage of cleaning operation is returned to the previous process to participate in the reaction.

[0058] The collector used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 consists of the following components by mass percentage: 78% sodium dithiophosphate, 19% sodium mercaptobenzothiazole, and 3% polyethylene glycol ether as a cosolvent.

[0059] Example 2 A beneficiation method for copper-zinc polymetallic ore containing pyrrhotite differs from Example 1 in that the components and proportions of the collector used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are different. The collector in this example, by mass percentage, includes 82% dithiophosphate, 15% sodium mercaptobenzothiazole, and 3% ethylene glycol ethyl ether as a co-solvent.

[0060] Example 3 A beneficiation method for copper-zinc polymetallic ore containing pyrrhotite differs from Example 1 in that the components and proportions of the collector used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are different. The collector in this example, by mass percentage, includes 75% ammonium dithiophosphate, 22% mercaptobenzothiazole ammonium, and 3% polyoxyethylene ether as a cosolvent.

[0061] Comparative Example 1 A beneficiation method for a copper-zinc polymetallic ore containing pyrrhotite, wherein the ore contains 0.45% chalcopyrite, 4.75% sphalerite, 1.76% pyrrhotite, 0.16% copper, and 2.90% zinc. This comparative beneficiation method employs a copper-zinc-sulfur mixed flotation-zinc-sulfur separation process, using different types of collectors in the copper and zinc flotation operations. The method includes the following steps, the process flow of which is described in [link to flow chart]. Figure 2 : Step S1, slurry preparation: The raw ore is ground to a fineness of -0.074 mm, accounting for 85%, and the slurry concentration is 30%.

[0062] Step S2, Copper Flotation: The above slurry is mixed with a modifier and a collector and subjected to a first-stage roughing, two-stage scavenging, and two-stage cleaning stages to obtain copper concentrate and copper flotation tailings. The first roughing stage includes: adding conditioning agents and collectors to the copper flotation roughing stage for a first roughing stage. The conditioning agents added are humate, zinc sulfate, and sodium sulfite. The dosage of sodium humate is 200 g / t, zinc sulfate is 1000 g / t, sodium sulfite is 1000 g / t, and the dosage of collector ethyl thiocyanate is 100 g / t. The flotation time is 4 min.

[0063] The two-stage scavenging process includes: adding modifiers and collectors to the pulp obtained after roughing and performing two-stage scavenging. In the first stage, 200 g / t of zinc sulfate, 200 g / t of sodium sulfite, and 25 g / t of ethyl thiocyanate collector are added, and the flotation time is 3 min. In the second stage, 100 g / t of zinc sulfate, 100 g / t of sodium sulfite, and 10 g / t of ethyl thiocyanate collector are added, and the flotation time is 2 min.

[0064] The two-stage cleaning process includes: adding modifiers to the rough concentrate obtained after roughing and performing two-stage cleaning. In the first stage of cleaning, the amount of zinc sulfate added is 100 g / t and the amount of sodium sulfite added is 100 g / t. In the second stage of cleaning, the amount of zinc sulfate added is 50 g / t and the amount of sodium sulfite added is 50 g / t. The middlings are returned sequentially: the middlings remaining from the first stage of scavenging are returned to the copper roughing operation to participate in the reaction; the middlings remaining from the second stage of scavenging are returned to the first stage of scavenging to participate in the reaction; the middlings remaining from the first stage of cleaning are returned to the copper roughing operation to participate in the reaction; and the middlings remaining from the second stage of cleaning are returned to the first stage of cleaning to participate in the reaction.

[0065] Step S3, the copper flotation tailings are subjected to zinc flotation, wherein the zinc flotation includes: The copper flotation tailings were treated with conditioning agents, collectors, activators, and frothers, followed by a first-stage zinc-sulfur mixed roughing and a second-stage scavenging to obtain a zinc-sulfur mixed concentrate and tailings. The zinc-sulfur mixed concentrate was then subjected to zinc-sulfur separation, involving a first-stage zinc roughing, a second-stage zinc scavenging, and a fourth-stage zinc cleaning. The first-stage zinc-sulfur mixed roughing process includes: adding an activator, a collector, and a frother to the zinc-sulfur mixed flotation roughing stage for first-stage roughing. The dosage of the activator copper sulfate is 300 g / t, the dosage of the collector butyl xanthate is 300 g / t, the dosage of the frother No. 2 oil is 30 g / t, and the flotation time is 4 min.

[0066] The two-stage scavenging process includes: adding an activator, collector, and frother to the pulp after the zinc-sulfur mixed roughing process for two-stage scavenging. In the first stage, the dosage of copper sulfate activator is 60 g / t, the dosage of butyl xanthate collector is 100 g / t, and the dosage of No. 2 frother is 10 g / t, with a flotation time of 3 min. In the second stage, the dosage of copper sulfate activator is 30 g / t, the dosage of butyl xanthate collector is 30 g / t, and the dosage of No. 2 frother is 3 g / t, with a flotation time of 3 min.

[0067] Middlings return: The middlings remaining from the first stage of scavenging are returned to the zinc-sulfur mixed roughing operation to participate in the reaction, and the middlings remaining from the second stage of scavenging are returned to the first stage of scavenging to participate in the reaction.

[0068] The zinc-sulfur mixed concentrate is subjected to zinc-sulfur separation. The first stage of zinc roughing includes: adding conditioning agents to the zinc-sulfur mixed flotation roughing stage for first-stage roughing. The added conditioning agents are humate and calcium oxide. The dosage of sodium humate is 200 g / t and the dosage of lime is 38000 g / t. The flotation time is 4 min.

[0069] The two-stage zinc scavenging process includes: adding an activator to the zinc roughing slurry for two-stage scavenging; in the first stage, the amount of copper sulfate added as the activator is 60 g / t, and the flotation time is 3 min; in the second stage, the amount of copper sulfate added as the activator is 30 g / t, and the flotation time is 3 min.

[0070] The four-stage selection process includes: the first stage involves adding 150 g / t of sodium humate and 15,000 g / t of lime; the second stage involves adding 100 g / t of sodium humate and 3,000 g / t of lime; the third stage involves adding 50 g / t of sodium humate and 1,500 g / t of lime; and the fourth stage involves adding 25 g / t of sodium humate and 7,500 g / t of lime.

[0071] Mid-ore return: The mid-ore remaining from the first stage of zinc scavenging is returned to the zinc-sulfur separation operation to participate in the reaction; the mid-ore remaining from the second stage of zinc scavenging is returned to the first stage of scavenging operation to participate in the reaction; the mid-ore remaining from the fourth stage of beneficiation operation is returned to the previous process to participate in the reaction.

[0072] Comparative Example 2 A beneficiation method for copper-zinc polymetallic ore containing pyrrhotite differs from Example 1 in that the collectors used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are different. The collector used in the copper flotation operation is ethyl thiocyanate, and the collector used in the zinc flotation operation is butyl xanthate.

[0073] Comparative Example 3 A beneficiation method for copper-zinc polymetallic ore containing pyrrhotite differs from Example 1 in that the proportions of collectors used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are different. The collector in this example, by mass percentage, includes 60% sodium dithiophosphate, 35% sodium mercaptobenzothiazole, and 5% polyethylene glycol ether.

[0074] Comparative Example 4 A beneficiation method for copper-zinc polymetallic ore containing pyrrhotite differs from Example 1 in that the proportions of collectors used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are different. The collector in this example, by mass percentage, includes 90% sodium dithiophosphate, 8% sodium mercaptobenzothiazole, and 2% polyethylene glycol ether.

[0075] The performance of the materials obtained from the above embodiments and comparative examples was compared, and the results are shown in Table 1.

[0076] Table 1

[0077] As can be seen from Table 1 above, the process flow of the present invention achieves better copper and zinc recovery. In contrast, Comparative Example 1 employs a copper-zinc-sulfur co-flotation-zinc-sulfur separation beneficiation process, using Z-200 (ethyl thiocyanate) as the collector for copper flotation and butyl xanthate as the collector for zinc-sulfur co-flotation. This results in a lower zinc recovery rate and poorer zinc concentrate quality. Furthermore, this process requires a larger amount of lime, leading to higher beneficiation costs.

[0078] The cost of the mineral processing reagents used in Example 1 was compared with that used in Comparative Example 1, and the results are shown in Table 2.

[0079] Table 2

[0080] The results show that the mineral processing reagent cost of the copper-magnetic separation-zinc flotation process in Example 1 of the present invention is significantly lower than that of the copper-zinc-sulfur mixed flotation-zinc-sulfur separation process in Comparative Example 1, with a reduction of more than 50%.

[0081] Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A collector for the flotation of copper and zinc in copper-zinc polymetallic ores, characterized in that, The collector comprises, by weight percentage: Dithiophosphate and / or dithiophosphate: 70%~85%; Mercaptobenzothiazole salt: 15%~25%; Cosolvent: 1~5%.

2. The collector according to claim 1, characterized in that, The dithiophosphate is selected from one or more of ammonium dithiophosphate, sodium dithiophosphate, or potassium dithiophosphate.

3. The collector according to claim 1, characterized in that, The mercaptobenzothiazole salt is selected from one or more of mercaptobenzothiazole sodium or mercaptobenzothiazole ammonium.

4. The collector according to claim 1, characterized in that, The co-solvent is selected from one or more of polyethylene glycol ether, polyoxyethylene ether, or ethylene glycol ethyl ether.

5. A method for beneficiating copper-zinc polymetallic ores containing pyrrhotite, characterized in that, Includes the following steps: Step S1, Slurry preparation: The raw ore is ground to prepare slurry; Step S2, copper flotation: Add modifier and collector to the slurry to carry out copper flotation to obtain copper concentrate and copper flotation tailings; Step S3, magnetic separation: The copper flotation tailings are subjected to magnetic separation to remove pyrrhotite, resulting in magnetic concentrate and magnetic tailings; Step S4, Zinc flotation: Add modifier, collector, activator and frother to the magnetic separation tailings to carry out zinc flotation to obtain zinc concentrate; The collectors used in the copper flotation operation in step S2 and the zinc flotation operation in step S4 are the collectors according to any one of claims 1 to 4.

6. The mineral processing method according to claim 5, characterized in that, In step S2, the conditioning agent in the copper flotation operation includes one or more of humate, zinc sulfate, and sodium sulfite.

7. The mineral processing method according to claim 5, characterized in that, In step S4, the conditioning agent in the zinc flotation operation includes one or more of humic acid salts and lime; the activator includes copper sulfate; and the foaming agent includes one or more of polyethylene glycol, No. 2 oil, and methyl isobutyl methanol.

8. The mineral processing method according to claim 5, characterized in that, In step S2, the copper flotation operation includes one stage of roughing, two stages of scavenging, and two stages of cleaning. The first roughing stage includes: adding a modifier and a collector to the copper flotation roughing stage for a first roughing stage. The modifier added in the first roughing stage includes humate, zinc sulfate, and sodium sulfite. The amount of modifier used in the first roughing stage is 2100~4400 g / t. The amount of collector used in the first roughing stage is 40~80 g / t. The two-stage scavenging process includes: adding a modifier and a collector to the slurry obtained after roughing and performing two-stage scavenging; the modifiers added in both the first and second stages of the two-stage scavenging process include zinc sulfate and sodium sulfite; the dosage of the modifier in the first stage is 400~800 g / t; the dosage of the modifier in the second stage is 200~400 g / t; the dosage of the collector in the first stage is 20~40 g / t; and the dosage of the collector in the second stage is 10~20 g / t. The two-stage refining process includes: adding a modifier to the rough concentrate obtained after roughing and performing two-stage refining; the modifiers added to the first and second stages of the two-stage refining process both include zinc sulfate and sodium sulfite, with the modifier dosage for the first stage being 200~400g / t and the modifier dosage for the second stage being 100~200g / t.

9. The mineral processing method according to claim 5, characterized in that, In step S3, the magnetic separation includes: Step S31, First stage magnetic separation: The copper flotation tailings are subjected to a first stage magnetic separation, the intensity of which is 3000~5000 Oe; Step S32, Grinding: The rough concentrate after the first stage of magnetic separation is ground again to a fineness of -0.038mm, accounting for 80-95%; Step S33, Second stage magnetic separation: The slurry after re-grinding is subjected to a second stage magnetic separation. The intensity of the second stage magnetic separation is 3000~5000 Oe, to obtain magnetic concentrate and magnetic tailings.

10. The mineral processing method according to claim 5, characterized in that, In step S4, the zinc flotation operation includes one stage of roughing, two stages of scavenging, and four stages of cleaning. The first-stage roughing process includes: adding a modifier, a collector, an activator, and a frother to the zinc flotation roughing stage for a first-stage roughing process. The dosage of the modifier in the first-stage roughing process is 1100~2300 g / t; the dosage of the collector in the first-stage roughing process is 40~80 g / t; the dosage of the frother in the first-stage roughing process is 20~40 g / t; and the dosage of the activator in the first-stage roughing process is 100~300 g / t. The two-stage scavenging process includes: adding activator, collector, and frother to the slurry obtained after zinc roughing for two-stage scavenging; the dosage of activator in the first stage of the two-stage scavenging is 50-100 g / t, the dosage of collector is 20-40 g / t, and the dosage of frother is 10-20 g / t; the dosage of activator in the second stage of the two-stage scavenging is 20-50 g / t, the dosage of collector is 10-20 g / t, and the dosage of frother is 5-10 g / t. The four-stage beneficiation process includes: adding a modifier to the rough concentrate obtained after zinc roughing and then performing four-stage beneficiation; wherein the modifier dosage for the first stage beneficiation is 600~1300g / t, the modifier dosage for the second stage beneficiation is 300~650g / t, the modifier dosage for the third stage beneficiation is 145~325g / t, and the modifier dosage for the fourth stage beneficiation is 70~160g / t.

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