A copper oxide ore flotation collector and a preparation method and use method thereof

Abstract

The application provides a flotation collector for copper oxide ore and a preparation method and use method thereof, and relates to the technical field of flotation of copper oxide ore. Raw materials of the flotation collector include dimercaptoacetate and black drug; the mass ratio of the dimercaptoacetate and the black drug is 0.5-6.0:1. After compounding, on the surface of sulfidized copper oxide ore, the black drug is preferentially coordinated with copper ions through a dithiophosphoric acid group, and the dimercaptoacetate is further anchored and enhanced in hydrophobicity through a bimer capto group, so as to form a complementary co-adsorption layer. The synergistic effect not only retains the high selectivity of the black drug, but also makes up for the defect of insufficient collecting strength of the black drug, thereby effectively solving the problem that the selectivity of the collector to the copper oxide ore is not strong, resulting in fluctuation of flotation indexes.

Description

Technical Field

[0001] This application relates to the field of flotation technology for copper oxide ores, and more particularly to a flotation collector for copper oxide ores, its preparation method, and its application method. Background Technology

[0002] Currently, global copper resources mainly consist of two categories: copper sulfide ores and copper oxide ores. Among them, copper sulfide ores, due to their high grade and mature beneficiation and smelting processes, have long been the main source of copper metal production. However, with the extension of mining time, high-quality copper sulfide resources have gradually decreased, ore grades have continued to decline, and mining costs have been rising, making it difficult for the supply capacity of copper sulfide resources to meet the growing demand for copper metal.

[0003] The development of oxidized copper ores is limited by their inherent mineralogical characteristics. Specifically, oxidized copper ores typically exhibit high oxidation rates and complex mineral compositions (common minerals include malachite, azurite, cuprite, and chrysocolla). Furthermore, the ore surface is highly hydrophilic, resulting in poor natural floatability and making direct recovery via conventional flotation methods difficult. Simultaneously, the ores often contain high levels of mud, which easily encapsulates mineral particles, interfering with the flotation process and affecting separation parameters. In addition, the diverse and complex distribution of associated minerals, with copper minerals intertwined with other minerals, makes individual mineral liberation difficult. These combined factors significantly increase the difficulty of beneficiating oxidized copper ores, leaving a large amount of low-grade or complex oxidized copper resources unutilized.

[0004] Among existing copper oxide ore beneficiation technologies, sulfidation flotation is the most widely used. However, this method still has certain limitations in practical applications: the sulfidation process is greatly affected by the ore properties, and the sulfidation effect is difficult to control precisely; the copper sulfide film formed after sulfidation lacks stability and is prone to detachment during flotation; traditional collectors have poor selectivity for copper oxide minerals, and flotation indicators are prone to fluctuation. These problems restrict further improvement in the flotation recovery rate of copper oxide ore, making it difficult to achieve efficient recovery of this type of resource. Summary of the Invention

[0005] The purpose of this application is to provide a flotation collector for copper oxide ore, its preparation method, and its application method, so as to solve the above-mentioned problems.

[0006] To achieve the above objectives, this application adopts the following technical solution: This application provides a flotation collector for copper oxide ore, wherein the raw materials for the flotation collector include dimercaptoacetate and black dye; The mass ratio of the dimercaptoacetic acid ester to the black powder is 0.5-6.0:1.

[0007] Optionally, the structural formula of the dimercaptoacetic acid ester is: ; R includes one of ethyl, vinyl, n-propyl, isopropyl, n-butyl, and n-pentyl.

[0008] Optionally, the black powder comprises dialkyl dithiophosphate; The hydrocarbon group in the dialkyl dithiophosphate includes at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl, and tolyl.

[0009] This application also provides a method for preparing the flotation collector for the copper oxide ore, comprising: dissolving dimercaptoacetic acid ester in a strong alkaline solution at room temperature, and then dissolving the black reagent to obtain the flotation collector.

[0010] Optionally, the inorganic strong base in the inorganic strong base solution has a mass fraction of 4-12%.

[0011] This application also provides a method for using the flotation collector for the aforementioned copper oxide ore, including: The raw copper oxide ore is ground and then mixed with water to obtain a raw ore slurry; the raw ore slurry is then added to a sulfide ore collector for sulfide ore flotation and roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings; After adjusting the pH of the slurry of the sulfide mineral flotation tailings to alkaline, a sulfiding agent is added to sulfide the copper oxide minerals. Then, the flotation collector is added to perform oxide mineral flotation to obtain copper oxide concentrate and total tailings.

[0012] Optionally, the vulcanizing agent includes at least one of sodium sulfide, calcium sulfide, and sodium hydrosulfide.

[0013] Optionally, the pH value of the sulfide ore flotation tailings is adjusted to 8-12.

[0014] Optionally, the amount of the sulfiding agent used is 500-2000 grams per ton of the copper oxide ore.

[0015] Optionally, the flotation collector is used at a rate of 100-300 grams per ton of the copper oxide ore.

[0016] Compared with the prior art, the beneficial effects of this application include: This application provides a flotation collector for copper oxide ore. Black dye can form stable four-membered ring chelates with copper ions, but its direct collecting ability for copper oxide ore is weak; effective adsorption usually requires pre-sulfidation on the mineral surface to form a copper sulfide film. The dimercaptoacetic acid molecule has two ends... The SH group can form a bidentate chelate with copper ions (or sulfided copper ions) on the surface of copper oxide minerals, exhibiting high adsorption strength. When combined with the SH group, on the surface of sulfided copper oxide minerals, the dithiophosphate group preferentially coordinates with copper ions, while the dimercaptoacetate further anchors and enhances hydrophobicity through the dithiol group, forming a complementary co-adsorption layer. This synergistic effect retains the high selectivity of the dithiophosphate group while compensating for its insufficient collecting strength, thus effectively solving the problem of weak selectivity of the collector for copper oxide minerals, leading to fluctuations in flotation parameters.

[0017] This application also provides a method for preparing the flotation collector for the oxidized copper ore. On the one hand, dimercaptoacetate is dissolved first, followed by the dissolution of the black reagent, to avoid possible thioexchange or oxidation side reactions when the two are locally mixed at high concentrations, thus ensuring the activity of the reagent. On the other hand, the black reagent is easily hydrolyzed and degraded under acidic or neutral conditions, and an inorganic strong alkaline solution provides it with a stable alkaline storage environment. At the same time, the thiol groups of dimercaptoacetate are not easily oxidized under weakly alkaline conditions.

[0018] This application also provides a method for using the flotation collector for the copper oxide ore. The flotation collector for the copper oxide ore is used in combination with a sulfiding agent, which can effectively replace conventional collectors such as xanthate, significantly improve the flotation recovery rate of copper oxide ore, and can be widely used in the flotation of copper oxide ore and sulfide-copper oxide ore. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0020] Figure 1 A schematic diagram of the copper oxide flotation process flow, illustrating the application of flotation collectors for copper oxide ore. Detailed Implementation

[0021] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0022] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0023] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0024] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0025] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0026] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0027] To better explain the technical solution provided in this application, the technical solution provided in this application will be described in general before the specific implementation.

[0028] In a first aspect, this application provides a flotation collector for copper oxide ore, wherein the raw materials for the flotation collector include dimercaptoacetate and black dye; The mass ratio of the dimercaptoacetic acid ester to the black powder is 0.5-6.0:1.

[0029] Optionally, the mass ratio of dimercaptoacetate to black powder can be 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, or any value between 0.5 and 6.0:1.

[0030] In an optional embodiment, the structural formula of the dimercaptoacetic acid ester is: ; R includes one of ethyl, vinyl, n-propyl, isopropyl, n-butyl, and n-pentyl.

[0031] In an optional embodiment, the black powder comprises dialkyl dithiophosphate; The hydrocarbon group in the dialkyl dithiophosphate includes at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl, and tolyl.

[0032] Secondly, this application also provides a method for preparing the flotation collector for the copper oxide ore, comprising: dissolving dimercaptoacetic acid ester in a strong alkaline solution at room temperature, and then dissolving the black powder to obtain the flotation collector.

[0033] In one optional embodiment, the inorganic strong base solution contains 4-12% inorganic strong base by mass.

[0034] Optionally, the mass fraction of the inorganic strong base in the inorganic strong base solution can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or any value between 4% and 12%.

[0035] Thirdly, this application also provides a method for using the flotation collector for the aforementioned copper oxide ore, including: The raw copper oxide ore is ground and then mixed with water to obtain a raw ore slurry; the raw ore slurry is then added to a sulfide ore collector for sulfide ore flotation and roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings; After adjusting the pH of the slurry of the sulfide mineral flotation tailings to alkaline, a sulfiding agent is added to sulfide the copper oxide minerals. Then, the flotation collector is added to perform oxide mineral flotation to obtain copper oxide concentrate and total tailings.

[0036] In one optional embodiment, the vulcanizing agent includes at least one of sodium sulfide, calcium sulfide, and sodium hydrosulfide.

[0037] In an optional implementation, the pH of the sulfide ore flotation tailings is adjusted to 8-12.

[0038] Optionally, the pH value of the sulfide ore flotation tailings can be 8, 9, 10, 11, 12, or any value between 8 and 12.

[0039] In one optional embodiment, the amount of the sulfiding agent is 500-2000 grams per ton of the copper oxide ore.

[0040] Optionally, the amount of sulfiding agent used can be 500 grams per ton of the copper oxide ore, 600 grams per ton of the copper oxide ore, 700 grams per ton of the copper oxide ore, 800 grams per ton of the copper oxide ore, 900 grams per ton of the copper oxide ore, 1000 grams per ton of the copper oxide ore, 1100 grams per ton of the copper oxide ore, 1200 grams per ton of the copper oxide ore, or 1300 grams per ton of the copper oxide ore. The copper oxide ore, 1400 grams per ton, 1500 grams per ton, 1600 grams per ton, 1700 grams per ton, 1800 grams per ton, 1900 grams per ton, 2000 grams per ton, or any value between 500 and 2000 grams per ton of copper oxide ore.

[0041] In one optional embodiment, the flotation collector is used at a rate of 100-300 grams per ton of the copper oxide ore.

[0042] Optionally, the amount of flotation collector can be 100 grams per ton of the copper oxide ore, 200 grams per ton of the copper oxide ore, 300 grams per ton of the copper oxide ore, or any value between 100 and 300 grams per ton of the copper oxide ore.

[0043] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0044] The raw Kolwezi copper ore used in the examples and comparative examples has a copper grade of 3.15%, a cobalt grade of 0.12%, a copper sulfide mineral content of 35.2%, a copper oxide mineral content of 64.8%, a quartz content of 12.35%, a dolomite content of 4.42%, and a calcite content of 5.68%.

[0045] In the following examples and comparative examples, the grinding fineness was -200 mesh, accounting for 75%; all flotation experiments were conducted in a 500mL single-cell flotation machine at room temperature; the sulfidation stirring time was 3 minutes, the collector stirring time was 3 minutes, and the flotation skimming time was 5 minutes. Unless otherwise specified, the above operating parameters are the same in all examples and comparative examples. Example 1 This embodiment provides a flotation collector for copper oxide ore: The raw materials include dimercaptoacetate and black powder; the mass ratio of dimercaptoacetate to black powder is 2:1.

[0046] The structural formula of the dimercaptoacetic acid ester is:

[0047] The dimercaptoacetic acid ester was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0048] The black powder is sodium isobutyl dithiophosphate, purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.

[0049] This embodiment also provides a method for preparing the flotation collector for the above-mentioned copper oxide ore: The flotation collector is obtained by mixing dimercaptoacetate and black powder with an 8% sodium hydroxide solution.

[0050] Example 2 This embodiment provides a flotation collector for copper oxide ore: The raw materials include dimercaptoacetate and black powder; the mass ratio of dimercaptoacetate to black powder is 2:1.

[0051] The structural formula of the dimercaptoacetic acid ester is:

[0052] The dimercaptoacetic acid ester was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0053] The black powder is sodium isobutyl dithiophosphate, purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.

[0054] This embodiment also provides a method for preparing the flotation collector for the above-mentioned copper oxide ore: The flotation collector is obtained by mixing dimercaptoacetate and black powder with an 8% sodium hydroxide solution.

[0055] Example 3 This embodiment provides a flotation collector for copper oxide ore: The raw materials include dimercaptoacetate and black powder; the mass ratio of dimercaptoacetate to black powder is 2:1.

[0056] The structural formula of the dimercaptoacetic acid ester is:

[0057] The dimercaptoacetic acid ester was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0058] The black powder is sodium isobutyl dithiophosphate, purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.

[0059] This embodiment also provides a method for preparing the flotation collector for the above-mentioned copper oxide ore: The flotation collector is obtained by mixing dimercaptoacetate and black powder with an 8% sodium hydroxide solution.

[0060] Example 4 This embodiment provides a flotation collector for copper oxide ore: The raw materials include dimercaptoacetate and black powder; the mass ratio of dimercaptoacetate to black powder is 2:1.

[0061] The structural formula of the dimercaptoacetic acid ester is:

[0062] The dimercaptoacetic acid ester was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0063] The black powder is sodium isobutyl dithiophosphate, purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.

[0064] This embodiment also provides a method for preparing the flotation collector for the above-mentioned copper oxide ore: The flotation collector is obtained by mixing dimercaptoacetate and black powder with a 10% sodium hydroxide solution.

[0065] Example 5 This embodiment provides a method for using a flotation collector for copper oxide ore, the process flow of which is as follows: Figure 1 As shown, the specific steps are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0066] Sodium carbonate was used to adjust the pH value to 10 for oxidative ore flotation of sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent and stirred for 3 minutes for sulfidation treatment. Then, 200 g / t of the flotation collector from Example 1 (the mass ratio of black reagent to dimercaptoacetate was 1:2) was added and stirred for 3 minutes for roughing. The flotation skimming time was 5 minutes to obtain copper oxide concentrate and final tailings.

[0067] Example 6 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0068] Sodium carbonate was used to adjust the pH value to 10 to perform oxidative ore flotation on sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent, and then 200 g / t of flotation collector (raw materials are the same as in Example 1, with a mass ratio of black reagent to dimercaptoacetate of 1:1) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0069] Example 7 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0070] Sodium carbonate was used to adjust the pH value to 10 to perform oxidative ore flotation on sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide was added as a sulfiding agent, and then 200 g / t of flotation collector (raw materials are the same as in Example 1, with the mass ratio of black powder to dimercaptoacetate being 1:3) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0071] Example 8 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0072] Sodium carbonate was used to adjust the pH value to 10 for oxidative ore flotation of sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent, and then 200 g / t of flotation collector (raw material is the same as in Example 1, with the mass ratio of black reagent to dimercaptoacetate is 1:4) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0073] Example 9 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0074] Sodium carbonate was used to adjust the pH value to 8 to perform oxidative ore flotation on sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent, and then 200 g / t of flotation collector (raw material is the same as in Example 1, with the mass ratio of black powder to dimercaptoacetate is 1:2) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0075] Example 10 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0076] Sodium carbonate was used to adjust the pH value to 12 to perform oxidative ore flotation on sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent, and then 200 g / t of flotation collector (raw materials are the same as in Example 1, with the mass ratio of black powder to dimercaptoacetate being 1:2) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0077] Example 11 This embodiment provides a method for using a flotation collector for copper oxide ore. The only difference from Embodiment 5 is that the amount of flotation collector used is 100g / t for one roughing process to obtain copper oxide concentrate and final tailings.

[0078] Example 12 This embodiment provides a method for using a flotation collector for copper oxide ore. The only difference from Embodiment 5 is that the amount of flotation collector used is 300g / t for one roughing process to obtain copper oxide concentrate and final tailings.

[0079] Example 13 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0080] Sodium carbonate was used to adjust the pH value to 10 for oxidative ore flotation of sulfide ore tailings. First, 500 g / t of sodium hydrosulfide was added as a sulfiding agent, and then 200 g / t of flotation collector (sodium diethyl dithiophosphate, where the R group in dimercaptoacetate is ethyl, and the mass ratio of dithioacetate to dimercaptoacetate is 1:2) was added for roughing to obtain copper oxide concentrate and final tailings.

[0081] Example 14 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0082] Sodium carbonate was used to adjust the pH value to 10 for oxidative ore flotation of sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent. Then, 200 g / t of flotation collector (the black reagent is sodium dibutyl dithiophosphate, and the R group in dimercaptoacetate is n-propyl, with a mass ratio of 1:2 to dimercaptoacetate) was added for roughing to obtain copper oxide concentrate and final tailings.

[0083] Example 15 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0084] Sodium carbonate was used to adjust the pH value to 10 for oxidative ore flotation of sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent. Then, 200 g / t of the flotation collector provided in Example 2 (the mass ratio of black powder to dimercaptoacetate was 1:2) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0085] Example 16 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0086] Sodium carbonate was used to adjust the pH value to 10 for oxidative ore flotation of sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent. Then, 200 g / t of the flotation collector provided in Example 3 (the mass ratio of black powder to dimercaptoacetate was 1:2) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0087] Example 17 This embodiment provides a method for using a flotation collector for copper oxide ore, the specific steps of which are as follows: The raw copper oxide ore was ground and then mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation was carried out, with 60 g / t of pentyl xanthate (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) and 35 g / t of frother pine oil (purchased from Beikuang Chemical Technology (Cangzhou) Co., Ltd.) added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings.

[0088] Sodium carbonate was used to adjust the pH value to 10 to perform oxidative ore flotation on sulfide ore flotation tailings. First, 500 g / t of sodium hydrosulfide sulfide was added as a sulfiding agent. Then, 200 g / t of the flotation collector provided in Example 4 (the mass ratio of black powder to dimercaptoacetate was 1:2) was added for a roughing process to obtain copper oxide concentrate and final tailings.

[0089] Comparative Example 1 This comparative example provides a flotation method for copper oxide ore, the specific steps of which are as follows: After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of pentyl xanthate and 35 g / t of frother added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation, with 200 g / t of pentyl xanthate added for a first roughing to obtain copper oxide concentrate and final tailings.

[0090] Comparative Example 2 This comparative example provides a flotation method for copper oxide ore, the specific steps of which are as follows: After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of pentyl xanthate and 35 g / t of frother added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation, with 200 g / t of butyl xanthate added for a first roughing to obtain copper oxide concentrate and final tailings.

[0091] Comparative Example 3 After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of pentyl xanthate and 35 g / t of frother added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation, with 200 g / t of black dye (sodium diisobutyl thiophosphate) added for a first roughing to obtain copper oxide concentrate and final tailings.

[0092] Comparative Example 4 After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of pentyl xanthate and 35 g / t of frother added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation, with 200 g / t of dimercaptoacetate (1,4-butanediol bis(mercaptoacetate)) added for a first roughing to obtain copper oxide concentrate and final tailings.

[0093] Comparative Example 5 After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of pentyl xanthate and 35 g / t of frother added for roughing, to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation, with the pH value adjusted to 10 using sodium carbonate, 500 g / t of sodium sulfide added for sulfidation treatment, and 200 g / t of black powder (sodium diisobutyl thiophosphate) added for a first roughing, to obtain copper oxide concentrate and final tailings.

[0094] Comparative Example 6 After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of pentyl xanthate and 35 g / t of frother added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation. The pH value is adjusted to 10 with sodium carbonate, 500 g / t of sodium sulfide is added for sulfidation treatment, and 200 g / t of dimercaptoacetate (1,4-butanediol bis(mercaptoacetate)) is added for a first roughing to obtain copper oxide concentrate and final tailings.

[0095] Comparative Example 7 After grinding the raw ore, it is mixed with water to obtain a slurry with a concentration of 33%. First, sulfide ore flotation is carried out, with 60 g / t of amyl xanthate and 35 g / t of frother added for roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings. Then, the sulfide ore flotation tailings are subjected to oxide ore flotation. The pH value is adjusted to 10 with sodium carbonate, 1000 g / t of sodium sulfide is added for sulfidation treatment, and then 200 g / t of amyl xanthate is added for a first roughing to obtain copper oxide concentrate and final tailings.

[0096] The flotation test results of each embodiment and comparative example are shown in Table 1: Table 1. Flotation test results of the examples and comparative examples.

[0097] As shown in Table 1, the flotation collector described in this application (a mixture of xanthate and dimercaptoacetate) exhibits excellent collecting effects on copper oxide ore, with both the grade and recovery rate of the copper oxide concentrate being superior to those of traditional xanthate collectors. The mass ratio of xanthate to dimercaptoacetate has a significant impact on the flotation effect; a ratio of 1:1 to 1:4 yields good results, with the optimal ratio being 1:2 to 1:3. Effective flotation is achieved within a pH range of 8 to 12. Good flotation indicators are obtained within a collector dosage range of 100 to 300 g / t, with lower dosages resulting in higher concentrate grades and higher dosages in higher recoveries; the dosage can be flexibly adjusted according to actual process requirements. Furthermore, xanthates with different structures and dimercaptoacetates with different R groups all achieve good flotation results, indicating that the collector described in this application has good structural versatility. Compared with Comparative Examples 1-6, this application uses a combination of black reagent and dimercaptoacetate. Under the same dosage conditions, the grade and recovery rate of copper oxide concentrate produced by the combined collector are significantly better than those achieved by using black reagent or dimercaptoacetate alone, demonstrating the synergistic effect of the two. Compared with Comparative Example 7—the traditional sulfidation flotation process, the collector described in this application can achieve higher copper oxide concentrate grade and recovery rate with lower sulfidation agent dosage, which is beneficial for reducing sulfidation agent consumption and reagent costs, and has good prospects for industrial application.

[0098] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. 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 or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0099] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A flotation collector for copper oxide ore, characterized in that, The raw materials for the flotation collector include dimercaptoacetate and black powder; The mass ratio of the dimercaptoacetic acid ester to the black powder is 0.5-6.0:

1.

2. The flotation collector for oxidized copper ore according to claim 1, characterized in that, The structural formula of the dimercaptoacetic acid ester is: ； R includes one of ethyl, vinyl, n-propyl, isopropyl, n-butyl, and n-pentyl.

3. The flotation collector for oxidized copper ore according to claim 1 or 2, characterized in that, The black medicine includes dihydrodithiophosphate; The hydrocarbon group in the dialkyl dithiophosphate includes at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl, and tolyl.

4. A method for preparing a flotation collector for copper oxide ore according to any one of claims 1-3, characterized in that, include: Under normal temperature conditions, the flotation collector is obtained by first dissolving dimercaptoacetic acid ester in a strong alkaline solution and then dissolving the black powder.

5. The method for preparing the flotation collector for copper oxide ore according to claim 4, characterized in that, The inorganic strong base solution contains 4-12% inorganic strong base by mass.

6. A method of using the flotation collector for oxidized copper ore according to any one of claims 1-3, characterized in that, include: The raw copper oxide ore is ground and then mixed with water to obtain a raw ore slurry; The raw ore slurry is added to a sulfide ore collector for sulfide ore flotation and roughing to obtain copper sulfide concentrate and sulfide ore flotation tailings; After adjusting the pH of the slurry of the sulfide mineral flotation tailings to alkaline, a sulfiding agent is added to sulfide the copper oxide minerals. Then, the flotation collector is added to perform oxide mineral flotation to obtain copper oxide concentrate and total tailings.

7. The method of using the flotation collector for copper oxide ore according to claim 6, characterized in that, The vulcanizing agent includes at least one of sodium sulfide, calcium sulfide, and sodium hydrosulfide.

8. The method of using the flotation collector for copper oxide ore according to claim 6, characterized in that, The pH value of the sulfide ore flotation tailings is adjusted to 8-12.

9. The method of using the flotation collector for copper oxide ore according to claim 6, characterized in that, The amount of the sulfiding agent used is 500-2000 grams per ton of the copper oxide ore.

10. The method of using the flotation collector for oxidized copper ore according to any one of claims 6-9, characterized in that, The flotation collector is used at a rate of 100-300 grams per ton of the copper oxide ore.

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