Flotation reagent composition for recovering micro-fine particle copper sulfide from copper oxide acid leaching residues and beneficiation method of flotation reagent composition
By using a combination of reagents such as ethyl thioate, octadecyltriethoxysilane, and kerosene, the problem of recovering fine-grained copper sulfide minerals from copper oxide acid leaching residue was solved, achieving efficient flotation and cost control.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA NERIN ENGINEERING CO LTD
- Filing Date
- 2026-02-27
- Publication Date
- 2026-04-17
AI Technical Summary
In existing technologies, it is difficult to effectively recover fine-grained copper sulfide minerals from copper oxide acid leaching residue. Conventional reagents have poor stability in acidic environments, resulting in low recovery rates and high costs.
Ethyl thioethyl acetate was used as the collector, octadecyltriethoxysilane and kerosene as hydrophobic agglomerating agents, and terpineol or methyl isobutyl methanol as the frother. The recovery rate of fine copper sulfide particles was improved by flotation.
It significantly improves the recovery rate and concentrate grade of fine-grained copper sulfide, solves the problem of selective recovery of copper sulfide minerals under acidic conditions, and reduces beneficiation costs.
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Figure CN121869604A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of non-ferrous metal beneficiation technology, and in particular to a flotation reagent composition for recovering fine copper sulfide particles from copper oxide acid leaching residue and a beneficiation method thereof. Background Technology
[0002] Copper oxide acid leaching residue is a solid residue produced after processing copper oxide ore in a hydrometallurgical process. It often contains copper sulfide minerals that cannot be dissolved by acid. Because the acid leaching residue slurry is acidic (pH=4~6.5), conventional xanthates and thiocyanates have poor stability in acidic environments, and some copper sulfide minerals are finely embedded, making it difficult to effectively recover the copper sulfide minerals in the acid leaching residue.
[0003] Currently, the common process for flotation of copper sulfide minerals from acid leaching residue is the "pH adjustment-flotation" process. This involves first neutralizing the acidic environment with a large amount of pH adjuster to neutral or weakly alkaline conditions, followed by flotation using conventional xanthates or thiocyanates as collectors. This process is complex, has poor separation efficiency, and relatively high beneficiation costs.
[0004] Therefore, in order to improve the overall recovery rate of fine copper sulfide in some acid leaching residues, it is urgent to develop collectors with strong collecting ability for copper sulfide under acidic conditions and flotation processes for fine copper sulfide minerals in acidic environments. This is of great significance for the recovery of fine copper sulfide minerals from acid leaching residues. Summary of the Invention
[0005] Therefore, the purpose of this application is to overcome the shortcomings of the prior art and provide a flotation reagent composition and beneficiation method for recovering fine copper sulfide from copper oxide acid leaching residue. This addresses the problem of low recovery rate of fine copper sulfide in traditional copper oxide acid leaching residue recovery processes.
[0006] To achieve the above objectives, this application adopts the following technical solution:
[0007] First, this application provides a flotation reagent composition for recovering fine copper sulfide particles from copper oxide acid leaching residue, comprising a collector, a hydrophobic agglomerant, and a frother, wherein the collector is ethyl thiocarbamate;
[0008] Hydrophobic agglomerating agents include octadecyltriethoxysilane and kerosene;
[0009] The foaming agent is selected from terpineol, methyl isobutyl alcohol or 2-octanol.
[0010] Preferably, the hydrophobic agglomerant comprises 8-15 parts by weight of octadecyltriethoxysilane and 85-92 parts by weight of kerosene.
[0011] As a preferred option, the kerosene content is 85% to 92% based on the total mass of the hydrophobic agglomerant being 100%.
[0012] Based on a general inventive concept, this application also provides a beneficiation method for recovering fine-particle copper sulfide from copper oxide acid leaching residue, comprising the following steps:
[0013] S1. Pulping: Mix copper oxide acid leaching residue with water to obtain slurry;
[0014] S2. Roughing: Collector, hydrophobic agglomerant and frother are added to the slurry in sequence for roughing to obtain rough concentrate and rough tailings; wherein, the collector is ethyl thiocyanate; the hydrophobic agglomerant includes octadecyltriethoxysilane and kerosene; the frother is selected from terpineol, methyl isobutyl methanol or 2-octanol;
[0015] S3. Fine treatment: Fine treatment of rough concentrate to obtain copper sulfide concentrate;
[0016] S4. Scavenging: Collector, hydrophobic agglomerant and frother are added sequentially to the roughing tailings for scavenging to obtain tailings.
[0017] As a preferred method, the number of coarse selection operations is 1 to 3 times, the number of fine selection operations is 2 to 5 times, and the number of scanning operations is 2 to 4 times.
[0018] As a preferred option, in each roughing operation, the amount of collector added is 120~300g / t, the amount of hydrophobic agglomerant added is 20~40g / t, and the amount of foaming agent added is 20~40g / t.
[0019] As a preferred option, the amount of collector added in each roughing operation is 180~220g / t.
[0020] As a preferred option, the amount of hydrophobic agglomerates added in each roughing operation is 25~35g / t.
[0021] As a preferred option, the amount of foaming agent added in each roughing operation is 25~30g / t.
[0022] Preferably, in each scavenging operation, the amount of the collector added is 40~120g / t, the amount of the hydrophobic agglomerant added is 5~10g / t, and the amount of the foaming agent added is 10~20g / t.
[0023] Preferably, in each scavenging operation, the amount of the collector added is 40~120g / t, the amount of the hydrophobic agglomerant added is 8~10g / t, and the amount of the foaming agent added is 10~15g / t.
[0024] As a preferred method, the scavenging operation is performed twice. In the first scavenging operation, the amount of collector added is 75~85g / t; in the second scavenging operation, the amount of collector added is 40~50g / t.
[0025] Preferably, in each roughing operation, the collector is first added and stirred for 1-3 minutes, followed by the addition of the hydrophobic agglomerant and stirring for 10-20 minutes. Then, the frother is added and stirred for 10-20 seconds, followed by aeration and foam scraping for 0.5-2 minutes. Adding the collector first and stirring makes the fine copper sulfide minerals hydrophobic; then adding the hydrophobic agglomerant and stirring for 10-20 minutes allows the hydrophobic agglomerant to spread on the surface of the copper sulfide minerals hydrophobized by the collector, forming hydrophobic aggregates and increasing the floatability of the copper sulfide minerals. Aeration generates a suitable amount of foam in the slurry, which carries the hydrophobic flocs to the surface, forming a foam layer, which is beneficial for scraping and collection.
[0026] Preferably, when stirring after adding the collector, the stirring speed is 1800~2000 r / min.
[0027] Preferably, when stirring after adding the hydrophobic agglomerant, the stirring speed is 1800~2000 r / min.
[0028] Preferably, the stirring rate after adding the foaming agent is 1800~2000 r / min.
[0029] Preferably, the foaming time in each selection operation is 1-2 minutes. Preferably, in each scavenging operation, the collector is added and stirred for 1-3 minutes, then the hydrophobic agglomerant is added and stirred for 10-20 minutes, then the foaming agent is added and stirred for 10-20 seconds, followed by aeration and foaming for 0.5-2 minutes.
[0030] As a preferred option, during the roughing and scavenging stages of the flotation process, when the collector is added and the mixture is stirred, the stirring rate is 1800~2000 r / min.
[0031] Preferably, during the roughing and scavenging stages of the flotation process, when adding the hydrophobic agglomerant and stirring, the stirring rate is 1800~2000 r / min.
[0032] Preferably, during the roughing and scavenging stages of the flotation process, the stirring rate after adding the frother is 1800~2000 r / min.
[0033] Preferably, the copper oxide acid leaching residue has a particle size of less than 0.25 mm.
[0034] Preferably, the copper oxide leaching residue contains 85% to 95% copper oxide leaching residue with a particle size of less than 0.074 mm and 55% to 80% copper oxide leaching residue with a particle size of less than 0.037 mm.
[0035] Preferably, the Cu content in the copper oxide acid leaching residue is 0.30%~5.00%, and the Cu oxidation rate is 90%~97%. The copper sulfide minerals in the copper oxide acid leaching residue are mainly chalcocite, chalcocite, and covellite.
[0036] Preferably, the mass content of copper oxide acid leaching residue in the slurry obtained in step (1) is 15%~28%.
[0037] The mechanism of action of the flotation reagent composition for recovering fine copper sulfide particles from copper oxide acid leaching residue in this application is as follows:
[0038] This application discloses a flotation reagent composition for recovering fine copper sulfide particles from copper oxide acid leaching residue, comprising a collector, a hydrophobic agglomerant, and a frother. The collector, ethyl thioester, contains a thioether group (-S-) and a carbonyl group (C=O) in its molecular structure. In an acidic environment with pH 4-6.5, its thioether group can stably coordinate with copper ions on the surface of copper sulfide minerals in the acid leaching residue; the carbonyl oxygen atom also provides additional coordination sites, forming a four-membered ring chelate with copper ions, further stabilizing the adsorption on the mineral surface. Therefore, it exhibits strong affinity and selectivity for the copper sulfide mineral surface under acidic conditions. Simultaneously, the ethyl tail chain in the collector imparts strong hydrophobicity to the copper sulfide mineral surface. Compared to ethyl thioester, this collector's tail chain lacks a hydration layer. When two mineral surfaces adsorbed with ethyl thioester approach each other, there is no steric hindrance, which facilitates particle agglomeration after collision. Based on this, the octadecyltriethoxysilane in the hydrophobic agglomerant hydrolyzes during slurry formation, and its silanol groups undergo irreversible dehydration condensation with the hydroxyl groups on the mineral surface, forming strong Si-OM covalent bonds, thereby constructing a stable hydrophobic layer on the mineral surface. Subsequently, through stirring, kerosene molecules are fully dispersed in the slurry and, due to strong van der Waals forces, tightly bind to the alkyl chains of the silane, rapidly and uniformly spreading on the surface of the hydrophobic layer of copper sulfide minerals. Thus, the copper sulfide minerals covered with kerosene aggregate together under intense stirring, forming hydrophobic aggregates, which is beneficial for the separation and recovery of copper sulfide.
[0039] Furthermore, silane molecules on the surfaces of different mineral particles can further condense to form a robust Si-O-Si siloxane network, thereby "linking" multiple copper sulfide minerals together and further forming ultrafine-grained hydrophobic aggregates of copper sulfide minerals. This process significantly increases the floatability of fine-grained copper sulfide minerals in the acid leaching residue, ultimately effectively improving the recovery rate of fine-grained copper sulfide minerals.
[0040] Compared with the prior art, this application has the following beneficial effects:
[0041] (1) Compared with ethyl thiocyanate, the collector ethyl thiocyanate is chemically stable in acidic environment, has weak collecting ability for gangue minerals, and has good selectivity in the flotation of copper sulfide minerals, thus obtaining higher grade and recovery rate of copper sulfide concentrate.
[0042] (2) The mineral processing method provided in this application improves the recovery rate of copper sulfide minerals and solves the problem that the fine-grained copper sulfide minerals in copper oxide leaching residue have low kinetic energy, low probability of collision with bubbles, and low recovery rate. Attached Figure Description
[0043] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments of this application will be briefly introduced below. Obviously, the drawings described below are only some implementation methods of this application. For those skilled in the art, other drawings can be obtained based on the drawings without creative effort.
[0044] Figure 1 This is a process flow diagram of the copper oxide acid leaching residue recovery copper sulfide beneficiation method in Example 1. Detailed Implementation
[0045] The embodiments described in this specification are merely for explaining this application and are not intended to limit this application.
[0046] For simplicity, this paper only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, just as any upper limit can be combined with any other upper limit to form an undefined range. Furthermore, although not explicitly stated, every point or individual value between the endpoints of a range is included within that range. Therefore, each point or individual value can serve as its own lower or upper limit and be combined with any other point or individual value, or with other lower or upper limits, to form an undefined range.
[0047] Those skilled in the art will understand that the order in which the steps are written in the various embodiments or examples does not imply a strict execution order and does not limit the implementation process in any way. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but sequentially is preferred.
[0048] The present application is further illustrated below with reference to embodiments. It should be understood that these embodiments are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on mass, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.
[0049] In this application, the amount of each component added is expressed in g / t, where "t" refers to the mass of the copper oxide acid leaching residue to be floated, in tons.
[0050] The ethyl thioester used in this application has the chemical formula C4H8OS; its structural formula is as follows:
[0051]
[0052] Example 1
[0053] See Figure 1 In this embodiment, copper oxide acid leaching residue is subjected to flotation. The residue has a particle size less than 0.25 mm, with 92% of the residue having a particle size less than 0.037 mm, and 58% having a particle size less than 0.037 mm. The Cu grade is 2.03%, the Cu oxidation rate is 92%, and the copper sulfide minerals are mainly chalcocite, chalcocite, and covellite. The hydrophobic agglomerant used in this embodiment is octadecyltriethoxysilane and kerosene in a mass ratio of 1:9. The specific flotation steps are as follows:
[0054] (1) Pulping: Add copper oxide acid leaching residue to the flotation cell, add water and stir to adjust the slurry, and control the concentration of copper oxide acid leaching residue in the slurry to 20%.
[0055] (2) Roughing: Add 200 g / t of collector ethyl thiocyanate to the slurry and stir for 2 min at 2000 r / min; add 30 g / t of hydrophobic agglomerate and stir for 15 min at 2000 r / min; then add 30 g / t of frother terpineol and stir for 10 s at 2000 r / min to start roughing. The frothing time for roughing is 2 min, and roughing concentrate and roughing tailings are obtained.
[0056] (3) Scavenging: Add 80g / t of collector ethyl thiocyanate to the roughing tailings, stir for 2min at 2000r / min, add 10g / t of hydrophobic agglomerate, stir for 15min at 2000r / min, then add 10g / t of frother terpineol, stir for 10s at 2000r / min, and start the first scavenging. The scavenging and frothing time is 2min, and the first scavenging concentrate and scavenging tailings are obtained. The first scavenging concentrate is returned to the roughing step in step (2), and the scavenging tailings enter the second scavenging.
[0057] The second scavenging process is as follows: Add 40 g / t of ethyl thiocyanate collector to the tailings from the first scavenging and stir at 2000 r / min for 2 min; add 10 g / t of hydrophobic agglomerate and stir at 2000 r / min for 15 min; then add 10 g / t of frother terpineol and stir at 2000 r / min for 10 s to begin the second scavenging process. The frothing time is 2 min, resulting in a second scavenging concentrate and a second scavenging tailings. Collect the second scavenging tailings and return the second scavenging concentrate to the first scavenging step.
[0058] (4) Fine treatment: The rough concentrate obtained in step (2) is finely treated three times without the addition of any reagents. The skimming time for each fine treatment is 2 min, 1.5 min and 1 min respectively, to obtain copper sulfide concentrate. After each fine treatment, the fine ore is entered into the next fine treatment step, and the tailings are returned to the previous step.
[0059] Comparative Example 1
[0060] The flotation target of this comparative example is the same as that of Example 1, and the flotation method is also basically the same as that of Example 1. The main difference is that the collector used in this comparative example is ethyl thiocyanate (Z-200), and the amount used is the same as the mass of the flotation collector in Example 1. In addition, no hydrophobic agglomerating agent is added in this comparative example, and other flotation parameters are the same as those in Example 1.
[0061] Comparative Example 2
[0062] The flotation target in this comparative example is the same as that in Example 1, and the flotation method is also basically the same as that in Example 1. The main difference is that the collector used in this comparative example is ethyl thiocarbamate, and the amount used is the same as the mass of the flotation collector in Example 1. In addition, no hydrophobic agglomerating agent is added in this comparative example, and other flotation parameters are the same as those in Example 1.
[0063] Comparative Example 3
[0064] The flotation object in this comparative example is the same as that in Example 1, and the flotation method is also basically the same as that in Example 1. The main difference is that the collector used in this comparative example is ethyl thiocyanate, and the hydrophobic agglomerant used is the same as that in Example 1. The dosage of each is the same as that of the flotation collector and hydrophobic agglomerant in Example 1. Other flotation parameters are the same as those in Example 1.
[0065] The flotation results of each embodiment and comparative example are shown in Table 1.
[0066] Table 1. Flotation results of each embodiment and comparative example.
[0067]
[0068] Wherein, copper sulfide concentrate yield = mass of copper sulfide flotation concentrate / mass of copper oxide acid leaching residue flotation feed × 100%;
[0069] Tailings yield = Tailings mass / Feed mass × 100%;
[0070] Copper sulfide concentrate recovery rate = (concentrate yield × concentrate grade) / Cu content in copper oxide acid leaching residue;
[0071] Tailings recovery rate = (Concentrate yield × Concentrate grade) / Cu grade in copper oxide acid leaching residue.
[0072] As can be seen from Table 1, compared with Comparative Examples 1 to 3, Example 1, using the technical solution of this application, after flotation of the copper oxide acid leaching residue, yields a copper sulfide concentrate with a relatively high copper grade and a high copper recovery rate.
[0073] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.
Claims
1. A flotation reagent composition for recovering fine copper sulfide particles from copper oxide acid leaching residue, characterized in that, It includes a collector, a hydrophobic agglomerant, and a foaming agent, wherein the collector is ethyl thiocarbamate; The hydrophobic agglomerating agent comprises octadecyltriethoxysilane and kerosene; The foaming agent is selected from terpineol, methyl isobutyl alcohol, or octanol.
2. The pharmaceutical composition according to claim 1, characterized in that, The hydrophobic agglomerant comprises 8-15 parts octadecyltriethoxysilane and 85-92 parts kerosene by weight.
3. A mineral processing method for recovering copper sulfide from copper oxide acid leaching residue, characterized in that, Includes the following steps: S1. Pulping: Mix copper oxide acid leaching residue with water to obtain slurry; S2. Roughing: A collector, a hydrophobic agglomerant, and a frother are added sequentially to the slurry for roughing to obtain a roughing concentrate and roughing tailings; wherein the collector is ethyl thiocyanate; the hydrophobic agglomerant includes octadecyltriethoxysilane and kerosene; and the frother is selected from terpineol, methyl isobutyl methanol, or 2-octanol. S3. Fine treatment: Fine treatment of the rough concentrate to obtain copper sulfide concentrate; S4. Scavenging: Collector, hydrophobic agglomerant and frother are added sequentially to the roughing tailings to scavenging and obtain tailings.
4. The mineral processing method according to claim 3, characterized in that, The number of coarse selection operations is 1 to 3 times, the number of fine selection operations is 2 to 5 times, and the number of sweeping operations is 2 to 4 times.
5. The mineral processing method according to claim 4, characterized in that, The mineral processing method satisfies at least one of the following conditions: (1) In each roughing operation, the amount of the collector added is 120~300g / t, the amount of the hydrophobic agglomerant added is 20~40g / t, and the amount of the foaming agent added is 20~40g / t; (2) In each scavenging operation, the amount of the collector added is 40~120g / t, the amount of the hydrophobic agglomerant added is 5~10g / t, and the amount of the foaming agent added is 10~20g / t.
6. The mineral processing method according to claim 5, characterized in that, The mineral processing method satisfies at least one of the following conditions: (1) In each roughing operation, first add the collector and stir for 1 to 3 minutes, then add the hydrophobic agglomerant and stir for 10 to 20 minutes, then add the foaming agent and stir for 10 to 20 seconds, then aerate and scrape the bubbles for 0.5 to 2 minutes; (2) The time for scraping the foam in each selection operation is 1 to 2 minutes; (3) In each sweeping operation, first add the collector and stir for 1 to 3 minutes, then add the hydrophobic agglomerant and stir for 10 to 20 minutes, then add the foaming agent and stir for 10 to 20 seconds, then aerate and scrape the foam for 0.5 to 2 minutes.
7. The mineral processing method according to claim 3, characterized in that, The copper oxide acid leaching residue has a particle size of less than 0.25 mm.
8. The mineral processing method according to claim 7, characterized in that, The copper oxide acid leaching residue contains 85% to 95% copper oxide acid leaching residue with a particle size of less than 0.074 mm, and 55% to 80% copper oxide acid leaching residue with a particle size of less than 0.037 mm.
9. The mineral processing method according to claim 3, characterized in that, The Cu content in the copper oxide acid leaching residue is 0.30%~5.00%, and the Cu oxidation rate is 90%~97%.
10. The mineral processing method according to claim 3, characterized in that, The mass content of copper oxide acid leaching residue in the slurry obtained in step (1) is 15%~28%.