Three-component collecting agent and application thereof in sulfur-free activated flotation of siliceous refractory copper oxide ore

Abstract

The invention discloses a three-component collecting agent and application of the three-component collecting agent in sulfur-free activated flotation of siliceous refractory copper oxide ore, and belongs to the technical field of mineral flotation agents. The three-component collecting agent is prepared from the following components in parts by weight: 20 to 30 parts of a hydroximic acid chelating collecting agent, 30 to 40 parts of sulfydryl xanthate and 30 to 40 parts of potassium dodecyl phosphate. According to the three-component collecting agent provided by the invention, the flotation effect of the siliceous copper oxide ore is remarkably improved under the condition that a vulcanizing agent is not used through the action of the activating agent on the basis of the synergistic adsorption principle of a surfactant. The activating agent can effectively corrode the surface of the mineral and expose active sites, so that the energy barrier of chemical reaction between the collecting agent and the surface of the mineral is reduced. According to the three-component collecting agent, through the synergistic adsorption effect, the collecting performance of each single agent is enhanced, and the surface activity of the collecting agent is further enhanced. The synergistic effect mechanism not only improves the efficiency of the collecting agent, but also optimizes the selectivity of the flotation process, so that the flotation efficiency of the siliceous refractory copper oxide ore is remarkably improved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation reagents, and particularly relates to a three-component collector and its application in sulfur-free activation flotation of siliceous refractory copper oxide ores. Background Art

[0002] Due to its unique layered crystal structure (alternating [SiO4] tetrahedra and [CuO6] octahedra), chrysocolla forms a high density of surface hydroxyl groups, making it highly hydrophilic. This makes it difficult to effectively hydrophobize traditional flotation processes and collectors. Its difficulty in separation stems primarily from four major challenges: ① The layered silicate-copper hydroxide composite structure creates complex surface chemistry, making it difficult for reagents to adsorb; ② It closely intergrows with gangue minerals, forming a complex interbedded structure that easily forms intergrowths during dissociation; ③ The uneven spatial distribution of ore components leads to significant differences in physical properties; and ④ Existing flotation systems are insufficiently adaptable to specific surface active sites. These factors collectively restrict separation efficiency and concentrate quality improvements.

[0003] Currently, the separation processes for chrysocolla include flotation, gravity separation, magnetic separation, and bioleaching. Flotation relies on differences in mineral surface properties, allowing the minerals to selectively attach to bubbles under the action of flotation agents for separation. However, the flotation of chrysocolla faces many challenges, such as strong surface hydrophilicity, low sulfidation efficiency, uneven structure, and high collector costs. Gravity separation is based on differences in mineral density and is suitable for coarse-grained ores, but is less effective for fine-grained minerals. Magnetic separation utilizes differences in the magnetic properties of minerals for separation, but chrysocolla has weak magnetism and requires magnetization, which increases the complexity of the process. Bioleaching uses microorganisms to leach copper. Although it is environmentally friendly and low-cost, it has a long cycle, low efficiency, and requires stringent microbial culture and environmental conditions.

[0004] At present, the main flotation processes used in industrial practice include sulfide-xanthate method, chelating collector method and combined reagent method:

[0005] The sulfidation-xanthate process uses Na₂S·9H₂O to form a CuS sulfide film on the mineral surface. However, the sulfidation efficiency of chrysocolla is only 40-50%, far lower than that of malachite. Using this process at a siliceous copper mine in the Democratic Republic of the Congo, the concentrate yielded a copper grade of only 12.3% and a recovery rate of less than 55%. A significant amount of fine-grained minerals was lost in the tailings due to incomplete sulfidation.

[0006] The chelate collector method uses hydroxamic acid to form a five-membered ring chelate with copper ions, and the recovery rate of -0.074mm particle size can reach 65%. 2+ Mg 2+Plasma competes with collectors for coordination, leading to a sharp drop in selectivity when the gangue contains calcite. Industrial trials at a Peruvian mine showed that concentrate grade dropped from the designed 18% to 14.5%, while reagent costs increased by 30%. While bioleaching, a recently developed method, is environmentally friendly, it has a long leaching cycle of 60-90 days and yields less than 70% copper. Therefore, developing a cost-effective and efficient new flotation process for chrysocolla has become a pressing technical challenge in the global mineral resources sector. Summary of the Invention

[0007] To address the flotation difficulties of refractory siliceous copper oxide ores, the present invention provides a three-component collector and its application in the sulfur-free activation flotation of refractory siliceous copper oxide ores. By combining a combined inhibitor to synergistically suppress silicate gangue, and an activator to activate the copper oxide mineral surface, the three-component collector achieves hydrophobic enhanced adsorption, overcoming the technical bottleneck of poor floatability of chrysocolla, significantly improving the flotation efficiency of low-grade siliceous copper oxide ores, while also reducing reagent consumption and, consequently, lowering the beneficiation cost of refractory siliceous copper oxide ores.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] One of the technical solutions of the present invention is to provide a three-component collector, which comprises, by weight, 20 to 30 parts of a hydroxamic acid chelating collector, 30 to 40 parts of a mercapto xanthate, and 30 to 40 parts of a potassium dodecyl phosphate.

[0010] Optionally, the hydroxamic acid chelating collector includes octyl hydroxamic acid, salicylic hydroxamic acid, and the like.

[0011] Optionally, the mercapto xanthate includes sodium sec-octyl xanthate (sec-octyl xanthate), sodium amyl xanthate (amyl xanthate), and the like.

[0012] The second technical solution of the present invention is to provide an application of the above-mentioned three-component collector in the sulfur-free activation flotation of siliceous refractory copper oxide ore.

[0013] The third technical solution of the present invention is to provide a flotation method for siliceous refractory copper oxide ore, comprising the following steps:

[0014] After the siliceous refractory copper oxide ore is prepared into ore pulp, copper sulfide concentrate is first floated, and the residual slag is used to float the copper oxide concentrate; the collector used in the process of flotation of the copper oxide concentrate is the above three-component collector.

[0015] Preferably, the method used for flotation of copper oxide concentrate is one coarse flotation, one fine flotation and two sweeping flotation.

[0016] More preferably, the amount of the three-component collector in the roughing step is 600-700 g / t; the amount of the three-component collector in the cleaning step is 100-150 g / t; the amount of the three-component collector in the scavenging step I is 100-300 g / t; and the amount of the three-component collector in the scavenging step II is 50-80 g / t.

[0017] More preferably, the inhibitor used in the roughing and cleaning steps is a composition of phosphonocarboxylic acid copolymer (POCA) and sodium hexametaphosphate (SHMP) in a mass ratio of 2-3:7-8.

[0018] More preferably, the amount of the inhibitor used in the roughing step is 150-200 g / t; and the amount of the inhibitor used in the fine cleaning step is 30-50 g / t.

[0019] More preferably, the activator used in the roughing, scavenging I and scavenging II steps is an ammonium salt activator.

[0020] Further preferably, the amount of the ammonium salt activator in the roughing step is 5000 g / t; the amount of the ammonium salt activator in the scavenging step I is 1000 g / t; and the amount of the ammonium salt activator in the scavenging step II is 500 g / t.

[0021] The beneficial technical effects of the present invention are as follows:

[0022] The three-component collector provided by the present invention is based on the principle of synergistic adsorption of surfactants. Through the action of an activator, it significantly improves the flotation effect of siliceous copper oxide ore without using a sulfiding agent. The activator can effectively dissolve the mineral surface, exposing active sites, thereby reducing the energy barrier for chemical reactions between the collector and the mineral surface. The three-component collector strengthens the collection performance of each single agent through synergistic adsorption, further enhancing the surface activity of the collector. This synergistic mechanism not only improves the efficiency of the collector, but also optimizes the selectivity of the flotation process, thereby significantly improving the flotation efficiency of siliceous refractory copper oxide ore.

[0023] The three-component collector provided by the present invention can achieve efficient flotation recovery of siliceous refractory copper oxide ore, and has the advantages of low reagent consumption and high recovery rate of siliceous refractory copper oxide ore, which is of great significance for the efficient recovery and utilization of strategic mineral resources such as siliceous refractory copper oxide ore.

[0024] The three-component collector provided by the present invention is easy to obtain and is conducive to large-scale promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1is the recovery rate of copper oxide when a single collector is added in Example 1, wherein A is the recovery rate of copper oxide corresponding to different amounts of OHA added when ammonium sulfate is not added and when ammonium sulfate is added, B is the recovery rate of copper oxide corresponding to different amounts of OX added, and C is the recovery rate of copper oxide corresponding to different amounts of PLP added.

[0026] Figure 2 The copper oxide recovery rate when the combined collector is added in Example 1, where A is the amount of OX added of 5×10 - 4 mol / L, the amount of PLP added was 5×10 -4 mol / L, the recovery rate of copper oxide corresponding to different OHA addition amounts; B is the recovery rate of copper oxide corresponding to ... -4 mol / L, the amount of OHA added was 3×10 -4 mol / L, the recovery rate of copper oxide corresponding to different OX addition amounts; C is the recovery rate of copper oxide when the OX addition amount is 5×10 -4 mol / L, the amount of OHA added was 3×10 -4 mol / L, recovery rate of copper oxide corresponding to different PLP addition amounts.

[0027] Figure 3 The flotation flow chart of Example 3 and Example 4 for siliceous refractory copper oxide ore. DETAILED DESCRIPTION

[0028] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0029] It should be pointed out that the matters not described in detail in the present invention are conventional operating means in this field and are not the focus of the present invention.

[0030] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or stated range, and any other stated value or intervening value in the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention.

[0032] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0033] Unless otherwise specified, the "%" in the examples of the present invention refers to mass percentage.

[0034] Example 1

[0035] Effects of using different collectors in flotation of pure chrysocolla:

[0036] The chemical composition of the pure chrysocolla ore to be processed is as follows: copper content is 35.12%, silicon dioxide content is 31.64%, iron content is 5.23%, aluminum oxide (Al2O3) content is 0.432%, and calcium oxide (CaO) content is 0.261%. The ore contains relatively low levels of other impurities, and its overall purity is high.

[0037] Flotation of copper oxide:

[0038] The purity of the pure mineral of chrysocolla is more than 98%, and the particle size is 0.045-0.074 mm. The flotation experiment was carried out in an XFG hanging tank flotation machine at a flotation temperature of about 20°C. 2.00 g of ore sample was weighed each time, 35 mL of deionized water was added, and after stirring for 1 minute to obtain a uniform slurry, ammonium sulfate was added (the amount of ammonium sulfate added was 5×10 -3 mol / L) for catalytic activation for 3 minutes, and then the above-mentioned single collector or combined collector is added and flotation is carried out after 3 minutes to obtain foam products and tailings.

[0039] The copper oxide recovery rate when adding a single collector is shown in Figure 1 , where A is the recovery rate of copper oxide corresponding to different amounts of octyl hydroxamic acid (OHA) added when ammonium sulfate is not added and when ammonium sulfate is added, B is the recovery rate of copper oxide corresponding to different amounts of secondary octyl xanthate (OX), and C is the recovery rate of copper oxide corresponding to different amounts of potassium dodecyl phosphate (PLP).

[0040] The copper oxide recovery rate when adding combined collector is shown in Figure 2 , where A is the amount of OX added, which is 5×10 -4 mol / L, the amount of PLP added was 5×10 -4 mol / L, the recovery rate of copper oxide corresponding to different OHA addition amounts; B is the recovery rate of copper oxide corresponding to ... -4 mol / L, the amount of OHA added was 3×10 -4 mol / L, the recovery rate of copper oxide corresponding to different OX addition amounts; C is the recovery rate of copper oxide when the OX addition amount is 5×10 - 4 mol / L, the amount of OHA added was 3×10 -4mol / L, recovery rate of copper oxide corresponding to different PLP addition amounts.

[0041] Figure 1 and Figure 2 The results show that the combined collector has a stronger collection ability for pure chrysocolla, significantly improves the flotation recovery rate of copper oxide in pure chrysocolla, and reduces the dosage of reagents.

[0042] Example 2

[0043] Application of a three-component collector in the flotation of siliceous refractory copper oxide ores:

[0044] (1) The ore to be processed is artificially mixed with four pure mineral bodies of chrysocolla, dolomite, calcite and quartz to form an artificial mixed ore with a Cu grade of 0.98%. A 25wt.% ore slurry solution is prepared, and a composition of POCA and SHMP with a mass ratio of 2:8 is added as an inhibitor in an amount of 100g / t. The mixture is stirred for 3 minutes to ensure sufficient mixing;

[0045] (2) Add 5000 g / t of ammonium sulfate for activation treatment and stir the reaction for 5 minutes;

[0046] (3) Add 600 g / t of a three-component collector, wherein octyl hydroxamic acid, secondary octyl xanthate, and potassium dodecyl phosphate are mixed in a mass ratio of 1:2:2 and stirred for 3 min to fully react;

[0047] (4) Finally, an appropriate amount of 20 g / t of pine oil as a foaming agent was added and a roughing operation was performed to obtain copper oxide concentrate and tailings; the grade of the copper oxide concentrate was 23%, and the copper recovery rate was 85%.

[0048] Example 3

[0049] Flotation separation of refractory siliceous copper oxide ore in Zambia:

[0050] The ore to be processed is a large, high-oxidation copper oxide ore from the Konkola mine in Zambia, with a copper content of 2.36%. The copper oxide minerals primarily consist of malachite and chrysocolla, while the copper sulfides are chalcocite, bornite, and chalcopyrite. Copper phase analysis indicates that the copper in the ore is primarily present as copper oxide, with a total distribution of 70%. The gangue minerals primarily consist of quartz, calcite, and dolomite, making it a typical siliceous, refractory copper oxide ore.

[0051] The flotation process is to first float copper sulfide and then float copper oxide:

[0052] The ore powder with a grinding fineness of -0.074mm and accounting for 77% was made into a slurry (pH adjusted to 7.0, mass fraction 25%). In the copper sulfide roughing stage, 500g / t of sodium carbonate was added as a conditioning agent for 3 minutes, 50g / t of sodium butyl xanthate was added as a collector for 5 minutes, and 25g / t of pine oil was added as a foaming agent for 2 minutes. In the copper sulfide scavenging stage, 25g / t of sodium butyl xanthate was added as a collector for 5 minutes.

[0053] Through a process of coarse, fine and scavenging, copper sulfide concentrate was obtained with a grade of 22% and a recovery rate of 26%;

[0054] The slag after flotation of copper sulfide is used for flotation of copper oxide:

[0055] In the copper oxide roughing stage:

[0056] (1) adding a composition of POCA and SHMP in a mass ratio of 2:8 as an inhibitor at a dosage of 150 g / t for 5 min;

[0057] (2) Add ammonium sulfate as an activator at a dosage of 5 kg / t and an action time of 5 min;

[0058] (3) Add 600 g / t of a three-component collector consisting of 25% octyl hydroxamic acid, 35% sec-octyl xanthate, and 40% potassium dodecyl phosphate, and allow the reaction time to 5 min;

[0059] (4) Add pine oil as a foaming agent, the dosage is 25g / t, and the action time is 2min;

[0060] In the copper oxide concentration stage:

[0061] (1) adding a composition of POCA and SHMP in a mass ratio of 2:8 as an inhibitor at a dosage of 30 g / t for 5 min;

[0062] (2) adding 100 g / t of a three-component collector consisting of 25% octyl hydroxamic acid, 35% sec-octyl xanthate, and 40% potassium dodecyl phosphate, and reacting for 5 min;

[0063] In the copper oxide scavenging stage I:

[0064] (1) Add ammonium sulfate as an activator at a dosage of 1 kg / t and an action time of 5 min;

[0065] (2) adding 300 g / t of a three-component collector consisting of 25% octyl hydroxamic acid, 35% sec-octyl xanthate, and 40% potassium dodecyl phosphate, and reacting for 5 min;

[0066] In the copper oxide scavenging II stage:

[0067] (1) Add ammonium sulfate as an activator, the dosage is 500g / t, and the action time is 5min;

[0068] (2) adding 80 g / t of a three-component collector consisting of 25% octyl hydroxamic acid, 35% sec-octyl xanthate, and 40% potassium dodecyl phosphate, and reacting for 5 min;

[0069] Through a two-stage sweep process, copper oxide concentrate and tailings are obtained; the grade of the copper oxide concentrate is 16% and the recovery rate is 50%.

[0070] Example 4

[0071] Flotation separation of a siliceous refractory copper oxide ore in Qinghai:

[0072] The ore to be processed is a siliceous, refractory copper oxide ore in Qinghai Province, with a copper content of 1.267%. The copper oxide minerals are primarily malachite and chrysocolla, while the copper sulfide mineral is primarily chalcopyrite. Copper phase analysis results indicate that the copper in the ore exists primarily as copper oxide, with a total distribution of 60%. The gangue minerals primarily include calcium-iron garnet, almandine garnet, potassium feldspar, albite, copper-bearing aluminum silicate minerals, calcite, and biotite.

[0073] The flotation process is to first float copper sulfide and then float copper oxide:

[0074] The ore powder with a grinding fineness of -0.074mm and accounting for 77% was made into a slurry (pH adjusted to 7.0, mass fraction 25%). In the copper sulfide roughing stage, 500g / t of sodium carbonate was added as a conditioning agent for 3 minutes, 50g / t of sodium butyl xanthate was added as a collector for 5 minutes, and 25g / t of pine oil was added as a foaming agent for 2 minutes. In the copper sulfide scavenging stage, 25g / t of sodium butyl xanthate was added as a collector for 5 minutes.

[0075] Through a process of coarse, fine and scavenging, copper sulfide concentrate was obtained with a grade of 19% and a recovery rate of 35%;

[0076] The slag after flotation of copper sulfide is used for flotation of copper oxide:

[0077] In the copper oxide roughing stage:

[0078] (1) adding a composition of POCA and SHMP in a mass ratio of 3:7 as an inhibitor at a dosage of 200 g / t for 5 min;

[0079] (2) Add ammonium sulfate as an activator at a dosage of 5 kg / t and an action time of 5 min;

[0080] (3) adding 700 g / t of a three-component collector consisting of 30% salicylic acid, 40% amyl xanthate, and 30% potassium lauryl phosphate, and reacting for 5 min;

[0081] (4) Add pine oil as a foaming agent, the dosage is 25g / t, and the action time is 2min;

[0082] In the copper oxide concentration stage:

[0083] (1) adding a composition of POCA and SHMP in a mass ratio of 3:7 as an inhibitor at a dosage of 50 g / t for 5 min;

[0084] (2) adding 150 g / t of a three-component collector consisting of 30% salicylic acid, 40% amyl xanthate, and 30% potassium dodecyl phosphate, and reacting for 5 min;

[0085] In the copper oxide scavenging stage I:

[0086] (1) Add ammonium sulfate as an activator, the dosage is 1kg / t, the action time is 5min,

[0087] (2) adding 100 g / t of a three-component collector consisting of 30% salicylic acid, 40% amyl xanthate, and 30% potassium dodecyl phosphate, and the reaction time was 5 min;

[0088] In the copper oxide scavenging II stage:

[0089] (1) Add ammonium sulfate as an activator, the dosage is 500g / t, the action time is 5min,

[0090] (2) adding 50 g / t of a three-component collector consisting of 30% salicylic acid, 40% amyl xanthate, and 30% potassium dodecyl phosphate, and the reaction time was 5 min;

[0091] Through two sweeps, one coarse and one fine, copper oxide concentrate was obtained with a grade of 14% and a recovery rate of 40%.

[0092] The flotation flow chart of siliceous refractory copper oxide ore according to Examples 3 and 4 of the present invention is shown in FIG. Figure 3 .

[0093] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A three-component collector, characterized in that: Calculated by weight, the components include: 20-30 parts of hydroxamic acid chelating collector, 30-40 parts of mercapto xanthate and 30-40 parts of lauryl phosphate potassium salt.

2. Use of the three-component collector according to claim 1 in sulfur-free activation flotation of refractory siliceous copper oxide ore.

3. A flotation method for siliceous refractory copper oxide ore, characterized in that: The following steps are involved: After preparing the siliceous refractory copper oxide ore into ore pulp, the copper sulfide concentrate is first floated, and the residual slag is used to float the copper oxide concentrate; the collector used in the process of flotation of the copper oxide concentrate is the three-component collector described in claim 1.

4. The flotation method for siliceous refractory copper oxide ore according to claim 3, characterized in that: The method used for flotation of copper oxide concentrate is one coarse, one fine and two sweeping.

5. The flotation method for siliceous refractory copper oxide ore according to claim 4, characterized in that: The dosage of the three-component collector in the roughing step is 600-700 g / t; the dosage of the three-component collector in the fine selection step is 100-150 g / t; the dosage of the three-component collector in the scavenging step I is 100-300 g / t; and the dosage of the three-component collector in the scavenging step II is 50-80 g / t.

6. The flotation method for siliceous refractory copper oxide ore according to claim 4, characterized in that: The inhibitor used in the roughing and cleaning steps is a composition of phosphonocarboxylic acid copolymer and sodium hexametaphosphate in a mass ratio of 2-3:7-8.

7. The flotation method for siliceous refractory copper oxide ore according to claim 6, characterized in that: The amount of the inhibitor used in the roughing step is 150-200 g / t; the amount of the inhibitor used in the fine cleaning step is 30-50 g / t.

8. The flotation method for siliceous refractory copper oxide ore according to claim 4, characterized in that: The activator used in the roughing, scavenging I and scavenging II steps is an ammonium salt activator.

9. The flotation method for siliceous refractory copper oxide ore according to claim 8, characterized in that: The amount of the ammonium salt activator used in the roughing step is 5000 g / t; the amount of the ammonium salt activator used in the scavenging step I is 1000 g / t; and the amount of the ammonium salt activator used in the scavenging step II is 500 g / t.

Images