A comprehensive treatment method for potassium-containing fine-grained mixed copper ore

Abstract

The present invention provides a comprehensive treatment method for potassium-containing fine-grained mixed copper ore, which comprises the following steps: S1, dissociating and slurrying the potassium-containing fine-grained mixed copper ore to obtain ore pulp; S2, performing redox modification treatment on the ore pulp under an acidic environment, and then performing solid-liquid separation to obtain a liquid phase and a solid phase, wherein the liquid phase is a copper leaching solution; slurrying the solid phase again to obtain a floating copper ore pulp; S3, performing a flotation separation treatment on the floating copper ore pulp to obtain a copper sulfide concentrate and a floating copper tailing; S4, performing floating potassium separation on the floating copper tailing to obtain a potassium-containing mineral. The present invention realizes the efficient and comprehensive recovery of mixed copper ore resources, and at the same time reduces the discharge of waste.

Description

Technical Field

[0001] The invention relates to the technical field of comprehensive utilization of copper ore resources, and in particular to a comprehensive treatment method for potassium-containing fine-grained mixed copper ore. Background Art

[0002] There are more than 200 types of copper minerals reported, and 17 types of copper minerals available for industrial mining, including primary copper sulfide minerals such as chalcopyrite; secondary copper sulfide minerals such as chalcocite; and copper oxide minerals such as native copper and malachite. Affected by the geological conditions of copper deposit mineralization and changes in the external environment, the types of copper minerals in the same deposit are usually more, especially the transformation of copper sulfide ores to copper oxide ores caused by oxidative alteration, which causes the copper in the ore to exist in the form of mixed copper ores containing various types of sulfide ores and oxide ores. The complexity of the mineral composition makes it difficult to process and recover. In addition, the existing available copper resources have a prominent trend of being poor and fine. Statistics show that about 1 / 6 of the world's copper has not been effectively recovered due to its fine particle size. Improving resource utilization has become a common problem for copper ore resources. Therefore, the development of a new process for the comprehensive utilization of fine-grained mixed copper ores is of great significance to the efficient and green utilization of copper resources.

[0003] At present, the process of sulphide copper ore being concentrated by mineral processing and then smelting is dominant. When this type of method is used for mineral processing and enrichment, the mineral enrichment efficiency is mostly limited by the mineral composition and mineral occurrence characteristics, and some fine-grained and multi-phase copper minerals are often poorly recovered. Sulfide flotation is one of the most important methods for treating oxidized copper ore. When copper oxide sulfide flotation is used for recovery, its sulfide activation efficiency is poor due to the influence of mineral morphology, particle size and other factors, and the copper recovery rate is generally low. In addition, the oxidized copper ore can also be treated by direct leaching process. This process can greatly avoid the influence of fine particles on enrichment, but its extraction efficiency of sulfide phase minerals in the ore is low, which reduces the efficiency of resource extraction and processing. It can be seen that for the processing of mixed copper ore, it is inevitable to face the above-mentioned problems.

[0004] At present, the combination of copper sulfide flotation and copper oxide sulfide flotation is still the main flotation enrichment technology used for mixed copper ore. In the process of sulfide flotation of copper oxide minerals, the sulfiding agent is inevitably used, mainly sodium sulfide, sodium hydrosulfide, ammonium sulfide, calcium sulfide and sodium polysulfide, etc. The use of this type of agent has safety and environmental protection risks. In the flotation of copper sulfide ore, in order to solve the problem of difficult flotation of fine particles, the patents "A method for improving the flotation index of fine copper sulfide ore CN1071115974A" and "A method for improving the flotation index of fine copper sulfide ore CN107812617A" improve the flotation of fine copper sulfide ore from the perspectives of strengthening flotation collection capacity and adding floating carriers. While strengthening the flotation of fine copper minerals, it also reduces the quality of sulfide concentrate and has poor adaptability to ultra-fine particles (<20μm). Patent "A method for coarse-fine particle classification of copper oxide ore-enhanced fine particle sulfide flotation CN108160313A" uses a classification method to classify the crushed and ground materials into coarse and fine particles, and flots them separately with different activators and sulfidizers to eliminate the influence of primary and secondary ore muds. It can be used to treat copper oxide ore. Its copper recovery rate is about 87%, and the recovery rate is not too high. It should be because it does not effectively sulfide the fine copper minerals. The "flotation method of fine embedded copper ore CN108499741A" uses a classification method to improve the properties of the floating material and recover copper oxide ore, but its copper recovery rate is not high, which is limited by the difficult floating ore properties of copper oxide ore. In the combined beneficiation and smelting process, "A combined beneficiation and smelting method for treating fine-grained copper sulfide ore CN110449270A" first uses flotation to enrich the ore, and then conducts biological agitation leaching on the middling ore to improve the recovery rate of fine-grained copper. This method has a relatively complicated process and a relatively slow biological leaching rate.

[0005] On the other hand, available potassium is often associated with flotation tailings of many types of ores, such as gold, molybdenum, copper, phosphate, etc. Potassium, as an associated metal, is commonly found in copper ores, especially in copper oxide or mixed copper ores. With the improvement of solid waste disposal requirements and tailings utilization and processing technology, recovering valuable metals from sorted tailings has become one of the important directions of resource development. Flotation is still an effective method for effectively separating potassium from tailings; relatively speaking, in an acidic environment of pH 2 to 4, potassium is better separated and enriched from ores, and the recovery rate is relatively high. It is a relatively effective method to separate potassium minerals from acidic slurries. "A method for selecting potassium feldspar in potassium-containing tailings CN102441496A" provides a method for recovering potassium from non-ferrous metal tailings using modified amines as collectors.

[0006] In summary, it is necessary to provide a method for efficiently recovering copper minerals and their associated metals from fine-grained mixed copper ores to adapt to the problems of diversified mineral composition, fine-grained distribution, and difficulty in recovering metals in ores. Summary of the invention

[0007] The main purpose of the present invention is to provide a comprehensive treatment method for potassium-containing fine-grained mixed copper ore to solve the problem in the prior art that copper and associated metallic potassium in fine-grained mixed copper ore are difficult to be efficiently recovered and utilized.

[0008] In order to achieve the above object, according to one aspect of the present invention, a comprehensive treatment method for potassium-containing fine-grained mixed copper ore is provided, the method comprising the following steps:

[0009] S1, dissociating and slurrying the potassium-containing fine-grained mixed copper ore to obtain slurry;

[0010] S2, subjecting the ore pulp to oxidation-reduction modification treatment in an acidic environment, followed by solid-liquid separation to obtain a liquid phase and a solid phase, wherein the liquid phase is a copper leaching solution; and slurrying the solid phase again to obtain a floating copper ore pulp;

[0011] S3, performing flotation separation treatment on the copper flotation slurry to obtain copper sulfide concentrate and copper flotation tailings;

[0012] S4, separating the floating copper tailings from the floating potassium to obtain potassium-containing minerals.

[0013] Further, step S2 comprises: adding an inorganic acid and a redox active agent to the slurry for redox modification, wherein the pH of the acidic environment is 1 to 4, and the redox potential E h It is 0~0.4V(vs.NHE).

[0014] Further, the redox active agent is one or more of formic acid, oxalic acid, tartaric acid, malic acid, citric acid, glycine, ascorbic acid, hydrazine hydrate, hydroxylamine hydrochloride, glycolic acid, D-sorbitol and succinimide.

[0015] Furthermore, the inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.

[0016] Furthermore, the weight ratio of the total weight of the inorganic acid and the redox active agent to the potassium-containing fine-grained mixed copper mineral is (100-10000 g):1 t, preferably (1000-8000) g:1 t; preferably, the weight ratio of the inorganic acid and the redox active agent is 4:1-1:2.

[0017] Furthermore, the time of the redox modification treatment in step S2 is 0.5 to 12 hours, and the treatment temperature is 20 to 90° C.; preferably, the solid-liquid ratio when the solid phase is re-slurried in step S2 is 1:2 to 1:5.

[0018] Furthermore, after the dissociation in step S1, the grinding fineness is that the particles with a particle size less than 0.074 mm account for more than 90%; preferably, the solid-liquid ratio during slurry adjustment is 1: (2-10), and more preferably 1: (2-4).

[0019] Furthermore, the step of flotation separation treatment includes: adding a foaming agent to the floating copper ore slurry for flotation separation treatment, and the treatment time is 3 to 20 minutes; preferably, the foaming agent is a hydrophobic foaming agent having affinity with elemental sulfur or its hydrophobic derivatives; preferably, the foaming agent is one or more of methyl isobutyl carbinol, polyethylene glycol, polypropylene glycol ether, cresol acid and diethyl phthalate; more preferably, the weight ratio of the foaming agent to the potassium-containing fine-particle mixed copper mineral is (10 to 600) g: 1 t, preferably (40 to 200) g: 1 t.

[0020] Furthermore, before adding the foaming agent to the copper flotation slurry, the foaming agent is prepared into a foaming agent aerosol in advance, and then the foaming agent aerosol is pressed into the copper flotation slurry.

[0021] Further, in step S4, floating potassium separation is performed using a flotation collector, an adjuster, and a frother; preferably, the flotation collector includes oleic acid, amines and modified amines, amino esters, sulfonates, more preferably one or more of oleylamine, N-dodecyl-β-aminopropionic acid, and fatty acids; preferably, the adjuster is one or more of sulfuric acid, hydrofluoric acid, and sodium carbonate; preferably, the frother is one or more of methyl isobutyl carbinol, polyethylene glycol, polypropylene glycol ether, cresol acid, and diethyl phthalate; preferably, the pH of the floating copper tailings is adjusted to 1 to 4; preferably, the weight ratio of the floating collector to the potassium fine-grained mixed copper mineral is (200 to 800) g: 1 t; preferably, the weight ratio of the adjuster to the potassium fine-grained mixed copper mineral is (100 to 2000) g: 1 t; preferably, the weight ratio of the frother to the potassium fine-grained mixed copper mineral is (10 to 600) g: 1 t.

[0022] The invention provides a comprehensive treatment method for potassium-containing fine-grained mixed copper ore. The invention performs an oxidation-reduction modification treatment on the dissociated potassium-containing fine-grained mixed copper ore pulp in an acid environment, which can reduce the Cu 2+ / Cu +Selectively dissolve to obtain copper leaching solution; on the other hand, the surface of the mineral can be oxidized, and the residual strongly hydrophobic sulfur and its derivatives become the dominant phase, and the obtained solid phase is the surface-modified copper sulfide mineral; at the same time, the ore pulp is subjected to oxidation-reduction treatment, which can consume part of the dissolved oxygen in the ore pulp, regulate or alleviate the further oxidation of sulfur and its derivatives produced by the dissolved oxygen in the ore pulp on the surface of the mineral, thereby enhancing the hydrophobic activity of the mineral surface, and combined with the subsequent flotation separation process, a high-recovery, high-quality copper sulfide concentrate can be obtained. In addition, the above-mentioned modification step also provides a suitable acidic environment for the subsequent separation and enrichment of potassium, further promotes the flotation separation of potassium minerals and other ores, realizes the efficient and comprehensive recovery of resources, and at the same time reduces the emission of waste. DETAILED DESCRIPTION

[0023] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0024] In the present invention, "potassium-containing fine-grained mixed copper ore" is defined as copper minerals with a particle size of less than 20 μm, and copper minerals with a particle size of 10 μm account for more than 50%. In the field of mineral processing, there is no clear limit for fine particles. Based on the properties of the minerals in the ore and the influence of the flotation process, the lower limit of the flotation of non-ferrous metal ores is usually 5 to 10 μm with existing mineral processing technology.

[0025] In order to solve the above-mentioned problems in the prior art, according to one aspect of the present invention, a comprehensive treatment method for potassium-containing fine-grained mixed copper ore is provided, and the method comprises the following steps: S1, dissociating and slurrying the potassium-containing fine-grained mixed copper ore to obtain ore pulp; S2, performing oxidation-reduction modification treatment on the ore pulp in an acidic environment, and then performing solid-liquid separation to obtain a liquid phase and a solid phase, wherein the liquid phase is a copper leaching solution; slurrying the solid phase again to obtain a floating copper ore pulp; S3, performing a flotation separation treatment on the floating copper ore pulp to obtain a copper sulfide concentrate and a floating copper tailings; S4, performing a floating potassium separation on the floating copper tailings to obtain a potassium-containing mineral.

[0026] In the copper leaching solution, copper minerals of the oxide mineral type can be recovered; in the copper sulfide concentrate, copper minerals of the sulfide mineral type can be recovered.

[0027] The present invention performs an acidic oxidation-reduction modification treatment on the dissociated potassium-containing fine-particle mixed copper ore pulp in an acidic environment, which can dissolve copper in copper oxide minerals by acid to extract copper and obtain copper leaching solution; on the other hand, the copper on the surface of copper sulfide minerals that are slowly leached by acid can be leached by acid. 2+ / Cu +Selectively dissolving into the solution, the negatively charged sulfur (-2, -1 valence sulfur) on the surface of the copper sulfide mineral is oxidized to electrically neutral sulfur (0 valence sulfur), and the remaining strongly hydrophobic sulfur and its derivatives become the dominant phase, and the obtained solid phase is the surface-modified copper sulfide mineral; at the same time, the ore pulp is subjected to oxidation-reduction treatment, which can consume part of the dissolved oxygen in the ore pulp, regulate or alleviate the further oxidation of sulfur and its derivatives produced by the dissolved oxygen in the ore pulp on the surface of the mineral, thereby enhancing the hydrophobic activity of the mineral surface, and combined with the subsequent flotation separation process, a high-recovery, high-quality copper sulfide concentrate can be obtained. In addition, the above-mentioned modification step also provides a suitable acidic environment for the subsequent separation and enrichment of potassium, further promotes the flotation separation of potassium minerals and other ores, realizes the efficient and comprehensive recovery of resources, and at the same time reduces the emission of waste.

[0028] In the technical solution of the present invention, the "potassium-containing fine-grained mixed copper ore" includes various types of materials containing oxidation phases, sulfide phases and soluble copper mineral phases, and has strong adaptability to the mineral composition of mixed copper minerals.

[0029] In order to further improve the comprehensive recovery rate of minerals, in a preferred embodiment, step S2 includes: adding inorganic acid and redox active agent to the slurry to make the pH of the acidic environment be 1 to 4 and the redox potential E h 0~0.4V (vs. NHE). Under the above-mentioned implementation mode, the copper ion activity on the surface of the mineral after dissociation is further improved, tending to be leached to obtain a copper leaching solution, and the surface of the mineral is more easily hydrophobic. In actual operation, the copper leaching solution can be used for subsequent processing to recover copper oxide minerals, further improving the utilization value of mixed copper ore. The redox potential is regulated by the addition amount of inorganic acid and redox agent.

[0030] In order to further enhance the effect of surface modification, in a preferred embodiment, the redox active agent is one or more of formic acid, oxalic acid, tartaric acid, malic acid, citric acid, glycine, ascorbic acid, hydrazine hydrate, hydroxylamine hydrochloride, glycolic acid, D-sorbitol, and succinimide. Further preferably, the redox active agent is one or more of glycine, ascorbic acid, hydrazine hydrate, and hydroxylamine hydrochloride. In actual operation, the selection of redox agents is not limited to the types listed above, but the following conditions should be preferred as the criteria: strong reduction activity, easy complexation and dissolution of Cu on the surface of minerals; 2+ / Cu + , small molecules that are easily oxidized and decomposed. The redox active agent selected according to the above conditions can better complete the surface modification. On the one hand, it can make the Cu 2+ / Cu +The ions dissolve quickly, leaving electronegative sulfur species on the mineral surface. On the other hand, precise potential regulation is used to control the surface electronegative sulfur to tend to oxidize to electrically neutral single or aggregated states. Furthermore, competition consumes dissolved oxygen in the solution, limiting the one-step oxidation of electrically neutral hydrophobic sulfur-containing species, thus promoting the formation of a stable hydrophobic mineral surface on the surface of copper sulfide minerals and providing favorable conditions for subsequent hydrophobic floating.

[0031] In order to further promote the leaching effect of copper ions, in a preferred embodiment, the inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, etc. The above inorganic acids mainly dissolve copper in copper oxide minerals in the ore and some soluble alkaline minerals, and are used to regulate the pH and redox potential of the process.

[0032] In order to further improve the copper recovery rate, in a preferred embodiment, the weight ratio of the total weight of the inorganic acid and the redox active agent to the potassium-containing fine-grained mixed copper mineral is (100-10000 g): 1 t, preferably (1000-8000) g: 1 t; preferably, the weight ratio of the inorganic acid to the redox active agent is 4: 1 to 1: 2. According to the above parameters, the ratio of the inorganic acid and the redox active agent added can more fully complete the recovery of copper.

[0033] In a preferred embodiment, the redox modification treatment time in step S2 is 0.5 to 12 hours, and the treatment temperature is 20 to 90° C. Preferably, when the solid phase is re-slurried in step S2, the solid-liquid ratio used is 1:2 to 1:5. Under the above treatment conditions, it is more conducive to improving the recovery rate of the mineral. In actual operation, the modification treatment is preferably carried out under stirring conditions.

[0034] In a preferred embodiment, after the dissociation in step S1, the grinding fineness is that the particles with a particle size of ≤0.074 mm account for more than 90%; preferably, the solid-liquid ratio during slurry adjustment is 1:(2-10), and more preferably 1:(2-4). The above conditions are preferred, so that the copper mineral and the gangue mineral can be fully dissociated into monomers, thereby dissociating the target mineral and the gangue mineral while exposing the mineral surface, which is convenient for the subsequent leaching body copper and surface modification regulation.

[0035] For the purpose of further promoting the recovery efficiency of copper ore, in a preferred embodiment, the flotation separation treatment step includes: adding a foaming agent to the floating copper ore slurry, and the treatment time is 1:2 to 1:5; preferably, the foaming agent is a hydrophobic foaming agent having affinity with elemental sulfur or its hydrophobic derivatives; preferably, the foaming agent is one or more of methyl isobutyl carbinol, polyethylene glycol, polypropylene glycol ether, potassium phenolic acid, and diethyl phthalate; more preferably, the weight ratio of the foaming agent to the potassium-containing fine-particle mixed copper mineral is (10 to 600) g: 1t, preferably 40 to 200.

[0036] In a preferred embodiment, before adding the foaming agent to the copper flotation slurry, the foaming agent is prepared into a foaming agent aerosol in advance, and then the foaming agent aerosol is pressed into the copper flotation slurry. The method for preparing the foaming agent aerosol can be a method well known to those skilled in the art, and is not further specifically limited in the present invention. During the flotation process, the foaming agent forms microbubbles and adheres to the surface of the mineral, further strengthening the separation trend of copper sulfide and gangue minerals, and improving the quality of the floating concentrate.

[0037] In a preferred embodiment, in step S4, floating potassium separation is performed using a flotation collector, an adjuster, and a frother; preferably, the flotation collector includes oleic acid, amines and modified amines, amino esters, sulfonates, more preferably one or more of oleylamine, N-dodecyl-β-aminopropionic acid, and fatty acids; preferably, the adjuster is one or more of sulfuric acid, hydrofluoric acid, and sodium carbonate; preferably, the frother is one or more of methyl isobutyl carbinol, polyethylene glycol, polypropylene glycol ether, diethyl phthalate, and cresol acid; preferably, the pH of the floating copper tailings is adjusted to 1 to 4; preferably, the weight ratio of the floating collector to the potassium fine-grained mixed copper mineral is (200 to 800) g: 1 t; preferably, the weight ratio of the adjuster to the potassium fine-grained mixed copper mineral is (100 to 2000) g: 1 t; preferably, the weight ratio of the frother to the potassium fine-grained mixed copper mineral is (10 to 600) g: 1 t. Under the above preferred conditions, potassium resources can be better recovered.

[0038] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0039] Embodiment 1:

[0040] A mixed ore contains 1.9% copper grade, 65.4% oxidation rate and 7.5% binding rate. The copper oxide is mainly malachite, and the copper sulfide is mainly chalcopyrite and covellite. Among them, the copper minerals with a particle size of less than or equal to 0.025 mm account for more than 70%, and have a close symbiotic relationship with the gangue minerals. It is a fine-grained, difficult-to-float mixed copper ore. In addition, the content of associated potassium K2O in the ore is 4.3%, and potassium feldspar minerals account for the vast majority.

[0041] Step 1), the mixed copper ore is wet-grinded for ore dissociation, the ore is ground to a particle size of 70% or less than or equal to 0.038 mm, the slurry solid-liquid ratio is adjusted to 1:3, and the slurry is introduced into a copper ore leaching stirring tank and stirred evenly, completing the preparation operation for the dissociation of the mixed copper ore material.

[0042] Step 2), for the slurry prepared in step 1), sulfuric acid is used as the copper oxide leaching medium, and the acidity and free H + The ion concentration is 10-2 mol / L was used for leaching and copper extraction, and the pH was 1.8, so that the oxidized copper mineral was leached into the solution. During the leaching process, 200+100g / t of ascorbic acid + citric acid were added to adjust the redox potential of the mixed pulp to 0.27~0.33V (vs. NHE), and the surface of the copper sulfide mineral was selectively leached and modified synchronously, so that Cu was dissolved from the surface of the chalcopyrite. 2+ It tends to form a strongly hydrophobic surface layer of elemental S and its derivatives. After leaching modification at room temperature for 2 hours, the solid phase and the liquid phase are concentrated and separated to obtain a copper-dissolving leaching solution. The leaching solution relatively extracts 98% of copper oxide, and the extraction rate relative to the original copper ore reaches 65%. The solid phase is introduced into the subsequent microbubble self-hydrophobic floating.

[0043] Step 3), adjusting the solid phase material modified in step 2), adjusting the solid-liquid ratio to 1:3, and performing foaming self-hydrophobic flotation separation under weakly acidic conditions that are favorable for the floating of surface hydrophobic sulfur species, with a pH of about 4, and using a pressure-injection microbubble separation method to promote the attachment of fine modified minerals. During the process, 200+100+50g / t of MIBC is added as a foaming agent, and two scavenging operations are performed, one roughing operation, one fine selection operation, and each operation time is 6 minutes. The copper sulfide concentrate and the potassium-containing flotation tailings are separated. The copper recovery rate in the sulfide concentrate is 32%, the copper grade is greater than 32%, and a high-quality copper concentrate is obtained.

[0044] Step 4), the potassium-containing slurry obtained in step 3) is subjected to one-roughing, two-fine and one-scavenging closed-circuit aerated agitation flotation to separate potassium minerals and gangue minerals, using HF2000g / t as a regulator, oleylamine 1000g / t as a collector, and MIBC as a frother. The roughing and scavenging times are 4 minutes, and the concentrating time is 3 minutes, and potassium concentrate powder with a K2O grade of 12.2% and a recovery rate of 55% is recovered.

[0045] Ultimately, the copper recovery rate in the mixed copper ore was 97% and the potassium recovery rate was 55%.

[0046] Compared with the traditional process of copper sulfide flotation + copper oxide sulfide flotation, the copper recovery rate is increased by about 18%, and 55% of the potassium element is comprehensively recovered; the copper recovery rate of this method is equivalent to that of the copper recovery rate of full wet H2O2 strong oxidation leaching completed under optimized conditions.

[0047] Embodiment 2:

[0048] A mixed copper ore contains 2.3% copper grade, 35.4% oxidation rate and 11.5% binding rate. Among the copper oxides, chalcopyrite accounts for 40%, which is one of the important factors affecting the recovery efficiency of copper minerals. The copper sulfide is mainly chalcopyrite, covellite, etc. Among them, the proportion of copper minerals with a particle size of less than or equal to 0.038 mm exceeds 50%, and most of the useful minerals are fine particles. In addition, the content of associated potassium K2O in the ore is 2.5%, and the majority of it is potassium feldspar minerals.

[0049] Step 1), the mixed copper ore is wet-grinded for ore dissociation, the ore is ground to a particle size of -0.074 mm, accounting for 90%, the slurry solid-liquid ratio is adjusted to 1:4, and the slurry is introduced into the copper ore leaching stirring tank and stirred evenly, completing the preparation operation for the dissociation of the mixed copper ore material.

[0050] Step 2), for the slurry prepared in step 1), hydrochloric acid is used as the copper oxide leaching medium, and the acidity and free H are adjusted to control + The ion concentration is 10 -3 mol / L was used for leaching and copper extraction. During the leaching process, 200g / t of hydroxylamine hydrochloride was added to adjust the slurry redox potential to 0.18-0.22V (vs. NHE). The copper sulfide mineral was leached and modified with a reducing agent simultaneously, so that Cu was dissolved from the surface of chalcopyrite. 2+ It tends to form a strongly hydrophobic surface layer of elemental S and its derivatives. After leaching modification at room temperature for 1 hour, the solid phase and the liquid phase are concentrated and separated to obtain a copper-dissolving leaching solution. The leaching solution extracts 90% of copper oxide and the extraction rate relative to the original copper ore reaches 45%. The solid phase is introduced into the subsequent microbubble self-hydrophobic floating.

[0051] Step 3), adjusting the solid phase material modified in step 2), adjusting the solid-liquid ratio to 1:3, preparing a foaming agent aerosol with 40 mg / L of polypropylene glycol ether, and then pressing it into the self-hydrophobic floating slurry to perform microbubble self-hydrophobic floating separation, and separating and enriching copper sulfide by one roughing, one fine selection and one scavenging operation, wherein each operation time is 4 minutes, separating the copper sulfide concentrate and the potassium-containing flotation tailings, the copper recovery rate in the sulfide concentrate reaches 50%, and the copper grade is greater than 30%.

[0052] Step 4), the potassium-containing slurry obtained in step 3) is adjusted with 1000 g / t of sodium carbonate, 1000 g / t of fatty acid is used as a collector, and polypropylene glycol ether is used as a frother, and one roughing, two fines and one scavenging flotation is performed to separate potassium minerals and gangue minerals. The roughing and scavenging time is 5 minutes, and the fine time is 3 minutes. The K2O grade in the recovered potassium concentrate is 10.6%, and the recovery rate reaches more than 50%. The subsequent magnetic separation method can further improve the quality of K2O to more than 12.3%.

[0053] Ultimately, the copper recovery rate in the mixed copper ore was 95% and the potassium recovery rate was 52%.

[0054] Compared with the traditional process of copper sulfide flotation + copper oxide sulfide flotation, the copper recovery rate is increased by about 19%, and more than half of the potassium element is comprehensively recovered.

[0055] Embodiment 3:

[0056] A mixed ore contains 3.3% copper grade, 45.7% oxidation rate and 12.5% ​​binding rate. The copper oxide is mainly malachite and partly chrysocolla. The copper sulfide is mainly chalcopyrite and bornite. Among them, the copper minerals with a particle size of less than or equal to 0.020 mm account for more than 60%, and have a close symbiotic relationship with the gangue minerals. It is a fine-grained, difficult-to-float mixed copper ore. In addition, the content of associated potassium K2O in the ore is 4.1%, which is mainly potassium feldspar minerals.

[0057] Step 1), the mixed copper ore is wet-grinded for ore dissociation, the ore is ground to a particle size of 80% or less than or equal to 0.054 mm, the slurry solid-liquid ratio is adjusted to 1:2, and the slurry is introduced into a copper ore leaching stirring tank and stirred evenly, completing the preparation operation for the dissociation of the mixed copper ore material.

[0058] Step 2), for the slurry prepared in step 1), nitric acid is used as the copper oxide leaching medium, and the acidity and free H are adjusted to control + The ion concentration is 10 -1 mol / L was used for leaching and copper extraction, and the pH was 1.0, so that the copper oxide mineral was dissolved by acid. During the leaching process, 200+100g / t of hydroxylamine hydrochloride + succinic acid was added to adjust the redox potential of the mixed slurry to 0.35-0.4V (vs. NHE), and the surface of the copper sulfide mineral was selectively leached and modified synchronously, so that Cu 2+ was dissolved from the surface of the copper sulfide. 2+ It tends to form a strongly hydrophobic surface layer of elemental S and its derivatives. After leaching modification at room temperature for 1 hour, the solid phase and the liquid phase are concentrated and separated to obtain a copper-dissolving leaching solution. The leaching solution extracts 97% of copper oxide and the extraction rate relative to the original copper ore reaches 46%. The solid phase is introduced into the subsequent microbubble self-hydrophobic floating.

[0059] Step 3), adjusting the solid phase material modified in step 2), adjusting the solid-liquid ratio to 1:10, and performing foaming self-hydrophobic floating separation under weakly acidic conditions that are favorable for the floating of surface hydrophobic sulfur species, with a pH of about 2, and using a microbubble pressure method to promote the attachment of fine modified minerals. During the process, 600+200+100g / t of cresol acid is added as a foaming agent, and a roughing operation, a fine selection operation and two scavenging operations are performed, each operation time is 4 minutes, and the copper sulfide concentrate and the potassium-containing flotation tailings are separated. The copper recovery rate relative to the sulfide concentrate is 52%, the copper grade is greater than 30%, and a high-quality copper concentrate is obtained.

[0060] Step 4), the potassium-containing slurry obtained in step 3) is subjected to a one-roughing-one-fine-one-scavenging closed-circuit aerated agitation flotation separation of potassium minerals and gangue minerals using 2000 g / t of nitric acid as a regulator, 2000 g / t of N-dodecyl-β-aminopropionic acid as a collector, and potassium phenolic acid as a frother. The roughing, fine and scavenging time is 4 minutes, and potassium concentrate powder with a K2O grade of 12.3% and a recovery rate of 53% is recovered.

[0061] Ultimately, the copper recovery rate in the mixed copper ore was 98% and the potassium recovery rate was 53%.

[0062] Compared with the traditional process of copper sulfide flotation + copper oxide sulfide flotation, the copper recovery rate is increased by about 15%, and 53% of the potassium element is comprehensively recovered.

[0063] Comparative Example 1:

[0064] The same mixed copper ore is used as in Example 1, except that the ore is processed by conventional flotation of copper sulfide ore + sulfide flotation of copper oxide minerals;

[0065] The ore was ground to a particle size of 70% or less than 0.038 mm, the solid-liquid ratio of the slurry was adjusted to 1:3, and the copper sulfide mineral was subjected to one coarse, two fine and two scavenging with 160g / t amyl xanthate + 80g / t 2# oil to obtain a copper sulfide concentrate with a copper recovery rate of 30% and a grade of 32%;

[0066] The copper sulfide flotation tailings use 1000g / t sodium sulfide as the sulfiding agent, 200g / t amyl xanthate + 100g / t 2# oil as the floating agent, and carry out the flotation of copper oxide minerals in a process of one roughing, three fines and three sweeps to obtain a copper oxide concentrate with a copper grade of 23% and a recovery rate of 49%;

[0067] Combining copper sulfide concentrate and copper oxide concentrate, the total copper recovery rate is 79%.

[0068] Comparative Example 2:

[0069] The same mixed copper ore is used as in Example 2, except that the ore is processed by conventional flotation of copper sulfide ore + sulfide flotation of copper oxide minerals;

[0070] The ore was ground to a particle size of -0.074, accounting for 90%, and the solid-liquid ratio of the slurry was adjusted to 1:3, and 100g / t copper sulfate was used for adjustment. 120g / t butyl xanthate + 80g / t MIBC was used for one roughing, two fines and three sweeps of copper sulfide minerals to obtain a copper sulfide concentrate with a copper recovery rate of 44% and a grade of 27%;

[0071] The copper sulfide flotation tailings use 1000g / t sodium hydrosulfide as the sulfiding agent and 200g / t octyl xanthate + 80g / t MIBC as the floating agent to carry out the flotation of copper oxide minerals in a three-step process of roughing, refining and sweeping to obtain a copper oxide concentrate with a copper grade of 24% and a recovery rate of 32%.

[0072] Combining copper sulfide concentrate and copper oxide concentrate, the total copper recovery rate is 76%.

[0073] Comparative Example 3:

[0074] The same mixed copper ore is used as in Example 3, except that the ore is processed by conventional flotation of copper sulfide ore + sulfide flotation of copper oxide minerals;

[0075] The ore was ground to a particle size of 80% or less than 0.054 mm, and the solid-liquid ratio of the slurry was adjusted to 1:3. The copper sulfide mineral was subjected to one roughing, two fines and three sweeps with 160g / t amyl xanthate + 120g / t MIBC to obtain a copper sulfide concentrate with a copper recovery rate of 54% and a grade of 26%;

[0076] The copper sulfide flotation tailings use 1000g / t sodium sulfide as the sulfiding agent and 240g / t amyl xanthate + 160g / t MIBC as the floating agent to carry out the flotation of copper oxide minerals in a three-step process of roughing, refining and sweeping to obtain a copper oxide concentrate with a copper grade of 24% and a recovery rate of 33%.

[0077] Combining copper sulfide concentrate and copper oxide concentrate, the total copper recovery rate is 83%.

[0078] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0079] (1) By combining leaching and flotation, the technology of the present invention is more adaptable to materials with complex mineral components, and is suitable for the recycling of complex mixed copper ores with multiple types and mineral phases, thereby improving the recovery level of difficult-to-select copper-containing materials.

[0080] (2) The process uses leaching to extract copper oxide and microbubble self-hydrophobic floating to enrich copper sulfide, which improves the recovery and separation potential of the process for fine-grained minerals. It has strong adaptability to materials with fine-grained minerals and greatly avoids the problem of low mineral recovery rate affected by fineness.

[0081] (3) Using small molecule active agents as redox active agents to improve the redox state of the slurry and promote the formation of a strong hydrophobic surface on the surface of copper sulfide minerals.

[0082] (4) The copper in the copper oxide is extracted by acid leaching to improve the recovery level of copper oxide minerals, and the copper sulfide is recovered by self-hydrophobic flotation, avoiding the relatively low efficiency of sulfide flotation operation of mixed copper ore.

[0083] (5) The mixed copper ore is processed and recovered by an acidic system. While separating and recovering copper, it creates easy selection conditions for the recovery of potassium minerals in the subsequent floating copper tailings, improves the utilization rate of associated resources, reduces solid waste emissions, significantly improves the comprehensive utilization level of mineral resources, and has a strong self-consistency in the comprehensive resource process.

[0084] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A comprehensive treatment method for potassium-containing fine-grained mixed copper ore, characterized in that: The method comprises the following steps: S1, dissociating and slurrying the potassium-containing fine-particle mixed copper ore to obtain slurry; S2, performing redox modification treatment on the slurry in an acidic environment, and then performing solid-liquid separation to obtain a liquid phase and a solid phase, wherein the liquid phase is a copper leaching solution; and slurrying the solid phase again to obtain a floating copper slurry; S3, performing flotation separation treatment on the copper flotation slurry to obtain copper sulfide concentrate and copper flotation tailings; S4, performing floating potassium separation on the floating copper tailings to obtain potassium-containing minerals; Wherein, the step S2 comprises: adding an inorganic acid and a redox active agent to the slurry to perform the redox modification treatment, and the pH of the acidic environment is 1 to 4, and the redox potential E h is 0~0.4V(vs.NHE), and E h is not 0; the redox active agent is one or more of formic acid, oxalic acid, tartaric acid, malic acid, citric acid, glycine, ascorbic acid, hydrazine hydrate, hydroxylamine hydrochloride, glycolic acid, D-sorbitol and succinimide.

2. The method according to claim 1, characterized in that The inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.

3. The method according to claim 1 or 2, characterized in that: The weight ratio of the total weight of the inorganic acid and the redox active agent to the weight of the potassium-containing fine-grained mixed copper mineral is (100-10000 g): 1 t.

4. The method according to claim 3, characterized in that The weight ratio of the total weight of the inorganic acid and the redox active agent to the weight of the potassium-containing fine-grained mixed copper mineral is (1000-8000) g: 1 t.

5. The method according to claim 3, characterized in that: The weight ratio of the inorganic acid to the redox active agent is 4:1 to 1:

2.

6. The method according to claim 1 or 2, characterized in that: The time of the redox modification treatment in step S2 is 0.5 to 12 hours, and the treatment temperature is 20 to 90°C.

7. The method according to claim 6, characterized in that The solid-liquid ratio when the solid phase is re-slurried in the step S2 is 1:2 to 1:

5.

8. The method according to claim 1 or 2, characterized in that: After the dissociation in step S1, the grinding fineness is that the particles with a particle size less than 0.074 mm account for more than 90%.

9. The method according to claim 8, characterized in that The solid-liquid ratio during the slurry preparation is 1:(2-10).

10. The method according to claim 9, characterized in that The solid-liquid ratio during the slurry preparation is 1:(2-4).

11. The method according to claim 1 or 2, characterized in that: The flotation separation treatment step includes: adding a foaming agent to the copper ore slurry to perform the flotation separation treatment, and the treatment time is 3 to 20 minutes.

12. The method according to claim 11, characterized in that The foaming agent is a hydrophobic foaming agent having affinity with elemental sulfur or its hydrophobic derivatives.

13. The method according to claim 12, characterized in that The foaming agent is one or more of methyl isobutyl carbinol, polyethylene glycol, polypropylene glycol ether, cresol acid and diethyl phthalate.

14. The method according to claim 12, characterized in that The weight ratio of the foaming agent to the potassium-containing fine-grained mixed copper mineral is (10-600) g: 1 t.

15. The method according to claim 14, characterized in that The weight ratio of the foaming agent to the potassium-containing fine-grained mixed copper mineral is (40-200) g:1 t.

16. The method according to claim 11, characterized in that Before adding the foaming agent to the copper flotation slurry, the foaming agent is prepared into a foaming agent aerosol in advance, and then the foaming agent aerosol is pressed into the copper flotation slurry.

17. The method according to claim 1 or 2, characterized in that: In the step S4, the floating potassium separation is performed using a flotation collector, a regulator, and a frother.

18. The method according to claim 17, characterized in that The flotation collectors include oleic acid, amines and modified amines, amino esters and sulfonates.

19. The method according to claim 17, characterized in that The flotation collector is one or more of oleylamine, N-dodecyl-β-aminopropionate, and fatty acid.

20. The method according to claim 17, characterized in that The adjusting agent is one or more of sulfuric acid, hydrofluoric acid and sodium carbonate.

21. The method according to claim 17, characterized in that The foaming agent is one or more of methyl isobutyl carbinol, polyethylene glycol, polypropylene glycol ether, cresol acid and diethyl phthalate.

22. The method according to claim 17, characterized in that The pH of the floating copper tailings is adjusted to 1-4.

23. The method according to claim 17, characterized in that The weight ratio of the flotation collector to the potassium-containing fine-grained mixed copper mineral is (200-800) g:1 t, the weight ratio of the adjuster to the potassium-containing fine-grained mixed copper mineral is (100-2000) g:1 t; the weight ratio of the frother to the potassium-containing fine-grained mixed copper mineral is (10-600) g:1 t.