Beneficiation method for fine-fraction antimony oxide ore

Abstract

The invention provides a fine-fraction antimony oxide ore beneficiation method, and belongs to the technical field of ore separation processes. According to the method, the antimony oxide concentrate is obtained through the direct flotation technology, then the antimony oxide concentrate is subjected to the reverse flotation technology, the first inhibitor and the first collecting agent are matched, and efficient recovery of fine-grained antimony oxide is achieved. Wherein the first inhibitor comprises water glass, sodium carbonate and sodium tricarboxylate starch, the first collecting agent comprises modified oleic acid, alkyl hydroximic acid, sodium tetradecyl sulfonate and magnesium sulfate, and the separation effect of antimony oxide and gangue minerals is greatly enhanced. According to the fine-grained antimony oxide ore beneficiation method, the problem of recycling of fine-grained antimony oxide containing mud is effectively solved, a new effective method is provided for development and utilization of similar fine-grained antimony oxide resources, and the fine-grained antimony oxide ore beneficiation method is suitable for application and popularization.

Description

Technical Field

[0001] The invention relates to the technical field of ore separation technology, and in particular to a method for beneficiating fine-grained antimony oxide ore. Background Art

[0002] Antimony ore is one of the most scarce mineral resources in the world, but my country's antimony ore resources are relatively rich. According to data from the United States Geological Survey, the global antimony ore reserves will exceed 2 million tons in 2024, while China's antimony ore reserves will be 640,000 tons, accounting for more than 30%, ranking first in the world; at the same time, my country is the world's largest antimony producer, accounting for about 48% of the global antimony mining output; 63% of the antimony and its oxides imported by the United States from 2019 to 2022 came from China. Antimony, as an important strategic mineral resource, is widely used in the manufacture of lead-acid batteries, photovoltaic equipment, semiconductors, flame retardants, far-infrared devices and military products, especially in the military field. Antimonide semiconductor materials have broad application prospects in military and civilian fields such as lasers and sensors. They can be used to produce ammunition, infrared-guided missiles, nuclear weapons, night vision goggles, etc., and enjoy many reputations such as "industrial MSG", "photovoltaic metal", "energy metal" and "war metal". It is a raw material that is vital to economic and national security.

[0003] According to statistics, antimony oxide ore accounts for about 15% of the total proven antimony reserves in my country. Antimony oxide ore is a difficult ore to be separated. At present, antimony oxide ore beneficiation at home and abroad still uses gravity separation, but the recovery rate of fine antimony oxide ore gravity separation is low. Limited by the level of antimony oxide ore beneficiation technology, the comprehensive utilization rate of fine antimony oxide mineral resources has been at a low level for a long time, resulting in a great waste of antimony mineral resources in my country.

[0004] Therefore, it is urgent to develop a beneficiation method for fine-grained antimony oxide ore to improve the comprehensive utilization rate of antimony oxide ore resources in my country. Summary of the invention

[0005] In view of the technical problems existing in the background technology, the present application provides a beneficiation method for fine-grained antimony oxide ore, aiming to solve the problems of difficulty in beneficiation and low recovery rate of existing fine-grained antimony oxide ore.

[0006] The present application provides a method for beneficiating fine-grained antimony oxide ore, comprising the following steps:

[0007] S1. Add water to the ore sample, stir and mix, and obtain flotation ore pulp;

[0008] S2. using a positive flotation agent to perform positive flotation on the flotation ore pulp to obtain an antimony oxide concentrate and a positive flotation tailing;

[0009] S3. Use a reverse flotation agent to reverse flotate the antimony oxide concentrate to obtain an antimony concentrate and a reverse flotation tailing.

[0010] In the technical solution of the embodiment of the present application, antimony oxide concentrate is first obtained through a forward flotation process, and then the antimony oxide concentrate is subjected to a reverse flotation process, and a forward flotation agent and a reverse flotation agent are used to achieve efficient recovery of fine-grained antimony oxide.

[0011] In some embodiments, the positive flotation reagent includes: a first inhibitor and a first collector; the first inhibitor includes: water glass, sodium carbonate, sodium tricarboxylate starch, and the mass ratio thereof is 8-12:8-12:1-2; the first collector includes: modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate, and magnesium sulfate, and the mass ratio thereof is 0.5-1.5:0.5-1.5:1-2.5:1-2.5.

[0012] In this embodiment, the first inhibitor and the first collector obtained by compounding the raw materials in a specific ratio greatly enhance the separation effect of antimony oxide and gangue minerals in the positive flotation operation, wherein the inhibitor can weaken the effect of the collector and the mineral, thereby reducing the floatability of the mineral, and the collector can increase the hydrophobicity of the mineral surface, making it easy to adhere to the bubbles, thereby improving the floatability of the mineral.

[0013] In some embodiments, the positive flotation reagent also includes a frother and a pH adjuster. The frother is one or more of pineol, methyl isobutyl carbinol, and methoxypolypropylene glycol; and the pH adjuster is NaOH.

[0014] In this embodiment, by adding a frother during the flotation process, the surface tension of water can be reduced to form foam, so that the air bubbles in the aerated flotation slurry can adhere to the selectively floating mineral particles, thereby further separating antimony from the gangue minerals; by adjusting the pH value of the slurry to 6.5-8, the slurry environment is made neutral, which is conducive to the subsequent mineral processing process.

[0015] In some embodiments, the reverse flotation reagent includes: a second inhibitor and a second collector. The second inhibitor is NaOH; the second collector includes: coconut amine, oleic acid, and neutral oil.

[0016] In this embodiment, by adding the second depressant and the second collector in the reverse flotation operation, the antimony oxide concentrate is further subjected to reverse flotation to further separate the antimony in the ore and the minerals in the gangue.

[0017] In some embodiments, the positive flotation includes two roughing operations, two scavenging operations and two concentrating operations. In the first roughing operation, the dosage of the first depressant is 500-7000 g / t, the dosage of the first collector is 100-1200 g / t, the dosage of the frother is 10-60 g / t, and the dosage of the pH adjuster is 50-2000 g / t; in the second roughing operation, the dosage of the first collector is 50-800 g / t; in the first concentrating operation, the dosage of the first depressant is 50-1000 g / t, and in the second concentrating operation, the dosage of the first depressant is 20-600 g / t; in the first scavenging operation, the dosage of the first collector is 30-600 g / t, and in the second scavenging operation, the dosage of the first collector is 10-400 g / t.

[0018] In this embodiment, different amounts of positive flotation reagents are added in the two roughing, two scavenging and two cleaning positive flotation operations respectively, so that the antimony in the ore and the gangue minerals are fully separated, thereby achieving efficient separation of the antimony in the ore and the gangue minerals in the positive flotation operation.

[0019] In some embodiments, reverse flotation includes two reverse flotation operations. In the first reverse flotation operation, the dosage of the second depressant is 1000-5000 g / t, and the dosage of the second collector is 30-200 g / t; in the second reverse flotation operation, the dosage of the second depressant is 500-3000 g / t, and the dosage of the second collector is 10-150 g / t.

[0020] In this embodiment, the antimony in the antimony oxide concentrate is further separated from the gangue minerals by respectively adding the second depressant and the second collector in the two reverse flotation operations.

[0021] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0023] Figure 1 This is a flow chart of the beneficiation method of fine-grained antimony oxide ore in Example 1 of the present application;

[0024] Figure 2This is a flow chart of the beneficiation method of fine-grained antimony oxide ore in Comparative Example 9 of the present application;

[0025] Figure 3 This is a flow chart of the beneficiation method of fine-grained antimony oxide ore in Comparative Example 10 of the present application;

[0026] Figure 4 This is a flow chart of the fine-grained antimony oxide ore beneficiation method in Comparative Example 11 of the present application. DETAILED DESCRIPTION

[0027] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0029] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0030] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0031] In order to solve the problems of difficulty in beneficiation and low recovery rate of existing fine-grained antimony oxide ore, the present application provides a beneficiation method for fine-grained antimony oxide ore. The present application first obtains antimony oxide concentrate through a positive flotation process of two roughing selections, two scavenging selections and two fine selections, and then performs two reverse flotation processes on the antimony oxide concentrate, and cooperates with a first inhibitor and a first collector to achieve efficient recovery of fine-grained antimony oxide, wherein the first inhibitor includes: water glass, sodium carbonate, sodium tricarboxylate starch, and the first collector includes: modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate, and magnesium sulfate, which greatly enhances the separation effect of antimony oxide and gangue minerals. The method effectively solves the problem of recycling and utilizing fine-grained antimony oxide containing mud, provides a new and effective method for the development and utilization of similar fine-grained antimony oxide resources, and is suitable for promotion and application.

[0032] The present application provides a method for beneficiating fine-grained antimony oxide ore, comprising the following steps:

[0033] S1. Add water to the ore sample, stir and mix, and obtain flotation ore pulp;

[0034] S2. using a positive flotation agent to perform positive flotation on the flotation ore pulp to obtain an antimony oxide concentrate and a positive flotation tailing;

[0035] S3. Use a reverse flotation agent to reverse flotate the antimony oxide concentrate to obtain an antimony concentrate and a reverse flotation tailing.

[0036] In the technical solution of the embodiment of the present application, the antimony oxide concentrate is first obtained by the forward flotation process, and then the antimony oxide concentrate is subjected to the reverse flotation process, and the forward flotation agent and the reverse flotation agent are used to achieve efficient recovery of fine antimony oxide. If the reverse flotation operation is adopted first, the removal effect of using a weak collector is poor, and the use of a strong collector will result in a large amount of antimony oxide loss, resulting in a very low recovery rate.

[0037] Furthermore, in some embodiments, the positive flotation reagent includes: a first inhibitor and a first collector; the first inhibitor includes: water glass, sodium carbonate, sodium tricarboxylate starch, and their mass ratio is 8-12:8-12:1-2; the first collector includes: modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate, and magnesium sulfate, and their mass ratio is 0.5-1.5:0.5-1.5:1-2.5:1-2.5.

[0038] In the technical solution of the embodiment of the present application, the first inhibitor and the first collector obtained by compounding the raw materials in a specific ratio greatly enhance the separation effect of antimony oxide and gangue minerals in the positive flotation operation, wherein the inhibitor can weaken the effect of the collector and the mineral, thereby reducing the mineral floatability, and the collector can increase the hydrophobicity of the mineral surface, making it easy to adhere to the bubbles, thereby improving the mineral floatability, and greatly enhancing the separation effect of antimony oxide and gangue minerals. The addition of some inhibitors will cause antimony oxide and gangue to be unable to be separated, and some existing collectors have poor test results when used alone or in combination with agents. The present application uses three different types of collectors in combination, and magnesium sulfate is added at the same time to form a metal complex collector with the collector, which can enhance the separation of antimony oxide and gangue minerals.

[0039] Furthermore, in some embodiments, the positive flotation reagent also includes: a frother and a pH adjuster, wherein the frother is one or more of pineol, methyl isobutyl carbinol, and methoxypolypropylene glycol; and the pH adjuster is NaOH.

[0040] In the technical solution of the embodiment of the present application, by adding a frother during the flotation process, the surface tension of water can be reduced to form foam, so that the air bubbles in the aerated flotation slurry can adhere to the selectively floating mineral particles, thereby further separating antimony from the gangue minerals; by adjusting the pH value of the slurry to 6.5-8, the slurry environment is made neutral, which is conducive to the subsequent mineral processing process.

[0041] Furthermore, in some embodiments, the reverse flotation reagent includes: a second inhibitor and a second collector. The second inhibitor is NaOH; the second collector includes: coconut amine, oleic acid, and neutral oil. Furthermore, the mass ratio of coconut amine, oleic acid, and neutral oil in the second collector is preferably 0.5-1.5:2-4:0.5-1.5.

[0042] In the technical solution of the embodiment of the present application, by adding a second depressant and a second collector in the reverse flotation operation, the antimony oxide concentrate is further reversely floated to further separate the antimony in the ore and the minerals in the gangue.

[0043] Further, in some embodiments, the positive flotation includes two roughing selections, two scavenging selections and two cleaning selections, and the specific steps are as follows:

[0044] 1. Add water to the ore sample and stir to obtain flotation ore pulp;

[0045] 2. The raw ore pulp is subjected to the first roughing operation, 500-7000 g / t of the first depressant is added to the raw ore pulp, the mixture is fully stirred, 50-2000 g / t of the pH value regulator is added, 100-1200 g / t of the first collector is added, the mixture is fully stirred, and then 10-60 g / t of the frother is added, the mixture is fully stirred, and aeration flotation is performed to obtain a coarse concentrate 1 and a tailing 1; the tailing 1 enters the second roughing operation, 50-800 g / t of the first collector is added, the mixture is fully stirred, and aeration flotation is performed to obtain a coarse concentrate 2 and a tailing 2;

[0046] 3. After the rough concentrate 1 and the rough concentrate 2 are uniformly mixed, they enter the first concentration operation, add 50-1000g / t of the first depressant, fully stir, and aerate flotation to obtain concentrate 1 and middling 1; concentrate 1 enters the second concentration operation, adds 20-600g / t of the first depressant, fully stir, and aerate flotation to obtain concentrate 2 and middling 2. When the flotation is closed-loop, middling 1 returns to the second roughing operation, and middling 2 returns to the first concentration operation in sequence;

[0047] 4. The tailings 2 enter the first scavenging operation, add 30-600g / t of the first collector, fully stir, and aerate to obtain scavenging concentrate 1 and tailings 3; the tailings 3 enter the second scavenging operation, add 10-400g / t of the first collector, fully stir, and aerate to obtain scavenging concentrate 2 and tailings 4 (i.e., positive flotation tailings 1). When the flotation closed-loop circulation is performed, the scavenging concentrate 1 is returned to the second roughing operation, and the scavenging concentrate 2 is returned to the first scavenging operation in sequence.

[0048] In the technical solution of the embodiment of the present application, different amounts of positive flotation reagents are added in the positive flotation operations of two roughing selections, two scavenging selections, and two cleaning selections, respectively, so that the antimony in the ore and the minerals in the gangue are fully separated, thereby achieving efficient separation of the antimony in the ore and the gangue minerals in the positive flotation operation.

[0049] Furthermore, in some embodiments, in step 1, the ore sample is a gravity separation tailings of a certain ore dressing plant, and the content of minerals with a particle size less than 20 μm in the ore sample is 24-28%; the slurry concentration is 26-30%.

[0050] In the technical solution of the embodiment of the present application, the ore is fine-grained antimony oxide ore.

[0051] During the first reverse flotation operation, the dosage of the second depressant is 1000-5000 g / t, and the dosage of the second collector is 30-200 g / t; during the second reverse flotation operation, the dosage of the second depressant is 500-3000 g / t, and the dosage of the second collector is 10-150 g / t.

[0052] Further, in some embodiments, the reverse flotation includes two reverse flotation operations, and the specific steps are as follows:

[0053] The concentrate 2 is put into the first reverse flotation operation, 1000-5000g / t of the second depressant is added, and then 30-200g / t of the second collector is added, fully stirred, and aerated flotation is performed to obtain antimony concentrate and middling ore 3; the middling ore 3 is then put into the second reverse flotation operation, 500-3000g / t of the second depressant is added, and then 30-200g / t of the second collector is added, fully stirred, and aerated flotation is performed to obtain middling ore 4 and tailings 5 ​​(i.e., reverse flotation tailings 2). During the flotation closed-circuit test, the middling ore 4 is returned to the first reverse flotation operation in sequence.

[0054] In the technical solution of the embodiment of the present application, the second depressant and the second collector are respectively added in the two reverse flotation operations to further separate the antimony in the antimony oxide concentrate from the gangue minerals.

[0055] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be obtained commercially.

[0056] Example 1

[0057] This embodiment provides a method for beneficiating fine-grained antimony oxide ore. The beneficiation flow chart is as follows: Figure 1 As shown, the specific steps include:

[0058] (1) Weigh 500 g of ore sample, add clean water to a pulp concentration of 28%, and stir to obtain flotation ore pulp;

[0059] (2) Direct flotation process: add 2000 g / t of the first inhibitor (i.e., inhibitor DP-1) to the pulp, stir thoroughly for 3 min, add 500 g / t of NaOH to adjust the pulp pH to 7.5, then add 600 g / t of the first collector (i.e., collector CK-1), stir thoroughly for 3 min, add 20 g / t of pine oil, stir for 1 min, and aerate for 3 min to obtain a coarse concentrate 1 and a tailing 1; the tailings enter the second roughing operation, add 400 g / t of the first collector (i.e., collector CK-1), stir thoroughly for 3 min, and aerate for 2 min to obtain a coarse concentrate 2 and a tailing 2;

[0060] After the coarse concentrate 1 and the coarse concentrate 2 are evenly mixed, they enter the first concentration operation, add 100g / t of the first inhibitor (i.e., inhibitor DP-1), stir well for 3 minutes, and aerate and float for 2 minutes to obtain concentrate 1 and medium ore 1; concentrate 1 enters the second concentration operation, adds 60g / t of the first inhibitor (i.e., inhibitor DP-1), stir well for 3 minutes, and aerate and float for 2 minutes to obtain concentrate 2 and medium ore 2. When the flotation closed-loop cycle is in progress, medium ore 1 returns to the second roughing operation, and medium ore 2 returns to the first concentration operation in sequence;

[0061] Tailings 2 enters the first scavenging operation, adds 200g / t of the first collector (i.e., collector CK-1), fully stirs for 3 minutes, and aerates for 2 minutes to obtain scavenging concentrate 1 and tailings 3; Tailings 3 enters the second scavenging operation, adds 100g / t of the first collector (i.e., collector CK-1), fully stirs for 3 minutes, and aerates for 2 minutes to obtain scavenging concentrate 2 and tailings 4. When the flotation closed-loop cycle is in progress, the scavenging concentrate 1 is returned to the second roughing operation, and the scavenging concentrate 2 is returned to the first scavenging operation in sequence;

[0062] (3) Reverse flotation process: The concentrate 2 obtained by the direct flotation process enters the first reverse flotation operation, first adding 1500g / t of NaOH, then adding 120g / t of the second collector (i.e., collector CK-2), fully stirring for 3min, and aerating flotation for 2min to obtain antimony concentrate and medium ore 3. Medium ore 3 enters the second reverse flotation operation, first adding 500g / t of NaOH, then adding 80g / t of the second collector (i.e., collector CK-2), fully stirring for 3min, and aerating flotation for 2min to obtain medium ore 4 and tailings 5. During the flotation closed-circuit test, medium ore 4 is returned to the first reverse flotation operation in sequence.

[0063] The source and performance parameters of the ore samples are as follows: The tailings of a certain ore dressing plant are re-selected, of which the minerals with a particle size of less than 20μm account for about 26%, the antimony content in the original ore is 0.98%, and the main gangue minerals are quartz, kaolinite, calcite, mica, feldspar, etc.

[0064] The raw material ratios of the first collector (i.e., collector CK-1), the first inhibitor (i.e., inhibitor DP-1) and the second collector (i.e., collector CK-2) are as follows: the first collector (i.e., collector CK-1) is compounded from modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate and magnesium sulfate in a mass ratio of 1:1:2:2; the first inhibitor (i.e., inhibitor DP-1) is compounded from water glass, sodium carbonate and sodium tricarboxylate starch in a mass ratio of 10:10:1; the second collector (i.e., collector CK-2) is compounded from modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate and magnesium sulfate in a mass ratio of 1:1:2:2.

[0065] The test results of the separation index of antimony oxide ore in this embodiment are shown in Table 1.

[0066] Table 1 Antimony oxide ore separation index in Example 1

[0067]

[0068] Examples 2 to 5 and Comparative Examples 1 to 4

[0069] Examples 2 to 5 and Comparative Examples 1 to 4 respectively provide a method for beneficiating fine-grained antimony oxide ore. Compared with Example 1, the difference is that the ratio of raw materials in the first inhibitor (i.e., inhibitor DP-1) and the first collector (i.e., collector CK-1) is different. The other steps are roughly the same as those in Example 1 and will not be repeated here. The raw material ratio is shown in Table 2.

[0070] Table 2 Ratio of raw materials in the first inhibitor (i.e., inhibitor DP-1) and the first collector (i.e., collector CK-1) in Examples 2 to 5 and Comparative Examples 1 to 4

[0071]

[0072]

[0073] The test results of the separation indexes of antimony oxide ore in Examples 2 to 5 and Comparative Examples 1 to 4 are shown in Table 3.

[0074] Table 3 Antimony oxide ore separation indexes in Examples 2 to 5 and Comparative Examples 1 to 4

[0075]

[0076]

[0077] It can be seen from the test results of Examples 2 to 5 in Table 3 that the antimony oxide ore refloatation combined separation process of the present invention is used, wherein the mass ratio of water glass, sodium carbonate, and sodium tricarboxylate starch in the first inhibitor is 8 to 12:8 to 12:1 to 2, and the mass ratio of modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate, and magnesium sulfate in the first collector is 0.5 to 1.5:0.5 to 1.5:1 to 2.5:1 to 2.5. When, the separation of antimony oxide and gangue minerals can be effectively achieved, and better process indicators are obtained, and it has a good industrial application prospect; it can be seen from the test results of Comparative Examples 1 to 4 that it is difficult to achieve efficient separation of antimony oxide and gangue minerals by using a mixing ratio of reagents other than the present invention.

[0078] Among them, the principle of synergistic effect between the raw materials in the first inhibitor is that water glass and sodium carbonate can undergo physical and chemical reactions with the surface of gangue minerals in the slurry, change the surface electrical properties of fine particles, and disperse the slurry through electrostatic repulsion, while sodium carbonate can eliminate the influence of inevitable ions such as calcium and aluminum in the slurry on flotation, and groups such as hydroxyl groups of sodium tricarboxylate starch can bond with the surface of fine-grained gangue minerals, agglomerate the same type of fine-grained gangue minerals to form large particle clusters. The three agents purify the flotation environment by agglomerating fine-grained gangue and dispersing the slurry. The principle of the synergistic effect between the raw materials in the first collector is that magnesium ions react with the collector to first generate a metal complex collector. Due to the difference in active points on the mineral surface, different collectors in the combined collector can be "interspersed" and adsorbed on different active particles, ensuring a strong interaction between the agent and the mineral. At the same time, due to the difference in the electrical properties of the mineral surface or the electrical properties of the agents, the combined collector can enhance the electrostatic attraction between the agent and the mineral or weaken the electrostatic repulsion between the agent and the mineral to a certain extent. Therefore, the combined collector can enhance the collection ability of antimony oxide through co-adsorption, chelation with mineral surface ions and other modes of action.

[0079] Comparative Examples 5-6

[0080] This comparative example provides a method for beneficiating fine-grained antimony oxide ore. Compared with Example 1, the difference is that the raw material of the first inhibitor (i.e., inhibitor DP-1) is different. The first inhibitor (i.e., inhibitor DP-1) in Comparative Example 5 is water glass, and the first inhibitor (i.e., inhibitor DP-1) in Comparative Example 6 is compounded by water glass and starch in a mass ratio of 9:2. The other steps are roughly the same as those in Example 1 and are not repeated here.

[0081] Comparative Examples 7 to 8

[0082] This comparative example provides a method for beneficiating fine-grained antimony oxide ore. Compared with Example 1, the difference is that the raw material of the first collector (i.e., collector CK-1) is different. The first collector (i.e., collector CK-1) in Comparative Example 7 is sodium dodecyl sulfate, and the first collector (i.e., collector CK-1) in Comparative Example 8 is compounded with oleic acid, salicylic hydroxamic acid, and sodium petroleum sulfonate in a mass ratio of 9:1:1. The other steps are substantially the same as those in Example 1 and are not repeated here.

[0083] The test results of the separation indexes of antimony oxide ore in Comparative Examples 5 to 8 are shown in Table 4.

[0084] Table 4 Antimony oxide ore separation indexes in comparative examples 5 to 8

[0085]

[0086]

[0087] It can be seen from the test results of Comparative Examples 5 to 6 in Table 4 that, compared with Example 1, when the first inhibitor is water glass or water glass and starch, the grade and recovery rate of Sb are reduced; it can be seen from the test results of Comparative Examples 7 to 8 that, compared with Example 1, when the first collector is sodium dodecyl sulfate or a carboxyl group, a hydroxamate group, or a sulfonic acid group, the grade and recovery rate of Sb are greatly reduced, and the recovery effect is poor.

[0088] Comparative Example 9

[0089] This comparative example provides a method for beneficiating fine-grained antimony oxide ore. Compared with Example 1, the difference is that no reverse flotation operation is performed. The other steps are substantially the same as those in Example 1 and will not be described in detail herein. The beneficiation process is as follows: Figure 2 shown.

[0090] Comparative Example 10

[0091] This comparative example provides a method for beneficiating fine-grained antimony oxide ore. Compared with Example 1, the difference is that the second reverse flotation operation is not performed. The other steps are substantially the same as those in Example 1 and will not be described in detail herein. The beneficiation process is as follows: Figure 3 shown.

[0092] Comparative Example 11

[0093] This comparative example provides a fine-grained antimony oxide ore beneficiation method. Compared with Example 1, the difference is that the reverse flotation operation is cancelled, and a third concentration operation is added in the forward flotation operation, that is, the selected second concentrate enters the third concentration operation, no reagent is added, after fully stirring for 1 minute, aeration flotation is performed for 2 minutes to obtain a selected third concentrate and a selected third tailings, and the selected third tailings are returned in sequence and combined with the selected first concentrate to enter the third concentration operation. The other steps are roughly the same as those in Example 1 and will not be repeated here. The beneficiation process is as follows: Figure 4 shown.

[0094] Comparative Example 12

[0095] This comparative example provides a method for beneficiating fine-grained antimony oxide ore. Compared with Example 1, the difference is that reverse flotation is performed first and then forward flotation is performed. The other steps are roughly the same as those in Example 1 and will not be repeated here.

[0096] The test results of the separation indexes of antimony oxide ore in Comparative Examples 9 to 12 are shown in Table 5.

[0097] Table 5 Antimony oxide ore separation indexes in comparative examples 9 to 12

[0098]

[0099]

[0100] It can be seen from Table 5 that, compared with Example 1, whether the reverse flotation is cancelled to increase the concentrate operation, the reverse flotation operation is reduced, or the order of the forward flotation process and the reverse flotation process is exchanged, the grade and recovery rate of Sb are reduced, and the recovery effect is reduced.

[0101] In summary, the present application provides a method for beneficiating fine-grained antimony oxide ore, which first obtains antimony oxide concentrate through a positive flotation process of two roughing selections, two scavenging selections and two fine selections, and then performs two reverse flotation processes on the antimony oxide concentrate, and cooperates with a first inhibitor and a first collector to achieve efficient recovery of fine-grained antimony oxide. Among them, the first inhibitor and the first collector are compounded with a new combination of reagents, the first inhibitor includes: water glass, sodium carbonate, sodium tricarboxylate starch, and the first collector includes: modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate, and magnesium sulfate, which greatly enhances the separation effect of antimony oxide and gangue minerals. The method for beneficiating fine-grained antimony oxide ore provided by the present application effectively solves the problem of recycling and utilizing fine-grained antimony oxide containing mud, and provides a new and effective method for the development and utilization of similar fine-grained antimony oxide resources, which is suitable for promotion and application.

[0102] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A method for beneficiating fine-grained antimony oxide ore, characterized in that: The steps include: S1. Add water to the ore sample, stir and mix, and obtain flotation ore pulp; S2. using a positive flotation agent to perform positive flotation on the flotation ore pulp to obtain an antimony oxide concentrate and a positive flotation tailing; S3. Use a reverse flotation agent to reverse flotate the antimony oxide concentrate to obtain an antimony concentrate and a reverse flotation tailing.

2. The method for beneficiating fine-grained antimony oxide ore according to claim 1, characterized in that: The positive flotation reagent includes: a first inhibitor and a first collector; the first inhibitor includes: water glass, sodium carbonate, sodium tricarboxylate starch, and the first collector includes: modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate, and magnesium sulfate.

3. The method for beneficiating fine-grained antimony oxide ore according to claim 2, characterized in that: The mass ratio of water glass, sodium carbonate and sodium tricarboxylate starch in the first inhibitor is 8-12:8-12:1-2; the mass ratio of modified oleic acid, alkyl hydroxamic acid, sodium tetradecyl sulfonate and magnesium sulfate in the first collector is 0.5-1.5:0.5-1.5:1-2.5:1-2.

5.

4. The method for beneficiating fine-grained antimony oxide ore according to claim 2, characterized in that: The positive flotation reagent also includes: a frother and a pH regulator. The frother is one or more of terpineol, methyl isobutyl carbinol, and methoxy polypropylene glycol; and the pH regulator is NaOH.

5. The method for beneficiating fine-grained antimony oxide ore according to claim 1, characterized in that: The reverse flotation reagent includes: a second inhibitor and a second collector.

6. The method for beneficiating fine-grained antimony oxide ore according to claim 5, characterized in that: The second inhibitor is NaOH; the second collector includes: coconut amine, oleic acid, and neutral oil.

7. The method for beneficiating fine-grained antimony oxide ore according to claim 4, characterized in that: The positive flotation includes two roughing selections, two sweeping selections and two cleaning selections.

8. The method for beneficiating fine-grained antimony oxide ore according to claim 7, characterized in that: During the forward flotation, in the first roughing operation, the dosage of the first depressant is 500-7000 g / t, the dosage of the first collector is 100-1200 g / t, the dosage of the frother is 10-60 g / t, and the dosage of the pH adjuster is 50-2000 g / t; in the second roughing operation, the dosage of the first collector is 50-800 g / t; in the first concentrating operation, the dosage of the first depressant is 50-1000 g / t, and in the second concentrating operation, the dosage of the first depressant is 20-600 g / t; in the first scavenging operation, the dosage of the first collector is 30-600 g / t, and in the second scavenging operation, the dosage of the first collector is 10-400 g / t.

9. The method for beneficiating fine-grained antimony oxide ore according to claim 5, characterized in that: The reverse flotation includes two reverse flotation operations.

10. The method for beneficiating fine-grained antimony oxide ore according to claim 9, characterized in that: During the reverse flotation process, in the first reverse flotation operation, the dosage of the second depressant is 1000-5000 g / t, and the dosage of the second collector is 30-200 g / t; in the second reverse flotation operation, the dosage of the second depressant is 500-3000 g / t, and the dosage of the second collector is 10-150 g / t.

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