A method for recycling a flotation reagent and a desorbent

Abstract

The application discloses a kind of flotation reagent and desorption agent recycling method, steps as follows: (1), to the mineral pulp of the concentrate that the surface remains organic matter anion adsorption reagent, add desorption agent, and make organic matter anion adsorption reagent desorption under the assistance of high-speed stirring, then obtain the mineral that surface is clean and the desorption liquid containing beneficial reagent by solid-liquid separation;(2), after the supernatant and bottom flocculate obtained after standing and settling of desorption liquid, bottom flocculate is added to certain concentration of strong acid aqueous solution, then directly recycled after inorganic ceramic membrane oil-water separation or alkali saponification and is used for the flotation operation of purpose mineral;(3), the supernatant containing soluble metal salt obtained after oil-water separation is combined with the supernatant obtained in step (2) and is used for reagent desorption operation after recycling.The application can efficiently realize the selective separation of mineral and its surface beneficial reagent, realize the recycling of mineral surface collector and desorption agent, reduce cost, improve concentrate metallurgical efficiency.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mineral flotation and hydrometallurgy, and particularly relates to a method for recycling flotation reagents and desorption agents. BACKGROUND

[0002] In the field of flotation, mineral collectors are mainly divided into two categories: fatty acid and non-fatty acid. Fatty acid collectors include oleic acid and its derivatives, oxidized paraffin soap, tall oil, etc., non-fatty acid collectors include chelating collectors such as benzohydroxamic acid, salicylhydroxamic acid, octylhydroxamic acid, phosphonic acid collectors such as styrene phosphonic acid, and sulfonic acid collectors such as sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate. Fatty acid collectors have poor selectivity and strong collector ability, and are usually used for oxidized ores and non-metallic ores with few types of minerals, single target minerals, and simple and easy selection; non-fatty acid collectors such as benzohydroxamic acid have good selectivity and weak collector ability, and are usually used for oxidized ores and non-metallic ores with many types of minerals and complex and difficult selection, but due to high cost, their use in some application fields is limited. For this reason, many studies have mixed fatty acids and non-fatty acids for use.

[0003] In recent years, as the high-grade ore gradually decreases, low-grade and fine-grained disseminated ore has become the main object of mineral processing, which leads to an increase in the amount of collector used, and its cost accounts for a higher and higher proportion of the mineral processing cost. In order to meet the concept of efficient and low-pollution production, it is necessary to explore ways to reduce the cost of using collectors, which is a technical problem that needs to be solved urgently.

[0004] A large amount of beneficial reagents, mainly collectors, with high activity, remain on the surface of the mineral concentrate obtained after flotation. However, most mineral concentrates are directly subjected to metallurgy, and there is currently no efficient and low-cost treatment method. This not only wastes a large amount of valuable beneficial reagents, but also causes low metallurgical efficiency and damage to metallurgical equipment due to the residual reagents on the surface of the mineral concentrate, such as the poisoning of ion exchange resins or extractants. In addition, the organic matter of the collectors after metallurgy enters the wastewater pool, increasing the cost of wastewater treatment after metallurgy. SUMMARY

[0005] The present application aims to solve the problems of pollution of fatty acid, chelating, phosphonic acid and other reagents to the ecological environment, harm to the efficiency and equipment of metallurgical concentrate, high cost, low efficiency and high cost of smelting enterprise wastewater treatment, and high cost of desorption process.

[0006] The separation of minerals and reagents in flotation concentrate is still an industry blank. The present application realizes the desorption and separation of minerals and reagents in flotation concentrate. However, research has found that in order to successfully realize the desorption of reagents, it is necessary to properly solve the problems of selectivity of reagent desorption, prevention of reagent deactivation, reduction of desorption cost and leaching loss of minerals, etc.

[0007] The technical solution of the present application utilizes the chemical-physical synergistic effect of desorbent and high-speed collision (high-speed stirring) to improve the selective desorption separation of minerals and reagents, and also helps to avoid damage to the reagents and loss of minerals, and realizes the recycling of mineral surface reagents and desorbent. Based on the technical solution of the present application, selective desorption of mineral surface reagents can be realized, filling the technical gap in the industry.

[0008] Technical solution: a method for recycling flotation reagents and desorbent, comprising the following steps:

[0009] (1) adding a desorbent to a mineral slurry of a concentrate with organic anion adsorption reagents remaining on the surface, and desorbing the organic anion adsorption reagents under the assistance of high-speed stirring, and then obtaining a clean mineral surface and a desorption liquid containing beneficial reagents through solid-liquid separation;

[0010] (2) obtaining supernatant and flocculent at the bottom after the desorption liquid containing beneficial reagents obtained in step (1) is allowed to stand and settle, adding a strong acid aqueous solution with a certain concentration to the flocculent at the bottom, and then directly recycling or recycling after saponification for the flotation operation of the target mineral through inorganic ceramic membrane oil-water separation;

[0011] (3) combining the supernatant containing soluble metal salts obtained after oil-water separation and the supernatant obtained in step (2) for reagent desorption operation.

[0012] Further, the beneficial reagents in the desorption liquid containing beneficial reagents obtained in step (1) are one or more of fatty acid collectors, chelating collectors, phosphonic acid collectors, and sulfonic acid collectors.

[0013] The fatty acid collector is one or more of oleic acid and its derivatives, and oxidized paraffin soap.

[0014] The chelating collector is one or more of benzohydroxamic acid, salicylhydroxamic acid, and octylhydroxamic acid.

[0015] The phosphonic acid collector is one or more of styrene phosphonic acid and dodecyl amido bis-methylene phosphonic acid.

[0016] The sulfonic acid collector is one or more of dodecyl sodium sulfonate and dodecyl benzene sodium sulfonate.

[0017] Further, the desorbent in step (1) is a soluble metal salt of a metal ion chloride, a sulfuric acid compound, or a nitric acid compound, wherein:

[0018] The metal ion is one or more of Cu, Fe, Mn, Ba, Pb, Co, and Sn.

[0019] Further, the concentrate in the step (1) is one or more of wolframite, fluorite, cassiterite, rare earth ore, rutile, ilmenite, bauxite, hematite, magnetite, malachite.

[0020] The organic anion adsorption reagent can be ionized in water, and can form organic salt flocculation after adding the desorption agent, so as to realize the separation of the organic salt flocculation and the mineral through solid-liquid separation; the organic salt flocculation after the solid-liquid separation is concentrated and settled, the supernatant is reused, the bottom flocculation is dissolved in strong acid such as hydrochloric acid and nitric acid, and the organic acid is recovered.

[0021] The application benefits from the physical and chemical synergy of the desorption agent and high-speed collision, which helps to improve the separation selectivity of the concentrate and the beneficial reagent.

[0022] It is also found that further controlling the pulp concentration, the amount of the desorption agent, the high-speed collision stirring speed and other conditions in the treatment process helps to further improve the separation selectivity of the mineral and the reagent, helps to improve the reagent recovery rate, avoids the reagent inactivation, and also helps to avoid the mineral loss.

[0023] Further, the amount of the desorption agent in the step (1) is 50-500 g / t, preferably 100-400 g / t, based on the mass (dry mineral amount) of the concentrate with the organic anion adsorption reagent remaining on the surface.

[0024] Further, the stirring speed of the high-speed stirring in the step (1) is 1000-3500 r / min, preferably 2000-3000 r / min.

[0025] Further, the desorption time in the step (1) is 5-35 min, preferably 10-35 min.

[0026] Further, the pH value of the concentrate pulp with the organic anion adsorption reagent remaining on the surface in the desorption process in the step (1) is controlled to be 1-8, preferably 3-7.

[0027] As preferred, the pH adjusting agent is one of hydrochloric acid, sulfuric acid and nitric acid, and the anion of the pH adjusting agent is consistent with that of the desorption agent (soluble metal salt).

[0028] Further, the strong acid in the step (2) is one of hydrochloric acid, sulfuric acid and nitric acid, and the anion of the strong acid is consistent with that of the desorption agent, and the mass concentration of the strong acid aqueous solution is 5%-50%, preferably 10%-50%.

[0029] Further, the beneficial reagent obtained in step (1) is reused for the flotation of the next batch of minerals. The recycling method of the present application can effectively recycle the beneficial reagent on the surface of the floated minerals, reduce the difficulty of subsequent smelting of the minerals and the environmental pressure. Moreover, it is found that the recycling of the recycled beneficial reagent can further improve the flotation effect under the premise of reducing the amount of new reagent and the use amount, such as improving the recovery rate and / or grade of flotation.

[0030] Further, the recycled beneficial reagent and the reduced amount of flotation reagent are mixed and used for the flotation of the next batch of minerals. Based on the planned use amount of the flotation reagent, the recycled beneficial reagent and the reduced amount of flotation reagent are mixed and used, which reduces the planned use amount of the flotation reagent by 10% to 50%.

[0031] The technical scheme of the present application can reduce the amount of reagent through recycling, and not only can improve the flotation recovery rate and grade, but also can improve the performance under the premise of resource saving. In addition, the recycling process of the present application is simple, and the applied equipment is the common equipment in the mineral processing plant, which will not increase excessive investment and can realize the industrial application goal of low investment and high output.

[0032] Beneficial effects: The recycling method of the flotation reagent and the desorption agent disclosed by the present application has the following beneficial effects:

[0033] (1) Selective desorption of the beneficial reagent on the surface of the minerals - in the present application, based on the principle of solubility difference and the synergistic effect of high-strength stirring, the desorption agent competes for the adsorption of the active sites of the metal ions on the surface of the minerals, so that the organic reagent on the surface of the minerals is desorbed and forms organic salt flocculation in the ore pulp solution, which can avoid the inactivation of the reagent and the loss of the minerals, and lay a foundation for providing clean raw materials for subsequent metallurgy of the concentrate and recycling of the collector.

[0034] (2) Recycling of the desorption agent - the supernatant containing the desorption agent obtained after solid-liquid separation can be recycled for desorption operation, thereby reducing the cost of the desorption process.

[0035] (3) The desorbed reagent is recycled and used in the flotation process, thereby realizing the sustainable use of the reagent adsorption-desorption-recycling-adsorption. Not only can the organic collector be recycled and used sustainably, but also the cost of the flotation reagent can be reduced, the wastewater treatment cost of the smelting process can be reduced, the metallurgical efficiency can be improved, the ecological environment can be protected, the win-win of the mineral processing enterprises and the smelting enterprises can be realized, and the balance development of economic benefits and sustainable development can be ensured. DETAILED DESCRIPTION

[0036] The specific embodiments of the present application are described in detail below.

[0037] The ranges disclosed herein are intended to include both endpoints and intervening ranges. For example, a range of 10-50 is intended to include 10, 50, and any intervening range e.g., 10-40 and 20-50. Further, a range of 1-2 is intended to include 1, 2, and any intervening range e.g., 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, the use of "or" means "and / or" unless specifically stated otherwise, e.g., a condition is A or B means A or B or A and B. Unless otherwise stated, all ranges include any and all subranges, e.g., the range 6-10 is inclusive of 8-9. All ranges and amounts are inclusive of the endpoints and units.

[0038] All embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, unless otherwise specified.

[0039] All technical features and optional technical features of the present application can be combined with each other to form new technical solutions, unless otherwise specified.

[0040] Unless otherwise specified, all steps of the present application can be performed in sequence or randomly, and are preferably performed in sequence. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method also comprises step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0041] Unless otherwise specified, "including" and "including" mentioned in the present application means open or closed. For example, "including" and "including" can mean that other components not listed can also be included or contained, or only the listed components can be included or contained.

[0042] Unless otherwise specified, the reaction is carried out at room temperature and normal pressure.

[0043] Unless otherwise specified, all parts or percentages are weight parts or weight percentages.

[0044] In the present application, all the substances used are known substances, which can be purchased or synthesized by known methods.

[0045] In the present application, all the devices or equipment used are conventional devices or equipment known in the field, which can be purchased.

[0046] A recycling method of flotation reagents and desorption agents, the steps are as follows:

[0047] (1) adding a desorption agent to the ore pulp of the concentrate with organic anion adsorption reagents remaining on the surface, and desorbing the organic anion adsorption reagents under the assistance of high-speed stirring, and then obtaining a clean mineral surface and a desorption liquid containing beneficial reagents through solid-liquid separation;

[0048] (2) obtaining supernatant and flocculent at the bottom after the desorption liquid containing beneficial reagents obtained in step (1) is allowed to stand and settle, adding a strong acid aqueous solution with a certain concentration to the flocculent at the bottom, and then directly recycling or recycling after saponification for the flotation operation of the target mineral after oil-water separation through inorganic ceramic membrane;

[0049] (3) combining the supernatant containing soluble metal salts obtained after oil-water separation and the supernatant obtained in step (2) and recycling for reagent desorption operation.

[0050] Further, the beneficial reagents in the desorption liquid containing beneficial reagents obtained in step (1) are one or more of fatty acid collectors, chelating collectors, phosphonic acid collectors, and sulfonic acid collectors;

[0051] The fatty acid collector is one or more of oleic acid and its derivatives, and oxidized paraffin soap;

[0052] The chelating collector is one or more of benzohydroxamic acid, salicylhydroxamic acid, and octylhydroxamic acid;

[0053] The phosphonic acid collector is one or more of styrene phosphonic acid and dodecyl amine bis-methylene phosphonic acid;

[0054] The sulfonic acid collector is one or more of sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.

[0055] Further, the desorption agent in step (1) is a soluble metal salt of a metal ion chloride, a sulfuric acid compound, and a nitric acid compound, wherein:

[0056] The metal ion is one or more of Cu, Fe, Mn, Ba, Pb, Co, and Sn.

[0057] Further, the concentrate in step (1) is one or more of wolframite, fluorite, cassiterite, rare earth ore, rutile, ilmenite, bauxite, hematite, magnetite, malachite.

[0058] Further, the amount of desorption agent in step (1) is 50-500 g / t, preferably 100-400 g / t, based on the mass of the concentrate with the organic anion adsorption reagent remaining on the surface (dry ore mass).

[0059] Further, the stirring speed in step (1) is 1000-3500 r / min, preferably 2000-3000 r / min.

[0060] Further, the desorption time in step (1) is 5-35 min, preferably 10-35 min.

[0061] Further, the pH value of the concentrate pulp with the organic anion adsorption reagent remaining on the surface during the desorption process in step (1) is controlled at 1-8, preferably 3-7.

[0062] As a preference, the pH adjusting agent is one of hydrochloric acid, sulfuric acid, and nitric acid, and the anion of the pH adjusting agent is consistent with that of the desorption agent (soluble metal salt).

[0063] Further, the strong acid in step (2) is one of hydrochloric acid, sulfuric acid, and nitric acid, and the anion of the strong acid is consistent with that of the desorption agent, and the mass concentration of the aqueous strong acid solution is 5%-50%, preferably 10%-50%.

[0064] Further, the beneficial reagent obtained in step (1) is reused for the flotation of the next batch of minerals.

[0065] Further, the recovered beneficial reagent and the reduced amount of flotation reagent are mixed and used for the flotation of the next batch of minerals.

[0066] In one embodiment, a method for recycling flotation reagents and desorption agents, the steps are as follows:

[0067] (1) adding a desorption agent to a concentrate pulp with an organic anion adsorption reagent remaining on the surface, and desorbing the organic anion adsorption reagent under the assistance of high-speed stirring, and then obtaining a clean mineral with a clean surface and a desorption liquid containing beneficial reagents through solid-liquid separation;

[0068] (2) obtaining supernatant and flocculent at the bottom after the desorption liquid containing beneficial reagents obtained in step (1) is allowed to stand and settle, adding an aqueous strong acid solution with a certain concentration to the flocculent at the bottom, and then directly recycling or recycling after saponification for the flotation of the target mineral.

[0069] (3) the supernatant containing soluble metal salt obtained after oil-water separation and the supernatant obtained in step (2) are combined and reused for the desorption of the reagent.

[0070] Further, the beneficial reagent in the desorption solution containing the beneficial reagent obtained in step (1) is a mixture of fatty acid collectors, chelating collectors, phosphonic acid collectors, and sulfonic acid collectors in equal mass ratio.

[0071] The fatty acid collector is oleic acid, oleic acid derivatives, and oxidized paraffin soap in equal mass ratio.

[0072] The chelating collector is benzohydroxamic acid, salicylhydroxamic acid, and octylhydroxamic acid in equal mass ratio.

[0073] The phosphonic acid collector is styrene phosphonic acid.

[0074] The sulfonic acid collector is sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate in equal mass ratio.

[0075] Further, the desorption agent in step (1) is copper chloride. In another embodiment, the desorption agent in step (1) is iron chloride. In another embodiment, the desorption agent in step (1) is manganese chloride. In another embodiment, the desorption agent in step (1) is barium chloride. In another embodiment, the desorption agent in step (1) is cobalt chloride. In another embodiment, the desorption agent in step (1) is tin chloride. In another embodiment, the desorption agent in step (1) is a mixture of copper chloride, iron chloride, manganese chloride, barium chloride, cobalt chloride, and tin chloride in equal mass ratio.

[0076] Further, the concentrate in step (1) is black and white tungsten ore, fluorite ore, cassiterite ore, rare earth ore, rutile ore, ilmenite ore, bauxite ore, hematite ore, magnetite ore, and malachite ore in equal mass ratio.

[0077] Further, the amount of the desorption agent in step (1) is 50 g / t based on the mass of the concentrate with the organic anion adsorption reagent remaining on the surface (dry ore mass). In another embodiment, the amount of the desorption agent in step (1) is 100 g / t based on the mass of the concentrate with the organic anion adsorption reagent remaining on the surface (dry ore mass).

[0078] Further, the stirring speed of the high-speed stirring in step (1) is 1000 r / min. In another embodiment, the stirring speed of the high-speed stirring in step (1) is 2000 r / min.

[0079] Furthermore, the desorption time of the desorption in step (1) is 5 minutes. In another embodiment, the desorption time of the desorption in step (1) is 10 minutes.

[0080] Furthermore, the pH value of the slurry of the concentrate having the organic anion adsorption agent remaining on the surface during the desorption process in step (1) is controlled at 1. In another embodiment, the pH value of the slurry of the concentrate having the organic anion adsorption agent remaining on the surface during the desorption process in step (1) is controlled at 3.

[0081] Preferably, the pH adjuster is hydrochloric acid, and the anion of the pH adjuster is consistent with the anion of the desorbent (soluble metal salt).

[0082] Furthermore, the strong acid in step (2) is hydrochloric acid, and the anion of the strong acid is consistent with the anion of the desorbent, and the mass concentration of the strong acid aqueous solution is 5%. In another embodiment, the strong acid in step (2) is hydrochloric acid, and the anion of the strong acid is consistent with the anion of the desorbent, and the mass concentration of the strong acid aqueous solution is 10%.

[0083] Furthermore, the beneficial agent obtained in step (1) is recycled to the flotation of the next batch of minerals.

[0084] Furthermore, the recovered beneficial reagent and the reduced amount of flotation reagent are mixed and used for the flotation of the next batch of minerals.

[0085] In another embodiment, a method for recycling a flotation agent and a desorbent comprises the following steps:

[0086] (1) adding a desorbent to a slurry of a concentrate having an organic anion adsorption agent remaining on the surface, and desorbing the organic anion adsorption agent with the aid of high-speed stirring, and then obtaining a mineral with a clean surface and a desorption liquid containing a beneficial agent through solid-liquid separation;

[0087] (2) The desorption liquid containing the beneficial agent obtained in step (1) is allowed to settle to obtain a supernatant and flocs at the bottom, and the flocs at the bottom are added with a certain concentration of strong acid aqueous solution, and then directly reused after oil-water separation through an inorganic ceramic membrane or reused for the target mineral flotation operation after alkali saponification; (3) The supernatant containing the soluble metal salt obtained after oil-water separation and the supernatant obtained in step (2) are combined and reused for the agent desorption operation.

[0088] Furthermore, the beneficial agent in the desorption liquid containing the beneficial agent obtained in step (1) is a fatty acid collector.

[0089] The fatty acid-based collector is oleic acid. In another embodiment, the fatty acid-based collector is an oleic acid derivative. In another embodiment, the fatty acid-based collector is oxidized paraffin soap.

[0090] In another embodiment, the beneficial agent in the desorbed solution obtained from step (1) is a chelating collector;

[0091] The chelating collector is benzohydroxamic acid. In another embodiment, the chelating collector is salicylhydroxamic acid. In another embodiment, the chelating collector is octylhydroxamic acid.

[0092] In another embodiment, the beneficial agent in the desorbed solution obtained from step (1) is a phosphonic acid-based collector, which is dodecyl amine bis dimethyl phosphonic acid. In another embodiment, the beneficial agent in the desorbed solution obtained from step (1) is a phosphonic acid-based collector, which is a mixture of equal mass ratio of styrene phosphonic acid, dodecyl amine bis dimethyl phosphonic acid.

[0093] In another embodiment, the beneficial agent in the desorbed solution obtained from step (1) is a sulfonic acid-based collector.

[0094] The sulfonic acid-based collector is sodium dodecyl sulfonate. In another embodiment, the sulfonic acid-based collector is sodium dodecyl benzene sulfonate.

[0095] Further, the desorbing agent in step (1) is copper sulfate. In another embodiment, the desorbing agent in step (1) is ferric sulfate. In another embodiment, the desorbing agent in step (1) is manganese sulfate. In another embodiment, the desorbing agent in step (1) is cobalt sulfate. In another embodiment, the desorbing agent in step (1) is tin sulfate. In another embodiment, the desorbing agent in step (1) is a mixture of equal mass ratio of copper sulfate, ferric sulfate, manganese sulfate, cobalt sulfate and tin sulfate.

[0096] Further, the ore in step (1) is wolframite. In another embodiment, the ore in step (1) is fluorite. In another embodiment, the ore in step (1) is cassiterite. In another embodiment, the ore in step (1) is rare earth ore. In another embodiment, the ore in step (1) is rutile. In another embodiment, the ore in step (1) is ilmenite. In another embodiment, the ore in step (1) is bauxite. In another embodiment, the ore in step (1) is hematite. In another embodiment, the ore in step (1) is magnetite. In another embodiment, the ore in step (1) is malachite.

[0097] Further, the amount of the desorption agent used in step (1) is 500 g / t, based on the mass of the concentrate with the organic anion adsorption agent remaining on the surface (dry mass of the concentrate). In another embodiment, the amount of the desorption agent used in step (1) is 400 g / t, based on the mass of the concentrate with the organic anion adsorption agent remaining on the surface (dry mass of the concentrate).

[0098] Further, the stirring speed of the high-speed stirring in step (1) is 3500 r / min. In another embodiment, the stirring speed of the high-speed stirring in step (1) is 3000 r / min.

[0099] Further, the desorption time in step (1) is 35 min.

[0100] Further, the pH value of the slurry of the concentrate with the organic anion adsorption agent remaining on the surface during the desorption in step (1) is controlled at 8. In another embodiment, the pH value of the slurry of the concentrate with the organic anion adsorption agent remaining on the surface during the desorption in step (1) is controlled at 7.

[0101] Preferably, the pH adjusting agent is sulfuric acid, and the anion of the pH adjusting agent is consistent with the anion of the desorption agent (soluble metal salt).

[0102] Further, the strong acid in step (2) is sulfuric acid, and the anion of the strong acid is consistent with the anion of the desorption agent, and the mass concentration of the aqueous solution of the strong acid is 50%. In another embodiment, the strong acid in step (2) is sulfuric acid, and the anion of the strong acid is consistent with the anion of the desorption agent, and the mass concentration of the aqueous solution of the strong acid is 40%.

[0103] Further, the beneficial agent obtained in step (1) is reused for the flotation of the next batch of minerals.

[0104] Further, the recovered beneficial agent and the reduced amount of the flotation agent are mixed and used for the flotation of the next batch of minerals.

[0105] In yet another embodiment, a method for recycling a flotation agent and a desorption agent, the steps are as follows:

[0106] (1) adding a desorption agent to the slurry of the concentrate with the organic anion adsorption agent remaining on the surface, and desorbing the organic anion adsorption agent under the assistance of high-speed stirring, and then obtaining a clean mineral with the surface and a desorption liquid containing a beneficial agent through solid-liquid separation;

[0107] (2) The supernatant and the flocculent at the bottom of the desorption solution containing the beneficial reagent obtained in step (1) are allowed to stand and settle, a strong acid aqueous solution of a certain concentration is added to the flocculent at the bottom, and then the inorganic ceramic membrane is used to separate the oil and water, and the separated solution is directly reused or is used for the flotation of the target mineral after being saponified with an alkali;

[0108] (3) The supernatant containing the soluble metal salt obtained after the oil and water separation and the supernatant obtained in step (2) are combined and used for the reagent desorption operation.

[0109] Further, the beneficial reagent in the desorption solution containing the beneficial reagent obtained in step (1) is a fatty acid collector and a chelate collector in equal mass ratio.

[0110] The fatty acid collector is oleic acid and oxidized paraffin soap in equal mass ratio.

[0111] The chelate collector is benzohydroxamic acid and salicylhydroxamic acid in equal mass ratio.

[0112] Further, the desorption agent in step (1) is copper nitrate. In another embodiment, the desorption agent in step (1) is iron nitrate. In another embodiment, the desorption agent in step (1) is manganese nitrate. In another embodiment, the desorption agent in step (1) is barium nitrate. In another embodiment, the desorption agent in step (1) is lead nitrate. In another embodiment, the desorption agent in step (1) is cobalt nitrate. In another embodiment, the desorption agent in step (1) is a mixture of copper nitrate, iron nitrate, manganese nitrate, barium nitrate, lead nitrate and cobalt nitrate in equal mass ratio.

[0113] Further, the concentrate in step (1) is wolframite, fluorite and cassiterite in equal mass ratio.

[0114] Further, the amount of the desorption agent in step (1) is 300 g / t based on the mass of the concentrate with the organic anion adsorption reagent remaining on the surface (dry concentrate).

[0115] Further, the stirring speed of the high-speed stirring in step (1) is 2500 r / min.

[0116] Further, the desorption time in step (1) is 20 min.

[0117] Further, the pH value of the concentrate pulp with the organic anion adsorption reagent remaining on the surface during the desorption in step (1) is controlled at 5.

[0118] As a preferred embodiment, the pH adjuster is nitric acid, and the anion of the pH adjuster is consistent with the anion of the desorption agent (soluble metal salt).

[0119] Further, the strong acid in step (2) is nitric acid, and the anion of the strong acid is consistent with the anion of the desorbent, and the mass concentration of the strong acid aqueous solution is 35%.

[0120] Further, the beneficial reagent obtained in step (1) is reused for the flotation of the next batch of minerals.

[0121] Still further, the recovered beneficial reagent and the reduced amount of the flotation reagent are mixed and used for the flotation of the next batch of minerals.

[0122] Example 1

[0123] A scheelite in a certain concentrator in Chenzhou, Hunan, has a WO3 grade of 0.40%, and the gangue mainly includes garnet, quartz, pyroxene, and a small amount of fluorite and calcite.

[0124] The scheelite described above is subjected to the technical scheme of the present application, and the specific steps are as follows:

[0125] The scheelite concentrate slurry obtained from the concentrator is placed in a stirrer, the slurry concentration is adjusted to 25%, the pH value is 5.0, the stirring speed is 2700 r / min, then the desorbent copper sulfate 100 g / t (for the scheelite concentrate) is added, the solid-liquid separation is performed after stirring for 15 min, the concentration 30% sulfuric acid is added in the turbidity containing oleate flocculation until the flocculation disappears, and after standing for 10 min, the oleic acid is obtained through the inorganic ceramic membrane, and the filtrate under the filter membrane is returned to the collector desorption process for recycling.

[0126] The obtained oleic acid is added with sodium hydroxide to form sodium oleate, which is returned to the scheelite flotation process. The dosage of the oleate sodium without the collector reuse is 250 g / t, and the dosage of the depressant water glass is 3 kg / t, and the flotation results are shown in Table 1. After adding the desorbed collector, the dosage of the oleate sodium is reduced to 180 g / t, and the other flotation conditions are consistent, and the flotation results are shown in Table 1.

[0127] Table 1

[0128]

[0129] As shown by the results in Table 1, after adding the collector desorbed from the surface of the scheelite concentrate, the grade and recovery of the scheelite concentrate are increased, and the dosage of the collector is reduced by 28%.

[0130] Example 2

[0131] A tin ore in a certain concentrator in Gejiu, Guangxi, is subjected to flotation, and the Sn grade is 0.65%, and the gangue mainly includes quartz, feldspar, and mica.

[0132] The tin ore described above is subjected to the technical scheme of the present application, and the specific steps are as follows:

[0133] The tin concentrate slurry obtained from the concentrator is placed in a stirrer, and the slurry concentration is adjusted to 30%, the pH value is 4.0, and the stirring speed is 2800r / min. Then, 360g / t of lead nitrate as a desorbent (for tin concentrate) is added. After stirring for 20 minutes, the solid-liquid separation is carried out. 20% nitric acid is added to the turbid liquid containing benzohydroxamate flocs until the flocs disappear. After standing for 10 minutes, benzohydroxamic acid is obtained through an inorganic ceramic membrane, and the clear liquid under the filter membrane is returned to the collector desorption process for recycling.

[0134] The recovered benzohydroxamic acid can be directly recycled into the cassiterite flotation process. The roughing benzohydroxamic acid dosage for no collector recycling was 2200 g / t, and the inhibitor-modified water glass dosage was 300 g / t. The flotation results are shown in Table 2. After adding the desorbed collector, the benzohydroxamic acid dosage was reduced to 1430 g / t. Other flotation conditions remained the same, and the flotation results are shown in Table 2.

[0135] Table 2

[0136]

[0137] From the results in Table 2, it can be seen that after adding the collector that desorbs from the surface of the tin concentrate, the grade and recovery rate of the tin concentrate increase, and the amount of collector used is reduced by 35%.

[0138] Example 3

[0139] Flotation was carried out on a rutile mine in Zaoyang, Hubei, where the TiO2 grade was 3.45% and the gangue was mainly composed of amphibole, garnet, feldspar, mica, clay, quartz, etc.

[0140] The technical solution of the present invention is adopted for the above-mentioned rutile ore, and the specific steps are as follows:

[0141] The titanium concentrate slurry obtained from the concentrator is placed in a stirrer, and the slurry concentration is adjusted to 25%, the pH value is 7.0, and the stirring speed is 2800r / min. Then, 170g / t of ferric chloride (for tin concentrate) as a desorbent is added. After stirring for 20 minutes, the solid-liquid separation is carried out. 10% hydrochloric acid is added to the turbid liquid containing styrene phosphonate flocs until the flocs disappear. After standing for 10 minutes, styrene phosphonic acid is obtained through an inorganic ceramic membrane, and the clear liquid under the filter membrane is returned to the collector desorption process for recycling.

[0142] The obtained styrenephosphonic acid can be directly reused in the cassiterite flotation process. The roughing styrenephosphonic acid dosage for non-collector recycling was 1200 g / t, and the inhibitor sodium fluorosilicate was 1000 g / t. The flotation results are shown in Table 3. After adding the desorbed collector, the styrenephosphonic acid dosage was reduced to 840 g / t. Other flotation conditions remained the same, and the flotation results are shown in Table 3.

[0143] Table 3

[0144]

[0145]

[0146] From the results of Table 3, it can be seen that after adding the collector desorbed from the surface of the titanium concentrate, the grade and recovery of the titanium rough concentrate are increased, especially the recovery, and the dosage of the collector is reduced by 30%.

[0147] Comparative Example 1

[0148] Except that the dosage of the desorbent copper sulfate is 20 g / t, other conditions are the same as in Example 1. After reusing the desorbed collector, the grade and recovery of the tungsten rough concentrate are 1.88% and 67.92%, respectively, which are lower than the results in Table 1, indicating that the dosage of the desorbent has a greater effect on the desorption efficiency of the collector.

[0149] Comparative Example 2

[0150] Except that the concentration of the strong acid is 70%, other conditions are the same as in Example 1. After reusing the desorbed collector, the grade and recovery of the tungsten rough concentrate are 2.03% and 74.08%, respectively, which are unexpectedly lower than the results in Table 1, indicating that the concentration of the strong acid has a greater effect on the reuse efficiency of the collector.

[0151] Comparative Example 3

[0152] Except that the stirring speed of the slurry in the desorption process is 500 r / min, other conditions of the desorption process of the collector are the same as in Example 2. After reusing the desorbed collector, the grade and recovery of the tin rough concentrate are 6.25% and 67.80%, respectively, which are lower than the results in Table 2, indicating that the stirring speed of the slurry has a greater effect on the desorption efficiency of the collector.

[0153] Comparative Example 4

[0154] Except that the stirring speed of the slurry in the desorption process is 500 r / min, other conditions of the desorption process of the collector are the same as in Example 2. After reusing the desorbed collector, the grade and recovery of the tin rough concentrate are 6.25% and 67.80%, respectively, which are lower than the results in Table 2, indicating that the stirring speed of the slurry has a greater effect on the desorption efficiency of the collector.

[0155] Comparative Example 5

[0156] Except that the desorbent is calcium chloride, other conditions of the desorption process of the collector are the same as in Example 3. After reusing the desorbed collector, the grade and recovery of the titanium rough concentrate are 14.85% and 70.92%, respectively, which are lower than the results in Table 3, indicating that the desorbent has a greater effect on the desorption efficiency of the collector.

[0157] By the means of the application, based on the solubility of different organic acid salt flocculation, the physical and chemical synergistic effect of suitable desorbent type and dosage, pulp pH value, strong acid concentration, pulp stirring speed, etc. can realize efficient desorption and reuse of concentrate surface collector.

[0158] The above has described the embodiments of the application in detail. However, the application is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the application.

Claims

1. A method for recycling flotation reagents and desorbents, characterized in that: Here are the steps: (1) adding a desorbent to a slurry of a concentrate having an organic anion adsorption agent remaining on the surface, and desorbing the organic anion adsorption agent with the aid of high-speed stirring, and then obtaining a mineral with a clean surface and a desorption liquid containing a beneficial agent through solid-liquid separation; (2) The desorption liquid containing the beneficial agent obtained in step (1) is allowed to settle to obtain a supernatant and flocs at the bottom, a certain concentration of strong acid aqueous solution is added to the flocs at the bottom, and then the flocs are directly reused after oil-water separation through an inorganic ceramic membrane or reused for the target mineral flotation operation after alkali saponification; (3) After oil-water separation, the supernatant containing the soluble metal salt is obtained and the supernatant obtained in step (2) is combined and reused for the reagent desorption operation, wherein: The beneficial agent in the desorption liquid containing the beneficial agent obtained in step (1) is one or more of a fatty acid collector, a chelating collector, a phosphonic acid collector, and a sulfonic acid collector; The fatty acid collector is one or more of oleic acid and its derivatives, and oxidized paraffin soap; The chelating collector is one or more of benzohydroxamic acid, salicylic hydroxamic acid, and octylhydroxamic acid; The phosphonic acid collector is one or more of styrenephosphonic acid and dodecylaminobis(methylenephosphonic acid); The sulfonic acid collector is one or more of sodium dodecylsulfonate and sodium dodecylbenzenesulfonate; The desorbent described in step (1) is a soluble metal salt of a chloride, a sulfate compound, or a nitric acid compound of a metal ion, wherein: The metal ion is one or more of Cu, Fe, Mn, Ba, Pb, Co, and Sn; The pH value of the slurry of the concentrate with organic anion adsorption agent remaining on the surface during the desorption process in step (1) is controlled to be 1-8.

2. The method for recycling a flotation agent and a desorbent according to claim 1, wherein: The concentrate described in step (1) is one or more of tungsten ore, fluorite, cassiterite, rare earth ore, rutile, ilmenite, bauxite, hematite, magnetite, and malachite.

3. The method for recycling a flotation agent and a desorbent according to claim 1, wherein: Based on the mass of the concentrate with organic anion adsorption agent remaining on the surface, the amount of the desorbent in step (1) is 50-500 g / t.

4. A method for recycling flotation reagents and desorbents as claimed in claim 3, characterized in that: Based on the mass of the concentrate with organic anion adsorption agent remaining on the surface, the amount of the desorbent in step (1) is 100-400 g / t.

5. The method for recycling a flotation agent and a desorbent according to claim 1, wherein: The stirring speed of the high-speed stirring in step (1) is 1000-3500 r / min, and / or The desorption time of the desorption in step (1) is 5 to 35 minutes.

6. A method for recycling flotation reagents and desorbents as claimed in claim 5, characterized in that: The stirring speed of the high-speed stirring in step (1) is 2000-3000 r / min, and / or The desorption time of the desorption in step (1) is 10 to 35 minutes.

7. The method for recycling flotation reagents and desorbents according to claim 1, wherein: The pH value of the slurry of the concentrate with organic anion adsorption agent remaining on the surface during the desorption process in step (1) is controlled to be 3-7.

8. The method for recycling flotation reagents and desorbents according to claim 1, wherein: The pH adjuster is one of hydrochloric acid, sulfuric acid, and nitric acid, and the anion of the pH adjuster is consistent with the anion of the desorbent.

9. The method for recycling flotation reagents and desorbents according to claim 1, wherein: The strong acid in step (2) is one of hydrochloric acid, sulfuric acid and nitric acid, and the anion of the strong acid is consistent with the anion of the desorbent, and the mass concentration of the strong acid aqueous solution is 5% to 50%.

10. A method for recycling flotation reagents and desorbents according to claim 9, characterized in that: The strong acid in step (2) is one of hydrochloric acid, sulfuric acid and nitric acid, and the anion of the strong acid is consistent with the anion of the desorbent, and the mass concentration of the strong acid aqueous solution is 10% to 40%.

11. The method for recycling flotation reagents and desorbents according to claim 1, wherein: The beneficial agent obtained in step (1) is recycled to the flotation of the next batch of minerals.

12. A method for recycling flotation reagents and desorbents according to claim 11, characterized in that: The beneficial agent recovered in step (1) is mixed with the reduced amount of flotation agent and used for the flotation of the next batch of minerals.

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