Method for removing flotation reagents from potassium extraction tailings

Abstract

The application discloses a method for removing flotation reagents in potassium extraction tail liquid. The method comprises the following steps: uniformly mixing a photocatalyst, an organic weak acid and a magnesium salt solution to form a mixed slurry; uniformly mixing active magnesium oxide and a nucleating agent to form a mixed powder; uniformly mixing the mixed powder, a pore-forming agent and the mixed slurry, and then performing reaction molding to obtain a magnesium-based porous adsorption-photocatalytic material; fully contacting the magnesium-based porous adsorption-photocatalytic material with the potassium extraction tail liquid, so that the flotation reagents are adsorbed and enriched on the surface and / or inside of the magnesium-based porous adsorption-photocatalytic material, and then performing solid-liquid separation; and performing photocatalytic oxidation degradation treatment on the separated solid, so as to remove the flotation reagents. The removal method provided by the application can continuously remove the flotation reagents in the potassium extraction tail liquid in a circulation mode, is flexible in scale and easy to enlarge, does not cause secondary pollution to the tail liquid system, and can be used to solve the purification problem of the flotation reagents in the potassium extraction tail liquid.

Description

Technical Field

[0001] This invention relates to a method for removing flotation reagents, and more particularly to a method for removing flotation reagents from potassium extraction tail liquor by means of adsorption enrichment-solid-liquid separation-photocatalytic oxidation degradation, belonging to the field of potassium extraction tail liquor purification technology. Background Technology

[0002] Flotation reagents used in potash fertilizer production generally include collectors, depressants, and frothers. Collectors are classified into cationic and anionic collectors. Cationic collectors are diverse, including fatty amines, aminoamides, ether amines, quaternary ammonium salts, and alkylmorpholines. Currently, most salt lake potash fertilizer production both domestically and internationally uses octadecylamine and dodecylmorpholine as collectors. Anionic collectors are mainly sodium dodecyl sulfate, primarily used for the flotation of sulfate-type potassium salts such as soft potassium magnesium sulfate, potassium sulfate, and esperidin. Frothing agents mainly include alcohols, ethers, and esters, such as terpineol, polyvinyl alcohol, methyl pentanol, 3-methyl-1,3-butanediol, heptyl ether, polyethylene glycol dimethyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and methyl laurate. These flotation reagents tend to accumulate in the tailings of potash fertilizer production, negatively impacting the comprehensive utilization of potassium, lithium, sodium, and magnesium resources in the tailings. Therefore, it is essential to remove flotation reagents from the potassium extraction tailings.

[0003] Generally, methods for treating organic pollutants in industrial and domestic wastewater include microbial degradation, coagulation, adsorption, membrane filtration, oxidation, and photocatalytic degradation. Microbial degradation involves adding microorganisms that utilize their metabolic processes to degrade organic matter. In coagulation (flocculation), coagulants (such as polyaluminum chloride, aluminum sulfate, and polyacrylamide) are added to cause organic matter to precipitate and separate from the liquid phase. Adsorption methods for treating organic wastewater use hydrophobic resins, activated carbon, silica, or molecular sieves to adsorb and retain the organic matter. Membrane filtration utilizes membrane pore size to retain organic matter. Oxidation methods introduce oxidants (such as ozone, hydrogen peroxide, and chlorine) into the system to oxidize and decompose organic matter. Photocatalytic degradation involves adding a photocatalyst to the system, introducing light energy to catalyze the production of highly efficient oxidizing agents (such as hydroxyl radicals and oxygen radicals), thereby oxidizing and decomposing organic matter.

[0004] However, the above methods all have some drawbacks. For example, the microorganisms used in microbial degradation methods have difficulty surviving in high-salt environments and are not suitable for potassium extraction tailings. Coagulation, adsorption, and membrane methods involve coagulants, adsorbents, and membranes enriched with organic matter, which are difficult to regenerate, resulting in high treatment costs. Oxidation methods require the introduction of oxidants such as ozone, hydrogen peroxide, and chlorine into the system, inevitably leaving residues, and have limited oxidation efficiency. In photocatalytic degradation, photocatalyst materials are usually in powder form, making them difficult to recover after addition to the system, thus causing secondary pollution. Therefore, effective removal methods for flotation reagents in potassium extraction tailings are rarely reported. Summary of the Invention

[0005] The main objective of this invention is to provide a method for removing flotation reagents from potassium extraction tail liquor by means of adsorption enrichment-solid-liquid separation-photocatalytic oxidation degradation, so as to solve the purification problem of flotation reagents in potassium extraction tail liquor.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0007] This invention provides a method for removing flotation reagents from potassium extraction tailings, comprising:

[0008] The photocatalyst, organic weak acid, and magnesium salt solution are uniformly mixed to form a mixed slurry;

[0009] The active magnesium oxide and nucleating agent are mixed evenly to form a mixed powder;

[0010] The mixed powder, pore-forming agent and mixed slurry are mixed evenly, and then reacted and shaped to obtain magnesium-based porous adsorption-photocatalytic material;

[0011] The magnesium-based porous adsorption-photocatalytic material is brought into full contact with the potassium extraction tailings that may contain flotation reagents, so that the flotation reagents are adsorbed and enriched on the surface and / or inside of the magnesium-based porous adsorption-photocatalytic material, and then solid-liquid separation is performed.

[0012] The separated solids are subjected to photocatalytic oxidation degradation treatment to remove flotation reagents.

[0013] In some embodiments, the nucleating agent includes basic magnesium sulfate and / or basic magnesium chloride, wherein the basic magnesium sulfate is 5Mg(OH)2·MgSO4·7H2O (5·1·7 phase) and the basic magnesium chloride is 5Mg(OH)2·MgCl2·3H2O (5·1·3 phase).

[0014] Compared with the prior art, the beneficial effects of the present invention are at least as follows:

[0015] The method for removing flotation reagents from potassium extraction tailings provided by this invention utilizes an adsorption-enrichment-solid-liquid separation-photocatalytic oxidation degradation technology. After solid-liquid separation, the flotation reagents enriched on the solid are photocatalytically degraded. Compared to dispersing the photocatalyst in the tailings for photocatalysis, this method offers higher catalytic efficiency, and some intermediate products during degradation do not enter the tailings, thus avoiding secondary pollution. Furthermore, the degradation products on the material after photocatalytic oxidation degradation can be removed by washing with water, blowing air, or vacuum drying, while also regenerating the adsorption function. This enables the continuous and cyclical removal of flotation reagents from potassium extraction tailings. The entire process does not require the addition of oxidants or chemical desorbents to the system, making it green, efficient, flexible in scale, and easy to scale up. It can be used to solve the purification problem of flotation reagents in potassium extraction tailings. Detailed Implementation

[0016] In view of the shortcomings of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The main feature is a method of adsorption enrichment-solid-liquid separation-photocatalytic oxidation degradation for removing flotation reagents from potassium extraction tailings, thereby solving the purification problem of flotation reagents in potassium extraction tailings. The following will further explain and illustrate this technical solution, its implementation process, and its principles.

[0017] One aspect of the present invention provides a method for removing flotation reagents from potassium extraction tailings, comprising:

[0018] The photocatalyst, organic weak acid, and magnesium salt solution are uniformly mixed to form a mixed slurry;

[0019] The active magnesium oxide and nucleating agent are mixed evenly to form a mixed powder;

[0020] The mixed powder, pore-forming agent and mixed slurry are mixed evenly, and then reacted and shaped to obtain magnesium-based porous adsorption-photocatalytic material;

[0021] The magnesium-based porous adsorption-photocatalytic material is brought into full contact with the potassium extraction tailings that may contain flotation reagents, so that the flotation reagents are adsorbed and enriched on the surface and / or inside of the magnesium-based porous adsorption-photocatalytic material, and then solid-liquid separation is performed.

[0022] The separated solids are subjected to photocatalytic oxidation degradation treatment to remove flotation reagents.

[0023] The main technical concept of this invention is as follows: First, a magnesium-based porous adsorption-photocatalytic material is prepared. The flotation reagent in the potassium extraction tail liquid is enriched on the magnesium-based porous adsorption-photocatalytic material through adsorption. Then, solid-liquid separation is performed. The solid material is irradiated with a certain light source to perform photocatalytic oxidation degradation of the adsorbed flotation reagent.

[0024] The preparation principle of the magnesium-based porous adsorption-photocatalytic material of the present invention may be as follows: (1) In the magnesium salt solution, the metal oxide is surface activated under the action of organic weak acid and is fully dispersed; (2) The nucleating agent is fully mixed with active magnesium oxide to facilitate the full occurrence of nucleation reaction and rapid mass transfer; (3) Magnesium oxide reacts with water to form hydroxide ions, and magnesium sulfate or magnesium chloride reacts with hydroxide ions under the induction of nucleating agent to generate 5·1·7 phase or 5·1·3 phase, while growing eutectic with metal oxide, and solidifying and forming under the action of pore-forming agent.

[0025] In some preferred embodiments, the photocatalyst includes TiO2, ZnO, CuO, SnO2, FeO, and F. e2 The ingredients are any one or a combination of two or more of O3, MnO, CoO, NiO, Bi2O3, WO3, CeO2, etc., and are not limited to these, with a mass fraction of 5 to 20 parts.

[0026] In some preferred embodiments, the organic weak acid includes any one or a combination of two of the following: carboxylic acid R(COOH)n and hydroxycarboxylic acid HOR(COOH)n, wherein R is a hydrocarbon group, n is an integer greater than or equal to 1, and its mass fraction is 0.5 to 5 parts.

[0027] Furthermore, the organic weak acid can be any one or a combination of two or more of formic acid, itaconic acid, malic acid, tannic acid, salicylic acid, succinic acid, gluconic acid, lactic acid, maleic acid, glucoheponic acid, etc., and is not limited thereto.

[0028] The addition of a weak organic acid in this invention has two functions: First, it provides a certain amount of hydrogen ions, which react with the metal oxide to activate its surface and promote the eutectic growth of the 5.1.7 or 5.1.3 phase with the metal oxide, thus ensuring the charge conduction performance of the material and ensuring that the metal oxide is evenly and firmly dispersed; Second, the organic acid anions are adsorbed on the surface of magnesium oxide, inhibiting the production of magnesium hydroxide and promoting the growth of the 5.1.7 or 5.1.3 phase.

[0029] In some preferred embodiments, the magnesium salt solution comprises magnesium salt and water, wherein the magnesium salt includes magnesium sulfate and / or magnesium chloride, etc., in parts by mass of 5 to 25, and the water in parts by mass of 50 to 89.5.

[0030] In some preferred embodiments, the mass ratio of the photocatalyst, the organic weak acid, the magnesium salt, and water is (5-20):(0.5-5):(5-25):(50-89.5).

[0031] In some preferred embodiments, the nucleating agent includes powdered basic magnesium sulfate and / or powdered basic magnesium chloride, wherein the basic magnesium sulfate is (5Mg(OH)2·MgSO4·7H2O), the basic magnesium chloride is 5Mg(OH)2·MgCl2·3H2O, and the mass fractions are 5 to 15 parts, and the mass fractions of the active magnesium oxide are 85 to 95 parts.

[0032] In some preferred embodiments, the mass ratio of the nucleating agent to active magnesium oxide is 5–15:85–95.

[0033] In some preferred embodiments, the pore-forming agent includes any one or a combination of two or more of hydrogen peroxide (30% hydrogen peroxide), surfactant, protein solution, etc., and is not limited thereto, and its mass fraction is 0.5 to 5 parts.

[0034] Furthermore, the surfactant may be any one or a combination of two or more of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium lignosulfonate, calcium stearate, polyvinyl alcohol, lauroyl glutamic acid, sodium octadecyl sulfate, hexadecyltrimethylammonium bromide, etc., but is not limited thereto.

[0035] In some preferred embodiments, the mass ratio of the mixed powder, the pore-forming agent, and the mixed slurry is (20-50):(0.5-5):(45-79.5), that is, the mass fraction of the pore-forming agent is 0.5-5 parts, the mass fraction of the mixed powder is 20-50 parts, and the mass fraction of the mixed slurry is 45-79.5 parts.

[0036] In some preferred embodiments, the reaction molding temperature is room temperature, the time is basically maintained at more than 24 hours, and it is aged for more than 2 days before it can be used.

[0037] In summary, the magnesium-based porous adsorption-photocatalytic material prepared by this invention is easy to mold, has good mechanical strength, and facilitates solid-liquid separation. Furthermore, the magnesium-based porous adsorption-photocatalytic material prepared by this invention exhibits excellent photocatalytic activity.

[0038] In some preferred embodiments, the solid-liquid ratio of the magnesium-based porous adsorption-photocatalytic material mixed with the potassium extraction tailings is 1–50 g / L. The magnesium-based porous adsorption-photocatalytic material prepared by this invention also has a mesoporous structure, which can effectively adsorb flotation reagents, and it has good salt tolerance, making it suitable for high-salt systems.

[0039] Furthermore, the adsorption time is 0.5 to 8 hours.

[0040] As a preferred embodiment, the potassium extraction tailings include positive flotation tailings or reverse flotation tailings, etc.

[0041] As a preferred embodiment, the removal method includes: irradiating the separated solids to perform photocatalytic oxidation degradation; wherein the irradiation treatment uses an irradiation wavelength of 250–650 nm and an irradiation time of 0.5–24 h. This invention utilizes an adsorption-enrichment-solid-liquid separation-photocatalytic oxidation degradation technology to perform photocatalytic degradation of the flotation reagent enriched on the solid after solid-liquid separation. Compared to dispersing the photocatalyst in the tail liquid for photocatalysis, this method offers higher catalytic efficiency, and some intermediate products during degradation do not enter the tail liquid, thus avoiding secondary pollution.

[0042] As a preferred embodiment, the removal method further includes: cleaning and drying the magnesium-based porous adsorption-photocatalytic material obtained after photocatalytic oxidation degradation treatment, and then using it again for adsorption and enrichment of flotation reagents. The drying can be done by forced air or vacuum drying, and the drying temperature is 25–60°C.

[0043] This invention utilizes an adsorption-enrichment-solid-liquid separation-photocatalytic oxidation degradation technology. After photocatalytic oxidation degradation, the degradation products on the material can be removed by washing with water, blowing air or vacuum drying. At the same time, the adsorption function is regenerated, thereby realizing the continuous and cyclical removal of flotation reagents from potassium extraction tail liquid. The entire process does not require the addition of oxidants or chemical desorbents to the system, making it green, efficient, flexible in scale, and easy to scale up.

[0044] In some more specific embodiments, the method for removing flotation reagents from potassium extraction tailings of the present invention includes the following steps:

[0045] (1) Preparation of magnesium-based porous adsorption-photocatalytic material: Powdered photocatalyst, organic weak acid and magnesium sulfate or magnesium chloride aqueous solution are mixed to form a uniform mixed slurry. Active magnesium oxide and nucleating agent are mixed to form a uniform mixed powder. The mixed powder and pore-forming agent are added to the mixed slurry and mixed evenly. The mixture is then reacted and shaped in a mold to obtain magnesium-based porous adsorption-photocatalytic material.

[0046] (2) Adsorption and enrichment: The magnesium-based porous adsorption-photocatalytic material is fully contacted with the potassium extraction tail liquid containing flotation reagent in a certain proportion to carry out the adsorption and enrichment of flotation reagent. The solid-liquid ratio is 1-50 g / L and the adsorption time is 0.5-8 h.

[0047] The potassium extraction tailings include positive flotation tailings and reverse flotation tailings.

[0048] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0049] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalytic material separated in step (3) is irradiated with light of a certain wavelength. The wavelength of the irradiation light is 250-650 nm, and the irradiation time is 0.5-24 h.

[0050] (5) After the magnesium-based porous adsorption-photocatalytic material reacted in step (4) is washed with water and dried by blowing or vacuum, steps (2) to (4) are repeated. The blowing or vacuum drying temperature is 25-60℃.

[0051] Furthermore, after employing the removal method of the present invention, the removal rate of flotation reagents in the potassium extraction tailings is above 50%. The adsorption of the material in the present invention mainly relies on electrostatic and hydrophobic interactions, and is applicable to conventional flotation reagents.

[0052] In summary, the removal method provided by this invention can continuously remove flotation reagents from potassium extraction tailings, is flexible in scale and easy to scale up, and does not cause secondary pollution to the tailings system. It can be used to solve the purification problem of flotation reagents in potassium extraction tailings.

[0053] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be further described in detail below with reference to several preferred embodiments. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. For test methods in the following embodiments where specific conditions are not specified, the test methods in the embodiments are all performed under conventional conditions. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0054] All reagents used in the following examples are of analytical grade.

[0055] Example 1

[0056] (1) Preparation of magnesium-based porous adsorption-photocatalytic material: 5 parts of powdered TiO2, 0.5 parts of formic acid, 5 parts of magnesium sulfate, and 89.5 parts of water were mixed and stirred thoroughly to form a uniform slurry; 85 parts of active magnesium oxide and 15 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) were mixed and stirred thoroughly to form a uniform powder; 20 parts of the mixed powder and 0.5 parts of 30% hydrogen peroxide were added to 79.5 parts of the mixed slurry and stirred thoroughly and quickly mixed evenly. The mixture was then packaged into a 4cm×4cm×1cm mold for reaction molding to obtain a basic magnesium sulfate-TiO2 composite sheet.

[0057] (2) Adsorption and enrichment: The basic magnesium sulfate-TiO2 composite sheet was fully contacted with the positive flotation potassium extraction tail liquid containing flotation reagent at a solid-liquid ratio of 1 g / L to carry out the adsorption and enrichment of flotation reagent for 5 h.

[0058] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0059] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-350 nm for 6 h.

[0060] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried at 60°C by forced air drying. Then, steps (2) to (4) are repeated. After 5 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from the positive flotation is 85.3%.

[0061] Example 2

[0062] (1) Preparation of magnesium-based porous adsorption-photocatalytic materials: 10 parts of powdered Bi2O3, 2.5 parts of malic acid, 25 parts of magnesium chloride, and 62.5 parts of water were mixed and stirred thoroughly to form a uniform slurry; 90 parts of active magnesium oxide and 10 parts of powdered basic magnesium chloride 5Mg(OH)2·MgCl2·3H2O were mixed and stirred thoroughly to form a uniform powder; 40 parts of the mixed powder and 3 parts of sodium lauryl sulfate were added to 57 parts of the mixed slurry and stirred thoroughly and quickly until uniformly mixed, then dispensed into 4cm containers. 2 The reaction was carried out in a 0.5cm mold to obtain a basic magnesium chloride-Bi2O3 composite sheet.

[0063] (2) Adsorption enrichment: The basic magnesium chloride-Bi2O3 composite tablets were fully contacted with the reverse flotation potassium extraction tail liquid containing flotation reagents at a solid-liquid ratio of 10 g / L to carry out the adsorption enrichment of flotation reagents for 8 hours.

[0064] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0065] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-600 nm for 12 h.

[0066] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried under vacuum at 40°C. Then, steps (2) to (4) are repeated. After 10 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from the reverse flotation is 75.3%.

[0067] Example 3

[0068] (1) Preparation of magnesium-based porous adsorption-photocatalytic material: 20 parts of powdered ZnO, 5 parts of itaconic acid, 10 parts of magnesium sulfate, and 65 parts of water were mixed and stirred thoroughly to form a uniform slurry; 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) were mixed and stirred thoroughly to form a uniform powder; 50 parts of the mixed powder and 5 parts of sodium dodecylbenzenesulfonate were added to 45 parts of the mixed slurry and stirred thoroughly and quickly mixed evenly. The mixture was then packaged into a 4cm×4cm×4cm mold for reaction molding, ground, and passed through a 5-60 mesh sieve to obtain basic magnesium sulfate-ZnO composite particles.

[0069] (2) Adsorption enrichment: Basic magnesium sulfate-ZnO composite particles are fully contacted with the reverse flotation potassium extraction tail liquid containing flotation reagent at a solid-liquid ratio of 50 g / L to carry out the adsorption enrichment of flotation reagent for 5 h.

[0070] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0071] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-380 nm for 24 h.

[0072] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried under vacuum at 25°C. Then, steps (2) to (4) are repeated. After 20 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from the reverse flotation is 72.0%.

[0073] Example 4

[0074] (1) Preparation of magnesium-based porous adsorption-photocatalytic material: 12 parts of powdered WO3, 5 parts of powdered ZnO, 3 parts of tannic acid, 10 parts of magnesium sulfate, and 70 parts of water were mixed and stirred thoroughly to form a uniform slurry; 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7(5Mg(OH)2·MgSO4·7H2O) were mixed and stirred thoroughly to form a uniform powder; 50 parts of the mixed powder and 1 part of sodium dodecylbenzenesulfonate were added to 49 parts of the mixed slurry and stirred thoroughly and quickly mixed evenly. The mixture was then packaged into a 4cm×4cm×4cm mold for reaction molding, ground, and passed through a 5-60 mesh sieve to obtain basic magnesium sulfate-WO3 / ZnO composite particles.

[0075] (2) Adsorption enrichment: Basic magnesium sulfate-WO3 / ZnO composite particles are fully contacted with the positive flotation potassium extraction tail liquid containing flotation reagent at a solid-liquid ratio of 20g / L to carry out the adsorption enrichment of flotation reagent for 4h.

[0076] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0077] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-650 nm for 12 h.

[0078] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried at 35°C by forced air drying. Then, steps (2) to (4) are repeated. After 17 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from the positive flotation is 70.6%.

[0079] Example 5

[0080] (1) Preparation of magnesium-based porous adsorption-photocatalytic materials: 10 parts of powdered CuO, 5 parts of powdered NiO, 3 parts of salicylic acid, 20 parts of magnesium chloride, and 62 parts of water were mixed and stirred thoroughly to form a uniform slurry; 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium chloride 5Mg(OH)2·MgCl2·3H2O were mixed and stirred thoroughly to form a uniform powder; 40 parts of the mixed powder and 2 parts of sodium lignosulfonate were added to 58 parts of the mixed slurry and stirred thoroughly and quickly mixed evenly, then dispensed into 4cm containers. 2 The reaction is formed in a 0.5cm mold to obtain a basic magnesium chloride-CuO / NiO composite sheet.

[0081] (2) Adsorption enrichment: The basic magnesium chloride-CuO / NiO composite sheet is fully contacted with the reverse flotation potassium extraction tail liquid containing flotation reagent at a solid-liquid ratio of 10g / L to carry out the adsorption enrichment of flotation reagent for 3h.

[0082] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0083] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-600 nm for 16 h.

[0084] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried at 40°C by forced air drying. Then, steps (2) to (4) are repeated. After 8 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from reverse flotation is 63.0%.

[0085] Example 6

[0086] (1) Preparation of magnesium-based porous adsorption-photocatalytic materials: 15 parts of powdered FeO, 5 parts of powdered SnO2, 3 parts of salicylic acid, 15 parts of magnesium sulfate, and 62 parts of water were mixed and stirred thoroughly to form a uniform slurry; 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7(5Mg(OH)2·MgSO4·7H2O) were mixed and stirred thoroughly to form a uniform powder; 40 parts of the mixed powder and 5 parts of sodium lignosulfonate were added to 55 parts of the mixed slurry and stirred thoroughly and quickly mixed evenly, then dispensed into 4cm containers. 2 The reaction is shaped in a 0.5cm mold, ground, and passed through a 5-60 mesh sieve to obtain basic magnesium sulfate-FeO / SnO2 composite particles.

[0087] (2) Adsorption enrichment: Basic magnesium sulfate-FeO / SnO2 composite particles are fully contacted with the positive flotation potassium extraction tail liquid containing flotation reagent at a solid-liquid ratio of 5 g / L to carry out the adsorption enrichment of flotation reagent for 6 h.

[0088] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0089] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-600 nm for 16 h.

[0090] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried at 40°C by forced air drying. Then, steps (2) to (4) are repeated. After 8 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from the positive flotation is 80.3%.

[0091] Example 7

[0092] (1) Preparation of magnesium-based porous adsorption-photocatalytic materials: 15 parts of powdered Fe2O3, 5 parts of powdered MnO, 5 parts of succinic acid, 25 parts of magnesium sulfate, and 50 parts of water were mixed and stirred thoroughly to form a uniform slurry; 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7(5Mg(OH)2·MgSO4·7H2O) were mixed and stirred thoroughly to form a uniform powder; 30 parts of the mixed powder and 2 parts of 30% hydrogen peroxide were added to 68 parts of the mixed slurry and stirred thoroughly and quickly until uniformly mixed, then dispensed into 4cm containers. 2 The reaction was carried out in a 0.5cm mold to obtain a basic magnesium sulfate-Fe2O3 / MnO composite sheet.

[0093] (2) Adsorption and enrichment: The basic magnesium sulfate-Fe2O3 / MnO composite sheet was fully contacted with the reverse flotation potassium extraction tail liquid containing flotation reagent at a solid-liquid ratio of 12g / L to carry out the adsorption and enrichment of flotation reagent for 8h.

[0094] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0095] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-600 nm for 0.5 h.

[0096] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried at 40°C by forced air drying. Then, steps (2) to (4) are repeated. After 5 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from reverse flotation is 67.2%.

[0097] Example 8

[0098] (1) Preparation of magnesium-based porous adsorption-photocatalytic materials: 5 parts CoO, 10 parts powdered CeO2, 4 parts glucoheponic acid, 21 parts magnesium chloride, and 60 parts water were mixed and stirred thoroughly to form a uniform slurry; 95 parts active magnesium oxide and 5 parts powdered basic magnesium chloride 5Mg(OH)2·MgCl2·3H2O were mixed and stirred thoroughly to form a uniform powder; 30 parts of the mixed powder and 2 parts of 30% hydrogen peroxide were added to 68 parts of the mixed slurry and stirred thoroughly and quickly until uniformly mixed, then dispensed into 4cm containers. 2 The reaction was carried out in a 0.5cm mold to obtain a basic magnesium chloride-CoO / CeO2 composite sheet.

[0099] (2) Adsorption enrichment: The basic magnesium chloride-CoO / CeO2 composite tablets were fully contacted with the reverse flotation potassium extraction tail liquid containing flotation reagents at a solid-liquid ratio of 15 g / L to carry out the adsorption enrichment of flotation reagents for 0.5 h.

[0100] (3) Solid-liquid separation: The magnesium-based porous adsorption-photocatalytic material that has adsorbed flotation reagents is separated from the potassium extraction tail liquid.

[0101] (4) Photocatalytic oxidation degradation: The magnesium-based porous adsorption-photocatalysis separated in step (3) was irradiated with light of 250-650 nm for 10 h.

[0102] (5) After the magnesium-based porous adsorption-photocatalytic material from step (4) has been reacted, it is washed with water and dried under vacuum at 50°C. Then, steps (2) to (4) are repeated. After 10 cycles, the average removal rate of flotation reagents in the potassium extraction tail liquid from the reverse flotation is 51.6%.

[0103] Compare with Example 1

[0104] The difference between this comparative example and Example 1 is that the photocatalyst is directly dispersed in the potassium extraction tail liquid for photocatalysis.

[0105] Tests showed that the degradation rate of flotation reagents in the potassium extraction tail liquor from reverse flotation in this embodiment was 86.2%. However, degradation products such as nitrate and short-chain alkanes were also produced and entered the system. The total organic carbon removal rate was 57.5%, and 42.5% of organic carbon remained in the system.

[0106] Compare with Example 2

[0107] The difference between this comparative example and Example 1 is that formic acid was not added in step (1). The material in this comparative example was difficult to mold and powdered in water.

[0108] Compare with Example 3

[0109] The difference between this comparative example and Example 1 is that powdered basic magnesium sulfate was not added in step (2), which would affect the mechanical strength of the material.

[0110] Tests showed that the average removal rate of flotation reagents in the potassium extraction tail liquor from reverse flotation in this embodiment was 63.2%, and the material loss rate after 5 cycles was 9.3%.

[0111] Compare with Example 4

[0112] The difference between this comparative example and Example 1 is that no active magnesium oxide was added in step (2). The material in this comparative example could not be formed.

[0113] Compare with Example 5

[0114] The difference between this comparative example and Example 1 is that hydrogen peroxide was not added in step (3).

[0115] The material obtained in this comparative example has a reduced specific surface area, adsorption capacity, and catalytic efficiency. Testing showed that the average removal rate of flotation reagents in the potassium extraction tailings from the reverse flotation in this embodiment was 22.5%.

[0116] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0117] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the described embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method for removing flotation reagents from potassium extraction tailings, characterized in that, include: A photocatalyst, an organic weak acid, and a magnesium salt solution are uniformly mixed to form a mixed slurry. The organic weak acid is selected from any one or a combination of two or more of formic acid, itaconic acid, malic acid, tannic acid, salicylic acid, succinic acid, gluconic acid, lactic acid, maleic acid, and glucoheponic acid. The magnesium salt solution includes magnesium salt and water. The mass ratio of the photocatalyst, organic weak acid, magnesium salt, and water is (5~20):(0.5~5):(5~25):(50~89.5). Active magnesium oxide and a nucleating agent are uniformly mixed to form a mixed powder; the nucleating agent is selected from basic magnesium sulfate and / or basic magnesium chloride, wherein the basic magnesium sulfate is 5Mg(OH)2·MgSO4·7H2O, and the basic magnesium chloride is 5Mg(OH)2·MgCl2·3H2O; the mass ratio of the nucleating agent to active magnesium oxide is 5~15:85~95; The mixed powder, pore-forming agent, and mixed slurry are mixed evenly, and then reacted and shaped to obtain a magnesium-based porous adsorption-photocatalytic material; the mass ratio of the mixed powder, pore-forming agent, and mixed slurry is (20~50):(0.5~5):(45~79.5). The magnesium-based porous adsorption-photocatalytic material is brought into full contact with the potassium extraction tailings that may contain flotation reagents, so that the flotation reagents are adsorbed and enriched on the surface and / or inside of the magnesium-based porous adsorption-photocatalytic material, and then solid-liquid separation is performed. The separated solids are subjected to photocatalytic oxidation degradation treatment to remove flotation reagents.

2. The removal method according to claim 1, characterized in that: The photocatalyst includes at least one of TiO2, ZnO, CuO, SnO2, FeO, Fe2O3, MnO, CoO, NiO, Bi2O3, WO3, and CeO2.

3. The removal method according to claim 1, characterized in that: The magnesium salt is selected from magnesium sulfate and / or magnesium chloride.

4. The removal method according to claim 1, characterized in that: The pore-forming agent is selected from at least one of hydrogen peroxide, surfactant, and protein solution.

5. The removal method according to claim 4, characterized in that: The surfactant is selected from any one or a combination of two or more of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium lignosulfonate, and hexadecyltrimethylammonium bromide.

6. The removal method according to claim 1, characterized in that: The reaction is carried out at room temperature for more than 24 hours and aged for more than 2 days.

7. The removal method according to claim 1, characterized in that: The solid-liquid ratio of the magnesium-based porous adsorption-photocatalytic material mixed with the potassium extraction tailings is 1~50 g / L.

8. The removal method according to claim 1, characterized in that: The adsorption time is 0.5 to 8 hours.

9. The removal method according to claim 1, characterized in that: The potassium extraction tailings are either positive flotation tailings or reverse flotation tailings.

10. The removal method according to claim 1, characterized in that, include: The separated solids are subjected to photocatalytic oxidation degradation treatment by irradiation; wherein the irradiation treatment uses an irradiation wavelength of 250~650 nm and the irradiation time is 0.5~24 h.

11. The removal method according to claim 1, characterized in that, Also includes: The magnesium-based porous adsorption-photocatalytic material obtained after photocatalytic oxidation degradation is cleaned and dried, and then used again for the adsorption and enrichment of flotation reagents; wherein the drying temperature is 25~60℃.