Use method for activating minerals by utilizing ion waste liquid generated in preparation of alkyl thiophosphate

Abstract

The invention belongs to the technical field of flotation reagents, and discloses a use method for activating minerals by utilizing ion waste liquid generated by preparing alkyl thiophosphate. The method comprises the following steps: removing or reducing impurities in the waste liquid to obtain purified waste liquid which can be used as an activating agent; and then, in the flotation operation, ore to be treated is crushed, ground and pulped, an inhibitor, the activating agent, a collecting agent and a foaming agent are sequentially added, and target concentrate is obtained after stirring, air inflation and flotation. The activation potential of the alkyl thiophosphate waste liquid on minerals is found for the first time, industrial wastewater is converted into the efficient flotation activating agent, and a traditional activating agent can be replaced and strengthened. According to the method, the pollution problem of the alkyl thiophosphate waste liquid is solved, the flotation reagent cost is reduced, meanwhile, the concentrate grade and the recovery rate of valuable minerals such as zinc ore, gold ore, copper ore and pyrite can be improved, the requirement for green mine construction is met, and a new path is provided for efficient separation of low-grade ore.

Description

Technical Field

[0001] This invention belongs to the field of flotation reagent technology, and particularly relates to a method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates. Background Technology

[0002] Alkyl thiophosphates are commonly used collectors in mineral processing, with common examples including propanol black, butanol black, and aniline black. However, their preparation generates a large amount of process wastewater, or preparation waste liquid. This wastewater is rich in multiple ammonia-containing active components, including ammonium ions, alkylammonium ions generated during the reaction, and unreacted ammonia and alkylamines containing ammonia functional groups; it also contains small amounts of sulfur-containing byproducts such as thiosulfates, sulfates, and sulfides, as well as trace amounts of unseparated organophosphorus intermediates. Overall, it is weakly acidic to neutral with a high salt content. Due to its complex composition and high pollutant concentration, direct discharge can lead to serious environmental problems such as eutrophication and soil acidification, making it a critical pollution source that urgently needs to be treated in mineral processing reagent production. Current wastewater treatment technologies for the preparation of alkyl thiophosphates mainly include chemical precipitation and advanced oxidation methods. However, these technologies do not efficiently utilize the high-value components such as ammonium ions in wastewater. Instead, they extract and convert them into low-value fertilizer raw materials such as ammonium sulfate through conventional processes such as evaporation and crystallization. In essence, they still treat alkyl thiophosphate wastewater containing ammonia nitrogen and organophosphorus as "pollutants" for purification, resulting in a waste of ion resources.

[0003] Activators are essential reagents in flotation processes. They improve the hydrophobicity of target mineral surfaces and enhance their interaction with collectors, playing a crucial role in achieving efficient separation of valuable minerals. Their performance directly determines beneficiation efficiency and resource recovery value. Currently, the most widely used activators in the beneficiation of valuable minerals include copper sulfate, lead nitrate, and ammonium sulfate. Copper sulfate is the most commonly used activator, exhibiting rapid and stable activation of some sulfide minerals and having a wide range of applications, although its selectivity is relatively poor. Lead nitrate can effectively remove the oxide film restriction on the mineral surface and improve separation selectivity in the separation of certain oxide or complex sulfide ores, but it carries a high risk of contamination. As global mineral resources gradually exhibit characteristics of being "poor, fine, and complex," the proportion of low-grade and complex symbiotic ores being beneficiated is constantly increasing, further amplifying the performance defects of traditional activators and posing greater challenges to beneficiation work. At the same time, geopolitical and economic instability has led to the obstruction of mining of various valuable minerals, supply chain disruptions, and reduced production. However, market demand for valuable metals remains strong, and the supply-demand imbalance has led to a sharp rise in metal prices. The prices of traditional activators such as copper sulfate and lead nitrate, which use copper and lead as core raw materials, have also skyrocketed. As key reagents in mineral processing, the soaring prices of activators have significantly increased companies' reagent procurement costs, severely compressing profit margins, and even forcing some small and medium-sized enterprises to reduce production.

[0004] It is worth noting that, in addition to the difficulties caused by insufficient activation effect and high reagent costs, current research resources in the flotation field are heavily biased towards collectors and depressants, while research on activators has long lagged behind. The development of new and efficient activators lacks systematic theoretical support, which seriously restricts the development of flotation theory and industry. Therefore, developing efficient, environmentally friendly, and low-cost mineral activators is an urgent breakthrough direction for current concentrator production. Although existing technologies have revealed that ammonium salts such as ammonium chloride and ammonium sulfate have certain activation effects, the production waste liquid of alkyl thiophosphates is a complex mixture system containing, in addition to ammonium ions, alkyl ammonium ions, trace amounts of organophosphorus intermediates, thiosulfates, and other impurities. Research shows that those skilled in the art generally believe that these impurities interfere with the flotation process, and for a long time, this waste liquid has only been treated as a "pollutant." Currently, there are few reports on technologies for activating minerals using ionic waste liquid generated from the preparation of alkyl thiophosphates. Summary of the Invention

[0005] To enhance the resource utilization of wastewater, reduce the waste of ion resources, and solve the predicament faced by enterprises due to problems such as poor floatability of low-grade ores and rising prices of copper sulfate activators, the present invention aims to provide a method for recycling and reusing wastewater generated from the preparation of alkyl thiophosphates by activating flotation of valuable minerals.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] This invention discloses a method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates, comprising the following steps:

[0008] Step 1: Remove or reduce impurities in the ionic waste liquid generated during the preparation of alkyl thiophosphates; the impurities are selected from at least one of sulfates, chlorides, alcohols, organophosphorus intermediates, and reducing sulfur-containing byproducts.

[0009] Step two: Use the ionic waste liquid after removing or reducing impurities as a flotation activator;

[0010] Step 3, carry out flotation operation, the specific operation is as follows: (1) After crushing and grinding the mineral to be floated, a slurry with a mass percentage of -0.074mm particles of 70% to 85% is obtained; (2) Add inhibitor, activator, collector and frother to the slurry in step (1) in sequence and stir evenly; (3) Send the slurry after step (2) into the flotation machine for flotation, and obtain the frothy product as the target mineral concentrate.

[0011] In step one of this invention, the impurities are at least one of the following: inorganic salts such as sulfates and chloride ions; organic impurities such as alcohols (including unreacted alcohols) and organophosphorus intermediates; and reducing sulfur-containing byproducts such as thiosulfates and sulfides.

[0012] Preferably, the impurity removal method in step one is selected from at least one of the following schemes;

[0013] Option 1

[0014] Impurities are removed by a combination of chemical precipitation and filtration. Acid or alkali is added to the ionic waste liquid to control the pH and stir. Then, a precipitant is added, stirred, allowed to stand, and filtered to obtain the purified waste liquid.

[0015] Option 2

[0016] Impurities are removed by combining adsorption and separation. The ionic waste liquid is pretreated and filtered by adsorption material to adsorb organic impurities and some inorganic anions. After separation, the waste liquid is cleaned.

[0017] Option 3

[0018] Impurities are removed using a combined extraction and purification method. Organic impurities are removed by an extractant, and after separation, the aqueous phase is pH adjusted and aerated to remove volatile or easily decomposable sulfur-containing byproducts, resulting in a purified waste liquid. Preferably, the acid in Scheme 1 is sulfuric acid, hydrochloric acid, nitric acid, etc., which can dissociate into H+ in aqueous solution. + At least one of the acids, more preferably dilute sulfuric acid.

[0019] Preferably, the alkali described in Scheme 1 is sodium hydroxide, ammonia, calcium hydroxide, etc., which can dissociate into OH- in aqueous solution. - At least one of the bases, more preferably ammonia.

[0020] Preferably, the pH in Scheme 1 is controlled between 3 and 9.

[0021] Preferably, the precipitant in Scheme 1 is at least one of sulfate, hydroxide and calcium salt, and more preferably calcium chloride.

[0022] Preferably, if the chloride ion concentration in the filtrate is still too high after filtration, a small amount of silver nitrate solution can be added and stirred for 20-30 minutes before filtration again.

[0023] Preferably, Scheme 1 is applicable to waste liquid with sulfate content ≥10 g / L and chloride content ≥5 g / L, wherein the waste liquid is the waste liquid generated from the preparation of alkyl thiophosphate.

[0024] Further optimization requires that, after purification using Scheme 1, the sulfate content in the wastewater is ≤2 g / L, the chloride content is ≤1 g / L, the residual organic impurities are ≤50 mg / L, and the reducing sulfur-containing byproducts (such as...) are... S 2- Residual content ≤0.1g / L, no volatile sulfurous odor; contains ammonia-active ingredient (NH4). + The concentration of alkylammonium ions was 7.2~10.8 mol / L; there were no obvious suspended particles, precipitates or oily substances.

[0025] Preferably, the filter membrane used for pretreatment filtration in Scheme 2 is at least one of membrane materials with the function of intercepting suspended particles, such as microfiltration membrane and ultrafiltration membrane, and more preferably a microfiltration membrane with a pore size of 0.45 μm.

[0026] Preferably, the material for adsorbing organic impurities in Scheme 2 is at least one of the adsorbents such as granular activated carbon, powdered activated carbon, and activated carbon fiber, and more preferably granular activated carbon.

[0027] Preferably, the amount of granular activated carbon used in Scheme 2 is 1.0% to 2.5% of the waste liquid mass-volume ratio (g / L), and more preferably 1.5% to 2.0%.

[0028] Preferably, the temperature for adsorbing organic impurities in Scheme 2 is 25~45℃, more preferably 30~40℃, and the stirring time is 30~70 min, more preferably 40~60 min.

[0029] Preferably, the material for adsorbing inorganic anions in Scheme 2 is at least one of ion exchange materials such as strongly basic anion exchange resin and weakly basic anion exchange resin, and more preferably a 201×7 type strongly basic anion exchange resin.

[0030] Preferably, the flow rate of the resin chromatography column in Scheme 2 is 0.5~3 BV / h, and more preferably 1~2 BV / h (BV is the column volume).

[0031] Preferably, Scheme 2 is applicable to waste liquid containing 500-3000 mg / L of organic impurities and 0.5-5 g / L of inorganic anions, wherein the waste liquid is generated from the preparation of alkyl thiophosphates. More preferably, the organic impurities are at least one of alcohols (including unreacted alcohols) and organophosphorus intermediates; the inorganic anions are... , Cl - At least one of the following, wherein the waste liquid is the waste liquid generated from the preparation of alkyl thiophosphate.

[0032] Further optimization shows that, in Scheme 2, the content of alcohols (including unreacted alcohols) and organophosphorus intermediates in the waste liquid after impurity removal is ≤300 mg / L. or ≤0.1 g / L, Cl - ≤0.5 g / L; contains ammonia-active ingredient (NH4) + The concentration of alkylammonium ions was 7.2~10.8 mol / L.

[0033] Preferably, the extractant in Scheme 3 is at least one of organic solvents capable of extracting organic impurities, such as kerosene, diesel, and cyclohexane, and more preferably kerosene.

[0034] Preferably, the volume ratio (oil-water ratio) of the extractant to the waste liquid in Scheme 3 is 1:3 to 1:6, and more preferably 1:4 to 1:5.

[0035] Preferably, the extraction temperature of Scheme 3 is 20~40℃, more preferably 25~30℃, and the stirring time is 20~50 min, more preferably 30~40 min.

[0036] Preferably, in the purification step described in Scheme 3, dilute sulfuric acid is used to adjust the pH of the aqueous phase to 4-6, and compressed air is used for aeration for 10-30 minutes.

[0037] Preferably, Scheme 3 is applicable to waste liquid containing organic impurities with a content ≥3000 mg / L and reducing inorganic anions with a content ≥5 g / L, wherein the waste liquid is waste liquid generated from the preparation of alkyl thiophosphates. More preferably, the organic impurities are at least one of alcohols (including unreacted alcohols) and organophosphorus intermediates; the inorganic anions are... S 2- At least one of them.

[0038] Further optimization shows that, after purification using Scheme 3, the content of organic impurities such as alcohols (including unreacted alcohols) and organophosphorus intermediates in the waste liquid is ≤500 mg / L. ≤0.05 g / L, S 2- ≤1 mg / L; contains ammonia-active ingredient (NH4) + The concentration of alkylammonium ions was 7.2~10.8 mol / L.

[0039] Preferably, the ionic waste liquid in step one is derived from the waste liquid generated during the preparation of alkyl thiophosphates with the general formula (RO)2P(S)SM or (RO)2P(S)OM, wherein R is a C1-C8 alkyl, aryl, or alkylaryl group, and M is an ammonium ion, alkali metal ion, or alkylammonium ion. More preferably, it is the ionic waste liquid generated during the preparation of dibutyl dithiophosphate.

[0040] Preferably, in step two, active ingredients may be added to the ionic waste liquid after impurities have been removed.

[0041] Preferably, the active ingredient is Ag. + Bi 3+ Fe 2+ Cu + Cu 2+ Pb 2+ Au + Cd 2+ At least one of them, preferably Ag + Bi 3+ Cu 2+ Pb 2+ Cu + Cu is further preferred. 2+ and / or Pb 2+ .

[0042] Preferably, when the activating component is Cu 2+ and / or Pb 2+ When using this method, the amount of activating component should be 5-25% of the total amount of flotation activator.

[0043] Further preferably, when the activating component is Cu 2+ and / or Pb 2+At this time, the amount of activating component used is 8-20% of the total amount of flotation activator.

[0044] As a further preferred option, copper salts and / or lead salts may also be added to the flotation activator.

[0045] Preferably, the mineral to be floated in step two is at least one of lead-zinc ore, pyrite, gold ore, silver ore, and copper ore.

[0046] Preferably, the inhibitor in step three (2) is at least one of an organic inhibitor and an inorganic inhibitor, and more preferably sodium sulfite.

[0047] Preferably, in step three (2), the collector is at least one of xanthate, nitric acid or sulfur nitrogen collector, and more preferably butyl xanthate.

[0048] Preferably, in step three (2), the foaming agent is at least one of No. 2 oil, methyl isobutyl methanol or diethylene glycol ether, and more preferably No. 2 oil.

[0049] Preferably, in step three, during the roughing process, the dosage of inhibitor is 50~1000 g / t, the dosage of activator is 10~1000 g / t, the dosage of collector is 0~500 g / t, and the dosage of frother is 0~100 g / t; during the fine process, the dosage of inhibitor is 50~600 g / t; and during the scavenging process, the dosage of collector is 0~300 g / t.

[0050] Further optimization is performed when the minerals to be treated are sphalerite, iron sphalerite, gold ore, and copper sulfide ore. During roughing, the dosage of depressant is 250-800 g / t, activator is 200-800 g / t, collector is 10-300 g / t, and frother is 10-80 g / t. During cleaning, the dosage of depressant is 100-400 g / t. During scavenging, the dosage of collector is 5-200 g / t.

[0051] Preferably, in step three (3), the pH value of the flotation process is controlled at 4~12, and the flotation time is 1~20min.

[0052] Further optimization is made in step three (3), where the pH value of the flotation process is controlled at 6 to 10 and the flotation time is 5 to 15 min.

[0053] The preparation of alkyl thiophosphates can be divided into the preparation of monothiophosphates or dithiophosphates. Monothiophosphates are typically produced by alcoholysis of phosphorus trichloride (PSCl3) and alcohol (ROH); dithiophosphates are produced by esterification-sulfidation of alcohols or phenols as raw materials after dehydration with phosphorus sulfides under heating conditions.

[0054] The reaction formula for the formation of monothiophosphate is:

[0055] PSCl3+2ROH→(RO)2P(S)Cl+2HCl↑(1)

[0056] The reaction formula for the formation of dithiophosphate ((RO)2PSSH) is:

[0057] 4ROH+P2S5→2(RO)2PSSH+H2S↑(2)

[0058] Taking dibutyldithiophosphate (butylammonium black powder) as an example, its mainstream preparation process uses butanol, phosphorus pentasulfide, and ammonia as common raw materials. The specific preparation steps are divided into two steps: the first step is the synthesis of dibutyldithiophosphate, that is, using butanol and phosphorus pentasulfide as reactants, reacting at 130℃ to generate dibutyldithiophosphate; the second step is the neutralization reaction, that is, the generated dibutyldithiophosphate is neutralized by ammonia or sodium hydroxide solution, finally forming an ammonium salt structure. The corresponding specific reaction formulas are as follows:

[0059] 4CH3(CH2)3OH+P2S5→2(CH3(CH2)3O)2PSSH+H2S↑(3)

[0060] (CH3(CH2)3O)2PSSH+NH3→(CH3(CH2)3O)2PSSNH4(4)

[0061] The preparation of these two alkyl thiophosphates generates excess ammonia gas. Water or dilute acid is typically used to absorb the generated or excess ammonia, increasing the number of water cycles and thus the amount of ammonia absorbed. This ultimately results in wastewater containing sulfates, thiosulfates, chloride ions, and a large amount of ammonium ions as byproducts (the concentration of ammonia-containing active components can reach 4-12 mol / L depending on the absorption conditions and number of cycles). This type of wastewater usually requires treatment to meet discharge standards before being released. However, current technology has not recognized the significant activation potential of ammonium ions in the ionic wastewater generated during the preparation of alkyl thiophosphates.

[0062] This invention is the first to propose using ionic waste liquid generated during the preparation of alkyl thiophosphates for mineral flotation activation. Research has found that the ionic waste liquid, after preliminary impurity removal, retains multiple ammonia-containing active components, including ammonium ions, alkylammonium ions generated in the reaction, and unreacted ammonia and alkylamines, giving the waste liquid itself significant activation capabilities. When using the impurity-removed ionic waste liquid without added active components... It promotes the dissolution of the oxide layer on the mineral surface, exposes active sites, and enhances the adsorption of collectors; alkylammonium ions can be adsorbed on the mineral surface, enhancing its hydrophobicity; the amino groups of ammonia and alkylamines can react with sulfur ions (S) on the mineral surface.2- Stable coordination bonds are formed. Furthermore, the active ingredient, by incorporating into the ammonia-containing activation system of the purified waste liquid, becomes an "auxiliary factor" enhancing the activation effect of the waste liquid itself. When using ionic waste liquid with a small amount of added active ingredient, the high-purity ammonia-containing component in the purified waste liquid will form a stable coordination structure with metal ions, such as Cu. 2+ and Pb 2+ It can form [Cu(NH3)4] with ammonium ions or alkylammonium ions. 2+ / [Pb(NH3)4] 2+ Or [Cu(CH3CH2NH2)4] 2+ / [Pb(CH3CH2NH2)4] 2+ The complex not only maintains the effective concentration of metal ions in the slurry but also significantly enhances the diffusion capacity of metal ions in the system. This invention significantly improves the activation efficiency of minerals such as copper, zinc, gold, and silver, while drastically reducing the amount of activator (such as copper sulfate or lead nitrate) used in existing technologies (1000-2000 g / t), and provides a new approach for the resource utilization of industrial wastewater.

[0063] Advantages and benefits of the invention:

[0064] (1) It was discovered for the first time that the ionic waste liquid generated during the preparation of alkyl thiophosphate has a significant activation effect on minerals such as copper, zinc, gold, silver, and pyrite. This breaks the traditional technical path of mineral flotation relying on single activators such as copper salts and lead salts, fills the technical gap of "resource utilization of alkyl thiophosphate wastewater for mineral flotation", and provides a new idea for the efficient separation of low-grade ores.

[0065] (2) Successfully transforming alkyl thiophosphate wastewater, which is difficult to treat in industry and is prone to pollution, into a high-efficiency flotation activator to replace the traditional wastewater treatment method. This not only reduces environmental problems such as water eutrophication and soil pollution caused by wastewater discharge, but also achieves efficient conversion of pollutants into resources, which meets the needs of green mine construction.

[0066] (3) The activator described in this invention has a wide range of raw material sources and a simple preparation process. It exhibits excellent activation performance on the target minerals, effectively promotes the separation of minerals from the slurry, enhances the efficiency of the collector, and thus improves the grade and recovery rate of the concentrate and improves the overall production indicators of the beneficiation plant.

[0067] (4) This activator can replace and enhance the traditional activators such as copper sulfate used alone in the flotation process. While reducing reagent costs and resource consumption, it realizes the resource utilization of waste liquid and has significant practical application value and promotion potential. Attached Figure Description

[0068] Figure 1This is a flow chart of the flotation process. Detailed Implementation

[0069] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. The following embodiments are only used to illustrate the technical effects and implementation methods of this invention and should not be considered as limiting the scope of protection of this invention, but merely represent selected embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0070] It should be noted that in the actual production process of alkyl thiophosphates, due to differences in different stages or process control, the generated ionic waste liquids can be mainly classified into three types: high inorganic salt type, organic and anionic type, and high organic and high reducing sulfur type. This invention provides the following preferred purification and resource utilization embodiments for each of these three types of waste liquids.

[0071] I. Preparation of Activator

[0072] Example 1

[0073] Take 1 L of waste liquid containing sulfate and chloride ions from the preparation of dibutyldithiophosphate (butylammonium black powder) (i.e., the activator used in Comparative Example 2), with an initial pH of approximately 5.5. While stirring, slowly add dilute sulfuric acid to adjust the pH to 4.0, then add calcium chloride solution as a precipitant, stir for 30 min, allow to settle, and filter to obtain a clear, purified waste liquid. The resulting product is designated as reagent 1. The composition of the purified waste liquid (i.e., reagent 1) was determined to be: ammonium ion concentration of 6.18 mol / L, alkylammonium ion concentration of 0.9 mol / L, trace ammonia (NH3) concentration of 0.2 mol / L, sulfate content ≤1.8 g / L, chloride ion content ≤0.9 g / L, and reducing sulfur-containing byproducts (…). +S 2- The content is ≤0.08 g / L. It also contains a small amount of calcium ions from the precipitant calcium chloride.

[0074] Example 2

[0075] Take 1 L of waste liquid containing low concentrations of organic impurities and trace amounts of inorganic anions generated during the preparation of dibutyldithiophosphate (butylammonium black powder). (Before impurity removal, the pH of the waste liquid is 5.3-5.7, the concentration of ammonium ions is 7.9 mol / L, the concentration of alkylammonium ions is 1.2 mol / L, the concentration of NH3 is 0.21 mol / L, the content of alcohols (including unreacted alcohols) is 1300-1500 mg / L, and the content of organophosphorus intermediates is 1200-1400 mg / L.) The content is 0.6~0.8 g / L, Cl - The waste liquid (containing 2.5~3.0 g / L) was first pretreated with a 0.45 μm microfiltration membrane. Then, granular activated carbon (2.0% by weight of the waste liquid) was added to the filtrate, and the mixture was stirred and adsorbed at 35℃ for 50 min. After filtration to remove the activated carbon, the filtrate was passed through a 201×7 type strong basic anion exchange resin column at a flow rate of 1.5 BV / h. The effluent was collected to obtain the purified waste liquid. The resulting product is designated as reagent 2. The pH is 6.5. The composition of the purified waste liquid (reagent 2) was determined to be: ammonium ion concentration of 6.26 mol / L, alkylammonium ion concentration of 1.02 mol / L, trace ammonia concentration of 0.14 mol / L, alcohol (including unreacted alcohol) content ≤260 mg / L, and organophosphorus intermediate content ≤240 mg / L. Content ≤0.07 g / L, Cl - Content ≤0.4 g / L.

[0076] Example 3

[0077] Take 1 L of waste liquid containing high concentrations of organic impurities and reducing inorganic anions generated during the preparation of dibutyldithiophosphate (butylammonium black powder). (Before impurity removal, the pH of the waste liquid is 5.0~5.4, the concentration of ammonium ions is 7.4 mol / L, the concentration of alkylammonium ions is 1.19 mol / L, the concentration of NH3 is 0.11 mol / L; the content of alcohol (including unreacted alcohol) is 2000~2500 mg / L, and the content of organophosphorus intermediates is 1800~2000 mg / L.) The content is 5.2~5.8 g / L, Cl - The organic phase was added as an extractant at a volume ratio of 1:4 (1.0~1.5 g / L) and stirred at 30℃ for 35 min. After standing and separation, the organic phase was discarded. Dilute sulfuric acid was added to the obtained aqueous phase to adjust the pH to 5.0, and compressed air was introduced for aeration for 20 min. Finally, the mixture was filtered to obtain purified waste liquid. The obtained product is designated as reagent 3. The pH is 5.0. The composition of the waste liquid after impurity removal (reagent 3) was determined to be: ammonium ion concentration of 6.14 mol / L, alkylammonium ion concentration of 1.07 mol / L, trace ammonia (NH3) concentration of 0.08 mol / L, and organic impurity content ≤420 mg / L. The content is ≤0.04g / L, and no new interfering ions are added.

[0078] Example 4

[0079] All other conditions were the same as in Example 1, except that copper sulfate was added to reagent 1 of the product obtained in Example 1, and this was designated as reagent 4, with a pH of 3.9. The waste liquid after impurity removal (reagent 4) was determined to contain ammonium ion concentration of 6.19 mol / L, alkylammonium ion concentration of 0.92 mol / L, trace ammonia (NH3) concentration of 0.2 mol / L, and Cu... 2+ The concentration is 1.32 mol / L, sulfate content ≤1.8 g / L, chloride content ≤0.9 g / L, and reducing sulfur-containing byproducts ( +S 2- The content is ≤0.08 g / L. It contains a small amount of calcium ions from the precipitant.

[0080] Example 5

[0081] All other conditions were the same as in Example 1, except that lead nitrate was added to reagent 1 of the product obtained in Example 1, and this was designated as reagent 5, with a pH of 4.0. The composition of the waste liquid after impurity removal (reagent 5) was determined to be: ammonium ion concentration of 6.18 mol / L, alkylammonium ion concentration of 0.89 mol / L, trace ammonia (NH3) concentration of 0.19 mol / L, Pb²⁺ concentration of 1.14 mol / L, sulfate content ≤1.8 g / L, chloride ion content ≤0.9 g / L, and reducing sulfur-containing byproducts (…). +S 2- The content is ≤0.08 g / L.

[0082] Example 6

[0083] All other conditions were the same as in Example 2, except that copper sulfate was added to reagent 2 of the product obtained in Example 2, and this was designated as reagent 6, with a pH of 6.5. The waste liquid after impurity removal (reagent 6) was determined to contain ammonium ion concentration of 6.27 mol / L, alkylammonium ion concentration of 1.01 mol / L, trace ammonia concentration of 0.13 mol / L, and Cu... 2+ The concentration is 1.31 mol / L, the alcohol (including unreacted alcohol) content is ≤260 mg / L, and the organophosphorus intermediate content is ≤240 mg / L. Content ≤0.07 g / L, Cl - Content ≤0.4 g / L.

[0084] Example 7

[0085] All other conditions were the same as in Example 2, except that lead nitrate was added to reagent 2 of the product obtained in Example 2, and this was designated as reagent 7, with a pH of 6.4. The waste liquid after impurity removal (reagent 7) was determined to have the following components: ammonium ion concentration of 6.25 mol / L, alkylammonium ion concentration of 1.02 mol / L, trace ammonia concentration of 0.11 mol / L, Pb²⁺ concentration of 1.12 mol / L, unreacted alcohol content ≤260 mg / L, and organophosphorus intermediate content ≤240 mg / L. Content ≤0.07 g / L, Cl - Content ≤0.4 g / L.

[0086] Example 8

[0087] All other conditions were the same as in Example 3, except that copper sulfate was added to reagent 3 of the product obtained in Example 3, and this was designated as reagent 8, with a pH of 5.1. The waste liquid after impurity removal (reagent 8) was determined to contain ammonium ion concentration of 6.13 mol / L, alkylammonium ion concentration of 1.06 mol / L, trace ammonia (NH3) concentration of 0.08 mol / L, and Cu... 2+ The concentration was 1.33 mol / L, and the organic impurity content was ≤420 mg / L. Content ≤0.04 g / L, S 2- The content is ≤0.7 mg / L, and no new interfering ions were added.

[0088] Example 9

[0089] All other conditions were the same as in Example 3, except that lead nitrate was added to reagent 3 of the product obtained in Example 3, and this was designated as reagent 9, with a pH of 5.0. The waste liquid after impurity removal (reagent 9) was determined to have the following components: ammonium ion concentration of 6.13 mol / L, alkylammonium ion concentration of 1.07 mol / L, trace ammonia (NH3) concentration of 0.08 mol / L, Pb²⁺ concentration of 1.16 mol / L, and organic impurity content ≤420 mg / L. Content ≤0.04 g / L, S 2- The content is ≤0.7 mg / L, and no new interfering ions were added.

[0090] Comparative Example 1

[0091] No activators are added.

[0092] Comparative Example 2

[0093] A homologous ion waste liquid that had not undergone any impurity removal treatment (i.e., the same waste liquid raw material used in Example 1) was selected as the activator and designated as Comparative Agent 1. The pH of Comparative Agent 1 was measured to be 5.2–5.8; the ammonium ion concentration was 8.5 mol / L, the alkylammonium ion concentration was 1.1 mol / L, and the NH3 concentration was 0.3 mol / L. Content is 12~18 g / L, Cl - The content is 6~9 g / L; the alcohol (including unreacted alcohol) content is 1300~1800 mg / L, and the organophosphorus intermediate content is 400~900 mg / L; The content is 1.2~1.8 g / L, HS - The content is 0.3~0.5 g / L.

[0094] Comparative Example 3

[0095] All other conditions were the same as in Example 1, except that no acid or alkali was added, and the pH was maintained at 5.5. The resulting product was designated as Comparative Reagent 2. The pH of Comparative Reagent 2 was determined to be 5.5; the ammonium ion concentration was 6.13 mol / L, the alkylammonium ion concentration was 0.85 mol / L, and the NH3 concentration was 0.18 mol / L. The content is 6.5 g / L, Cl - The content was 4.8 g / L; the residual amount of organic impurities was 180 mg / L; +S 2- The content is 0.5 g / L;

[0096] Comparative Example 4

[0097] All other conditions were the same as in Example 2, except that granular activated carbon was not added and the anion exchange resin treatment was omitted. Instead, the ion-exchange waste liquid was pretreated using a 0.45 μm microfiltration membrane, and the resulting product was designated as Comparative Reagent 3. The pH of Comparative Reagent 3 was measured to be 6.6; the ammonium ion concentration was 6.3 mol / L, the alkylammonium ion concentration was 1.0 mol / L, and the NH3 concentration was 0.18 mol / L. The content is 0.9 g / L. The content is 0.35 g / L, Cl - The content is 3.3 g / L; the alcohol (including unreacted alcohol) content is 1200 mg / L, and the organophosphorus intermediate content is 850 mg / L.

[0098] Comparative Example 5

[0099] All other conditions were the same as in Example 3, except that kerosene extraction and compressed air aeration were not performed. The resulting product was designated as Comparative Agent 4. The pH of Comparative Agent 4 was determined to be 5.3; the ammonium ion concentration was 6.0 mol / L, the alkylammonium ion concentration was 1.05 mol / L, the NH3 concentration was 0.09 mol / L, the alcohol (including unreacted alcohol) content was 3500 mg / L, and the organophosphorus intermediate content was 1600 mg / L. The content is 3.1 g / L, S 2- The content is 1.1 g / L.

[0100] Comparative Example 6

[0101] Copper sulfate was selected as the activator.

[0102] Comparative Example 7

[0103] Lead nitrate was selected as the activator.

[0104] II. Flotation Experiment

[0105] 1. Raw materials

[0106] The ore raw materials were all taken from the tailings after lead beneficiation in a lead-zinc mine in Chenzhou, Hunan Province. The ore contained approximately 5.3% zinc, approximately 11.5% iron, and approximately 14.2% sulfur. The activators used in the experiment were the activators obtained in Examples 1-9 and Comparative Examples 1-7. The inhibitor was sodium sulfite, the collector was xanthate, and the frother was No. 2 oil.

[0107] 2. Operating procedures and technical conditions

[0108] 500g of feed material was crushed and ground (to a particle size of -200 mesh of 80±2%), and water was added to adjust the slurry concentration to 30-45%. The slurry pH was controlled at 9. 500 g / t of depressant was added and stirred for 3 min, followed by 600 g / t of activator and stirring for 3 min, then 120 g / t of collector and stirring for 2 min, and finally 20 g / t of frother and stirring for 1 min. Roughing was then performed to obtain a rough concentrate and tailings. 300 g / t of depressant was added to the rough concentrate from the roughing process, and 50 g / t of flotation collector was added to the tailings. Two cleaning and scavenging processes were then performed. The scavenged concentrate was returned sequentially to the previous flotation process, and the middlings from the cleaning process were returned sequentially to the roughing process. The roughing time was 3 min, the cleaning time was 1 min, and the scavenging time was 2 min. The experimental comparison results are shown in Table 1.

[0109]

[0110]

[0111]

[0112] The flotation experiment results of Examples 1-9 and Comparative Examples 1-7 show that the activator prepared by the technical solution disclosed in this invention has a significant activating effect on the ore, specifically manifested as follows:

[0113] (1) The waste liquid after impurity removal provided by the present invention (Examples 1, 2, 3) itself has obvious activation ability, and its effect is far better than that of the working condition without adding any activator (Comparative Example 1).

[0114] (2) After removing impurities and adding a small amount of active metal ions (Examples 4-9), its activation effect is better than that of traditional copper sulfate and lead nitrate (Comparative Examples 6 and 7), achieving the goal of "using waste to replace medicine";

[0115] (3) Waste liquid removal is a necessary step. Waste liquid that has not been removed (Comparative Example 2) has a significantly reduced flotation index due to interference from impurities.

[0116] In summary, under the same raw materials and beneficiation system, the technical solution of this invention can achieve a higher recovery rate and better comprehensive beneficiation indicators than traditional activators such as copper sulfate and ammonium sulfate. Meanwhile, the results of Comparative Examples 1-7 show that reagent synthesis ratios outside the scope of this invention or the use of single-component reagents cannot achieve effective activation and harvesting of the ore. Through comparison of Examples 1, 2, and 3, Comparative Examples 6 and 7, and Examples 4-9, it is easy to see that using the waste liquid after impurity removal as an activator not only has outstanding activation ability itself, but also significantly enhances the activation effect of traditional activators (such as copper sulfate and lead nitrate). This invention not only provides a high-value resource utilization pathway for the ionic waste liquid generated from the preparation of alkyl thiophosphates, but also produces an activator with excellent performance, effectively replacing traditional copper sulfate, reducing production costs, and meeting the development requirements of green mines.

[0117] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and such modifications or equivalent substitutions shall not cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates, characterized in that, Includes the following steps: Step 1: Remove or reduce impurities in the ionic waste liquid generated during the preparation of alkyl thiophosphates; the impurities are selected from at least one of sulfates, chlorides, alcohols, organophosphorus intermediates, and reducing sulfur-containing byproducts. Step two: Use the ionic waste liquid after removing or reducing impurities as a flotation activator; Step 3, flotation operation, which includes: (1) crushing and grinding the mineral to be floated to obtain a slurry with a mass percentage of -0.074mm particles of 70% to 85%; (2) adding inhibitor, activator, collector and frother to the slurry in step (1) in sequence and stirring evenly; (3) sending the slurry after step (2) into a flotation machine for flotation to obtain the frothy product, which is the target mineral concentrate.

2. The method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 1, characterized in that: The impurity removal method described in step one is selected from at least one of the following schemes; Option 1 Impurities are removed by chemical precipitation combined with filtration. Acid or alkali is added to the ionic waste liquid to control the pH and stir. Then, a precipitant is added and stirred, allowed to stand, and filtered to obtain the impurity-removed waste liquid. Option 2 Impurities are removed by combining adsorption and separation. The ionic waste liquid is pretreated and filtered by adsorption material to adsorb organic impurities and some inorganic anions. After separation, the waste liquid with impurities removed is obtained. Option 3 Impurities are removed by a combination of extraction and purification. Organic impurities are removed by an extractant, and after separation, the pH of the aqueous phase is adjusted and aerated to remove volatile or easily decomposed sulfur-containing byproducts, resulting in a purified waste liquid.

3. The method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 2, characterized in that: The acid described in Scheme 1 is sulfuric acid, hydrochloric acid, nitric acid, etc., which can dissociate into H+ in aqueous solution. + At least one of the acids, more preferably dilute sulfuric acid; The alkali mentioned in Scheme 1 is sodium hydroxide, ammonia, calcium hydroxide, etc., which can dissociate into OH- in aqueous solution. - At least one of the bases, more preferably ammonia; The pH level described in Scheme 1 is controlled between 3 and 9; The precipitant described in Scheme 1 is at least one of sulfate, hydroxide and calcium salt, and is more preferably calcium chloride.

4. The method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 2, characterized in that: Scheme 1 is applicable to waste liquid with sulfate content ≥10 g / L and chloride content ≥5 g / L, wherein the waste liquid is the waste liquid generated from the preparation of alkyl thiophosphate; After purification using Scheme 1, the wastewater contains ≤2 g / L sulfate and ≤1 g / L chloride; ≤50 mg / L residual organic impurities; ≤0.1 g / L residual reducing sulfur-containing byproducts; and 7.2–10.8 mol / L concentration of ammonia-containing active ingredients. There are no obvious suspended particles, precipitates, or oily substances. The ammonia-containing active ingredient is NH4+. + And alkylammonium ions.

5. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 2, characterized in that: The filter membrane used in the pretreatment filtration described in Scheme 2 is at least one of the membrane materials with the function of intercepting suspended particles, such as microfiltration membrane and ultrafiltration membrane, and is more preferably a microfiltration membrane with a pore size of 0.45 μm; The material for adsorbing organic impurities in Scheme 2 is at least one of the adsorbents such as granular activated carbon, powdered activated carbon, and activated carbon fiber, and is more preferably granular activated carbon; In Scheme 2, the amount of granular activated carbon used is 1.0% to 2.5% of the waste liquid mass-volume ratio, more preferably 1.5% to 2.0%. The temperature for adsorbing organic impurities described in Scheme 2 is 25~45℃, more preferably 30~40℃, and the stirring time is 30~70min, more preferably 40~60min; The material for adsorbing inorganic anions in Scheme 2 is at least one of ion exchange materials such as strong basic anion exchange resin and weak basic anion exchange resin, and is more preferably a 201×7 type strong basic anion exchange resin. In Scheme 2, the flow rate of the resin chromatography column is 0.5~3 BV / h, and more preferably 1~2 BV / h, where BV is the column volume.

6. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 2, characterized in that: Scheme 2 is applicable to waste liquids containing 500-3000 mg / L of organic impurities and 0.5-5 g / L of inorganic anions. More preferably, the organic impurities are at least one of alcohols (including unreacted alcohols) and organophosphorus intermediates; the inorganic anions are... , Cl - At least one of the following, wherein the waste liquid is the waste liquid generated from the preparation of alkyl thiophosphate; Option 2: After impurity removal, the content of alcohols (including unreacted alcohols) and organophosphorus intermediates in the waste liquid is ≤300 mg / L. or ≤0.1 g / L, Cl - ≤0.5 g / L; contains ammonia-active ingredient (NH4) + The concentration of alkylammonium ions was 7.2~10.8 mol / L.

7. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 2, characterized in that: The extractant described in Scheme 3 is at least one of organic solvents capable of extracting organic impurities, such as kerosene, diesel, and cyclohexane, with kerosene being a more preferred choice. The volume ratio of the extractant to the waste liquid in Scheme 3 is 1:3 to 1:6, and more preferably 1:4 to 1:5; The extraction temperature described in Scheme 3 is 20~40℃, more preferably 25~30℃, and the stirring time is 20~50min, more preferably 30~40min; In the purification steps described in Scheme 3, dilute sulfuric acid is used to adjust the pH of the aqueous phase to 4-6, and compressed air is used for aeration for 10-30 minutes. Scheme 3 is applicable to waste liquids containing organic impurities ≥3000 mg / L and reducing inorganic anions ≥5 g / L; the organic impurities are at least one of alcohols (including unreacted alcohols) and organophosphorus intermediates; the inorganic anions are... S 2- At least one of them; After purification using Scheme 3, the content of organic impurities such as alcohols (including unreacted alcohols) and organophosphorus intermediates in the waste liquid is ≤500mg / L. ≤0.05 g / L, S 2- ≤1 mg / L; contains ammonia-active ingredient (NH4) + The concentration of alkylammonium ions is 7.2~10.8 mol / L.

8. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 3, characterized in that: The active ingredient is Ag. + Bi 3+ Fe 2+ Cu + Cu 2+ Pb 2+ Au + Cd 2+ At least one of them, preferably Ag + Bi 3+ Cu 2+ Pb 2+ Cu + Cu is further preferred. 2+ and / or Pb 2+ ; When the activating component is Cu 2+ and / or Pb 2+ When using this method, the amount of activating component should be 5-25% of the total amount of flotation activator.

9. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 3, characterized in that: The mineral to be floated in step two is at least one of lead-zinc ore, pyrite, gold ore, silver ore, and copper ore.

10. A method for activating minerals using ionic waste liquid generated during the preparation of alkyl thiophosphates according to claim 1, characterized in that: The inhibitor mentioned in step three (2) is at least one of organic inhibitors and inorganic inhibitors, and is more preferably sodium sulfite; In step three (2), the collector is at least one of xanthate, nitric acid or sulfur nitrogen collector, and is more preferably butyl xanthate; In step three (2), the foaming agent is at least one of No. 2 oil, methyl isobutyl methanol or diethylene glycol ether, and is more preferably No. 2 oil; In step three, during roughing, the dosage of inhibitor is 50-1000 g / t, the dosage of activator is 10-1000 g / t, the dosage of collector is 0-500 g / t, and the dosage of frother is 0-100 g / t; during cleaning, the dosage of inhibitor is 50-600 g / t; and during scavenging, the dosage of collector is 0-300 g / t. When the minerals to be processed are sphalerite, iron sphalerite, gold ore, and copper sulfide ore, the dosage of depressant during roughing is 250~800 g / t, activator is 200~800 g / t, collector is 10~300 g / t, and frother is 10~80 g / t; the dosage of depressant during cleaning is 100~400 g / t; and the dosage of collector during scavenging is 5~200 g / t. In step three (3), the pH value of the flotation process is controlled at 4~12, and the flotation time is 1~20min.

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