Method for sorting aluminosilicate minerals

Abstract

This invention belongs to the field of mineral flotation and separation technology, and discloses a method for separating aluminosilicate minerals, including: adjusting the ground slurry with a hard alkali modifier to obtain a first modified slurry; adjusting the first modified slurry with a soft alkali modifier to obtain a second modified slurry; adding a metal ion activator to the second modified slurry to obtain a third modified slurry; adding an anionic collector to the third modified slurry for selective collection and mineralization; and using a foaming flotation process to separate the target mineral concentrate and flotation tailings. This invention achieves highly selective separation and enrichment recovery of the target aluminosilicate minerals by utilizing the theory of hard and soft acids and bases for multiple stages of mineral surface property enhancement and adjustment, followed by selective collection and mineralization separation with an anionic collector.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation and separation technology, and in particular to a separation method for aluminosilicate minerals. Background Technology

[0002] Some important metallic mineral ores are primarily supported by aluminosilicate minerals, such as spodumene / lepidolite (Li), potassium feldspar (K), beryl (Be), garnet (Ce), kaolinite (Al), and kyanite (Al). The enrichment and separation of these target minerals often involves selective separation from different aluminosilicate minerals with similar physicochemical properties, as well as between different silicate minerals. Among these methods, flotation, which utilizes differences in the hydrophobicity of mineral surfaces, remains the most adaptable and widely used method for separating these minerals. However, due to the influence of important factors such as ore-forming factors and their composition, mineral crushing and liberation, and their natural floatability, the technical basis for selective flotation separation of target minerals in the flotation recovery system for these aluminosilicate minerals largely lies in the selective modification of different mineral surfaces by modifiers. In other words, the effective application of modifiers and their surface modification strategies is a prerequisite for the flotation separation of these silicate minerals. Therefore, selective modifiers and their efficient application are one of the key research directions for the flotation separation of this type of oxide / silicate minerals.

[0003] The flotation separation of aluminosilicate minerals / alumina oxide minerals typically involves several processes. The first is intermineral liberation and surface hydrolysis, which generally occurs or is rapidly completed during grinding liberation. Aluminosilicate minerals with different crystal structures, such as island-like [SiO4]... 4- Circular [Si3O9] 6- / [Si6O 12 ] 12- Chain-like [Si2O6] 4- / [Si4O 11 ] 6- Layered [Si4O] 10 ] 4- Framework (Si, Al) n O 2n After grinding and dissociation, minerals often exhibit negatively charged surfaces across a wide pH range due to the breakage and hydrolysis of metal ion -O bonds, Si-O bonds, and Al-O bonds. In alkaline solutions, Al-OH and Si-OH groups form, leading to homogenization of mineral surface properties. Furthermore, the mineral grinding and dissociation process inevitably introduces Ca2+ from the flotation solution. 2+ / Mg 2+ / Al 3+ and abrasion Fe 3+ / 2+The adsorption effect of these minerals makes the responses of the collectors similar, thus making it difficult to directly achieve the separation and enrichment of the target mineral. Therefore, in mineral separation and processing, to enhance the selectivity of mineral separation, modifiers are added during the grinding process to strengthen the modification of the surface properties of different minerals, such as adding sodium carbonate in the grinding of spodumene flotation systems. Secondly, there is mineral surface slurry modification, which adjusts the flotation process by using the differences in competitive adsorption of active components in the modifier on different mineral surfaces, such as using S-containing anionic surfactants. 2- The differences in solubility products of different sulfides promote the formation of active metal-Me-S components, achieving different adsorption capping effects of metal ions on different mineral surfaces and providing a mineral surface basis for mineral separation. Thirdly, surfactants adsorb minerals, utilizing different active sites on the mineral surface and employing different surfactant components / functional groups to achieve selective adsorption. This is followed by aeration and foaming to create mineralized foam loaded with the target mineral for separation. It can be considered that for aluminosilicate mineral separation systems, one of the key technologies for achieving effective flotation separation of aluminosilicate minerals with similar physicochemical properties is the discovery and application of selective modifiers.

[0004] Through research and practice on numerous flotation and separation technologies for aluminosilicate minerals, inorganic modifiers are commonly used in the flotation process of aluminosilicate minerals, in addition to organic macromolecular modifiers. Among them, phosphate, carbonate, and their combination modifiers are used in the flotation process of bauxite, lepidolite, and kyanite. Na2CO3-NaOH-Mg / CaCl2 is a widely used modifier in the flotation of spodumene. Chinese patent CN115814956B discloses a beneficiation method for low-grade spodumene ore. In order to solve the problem of fine mud covering the mineral surface and affecting ore separation, a new modifier YLH-01 was developed. It is obtained by mixing and stirring a nitrogen-based (sodium trimethylene phosphonate), poly(sodium 4-styrene sulfonate), and carboxymethyl cellulose. The modifier YLH-01-activator CaCl2-collector PL2-01 system is used for the flotation of low-grade lithium. Sodium sulfide (Na2S) is often used as a depressant, activator, or descaling agent in the flotation of silicate minerals. The specific application effect depends on the mineral to be flotated and the process. For example, it can be used as a depressant for garnet to separate it from other valuable minerals (such as scheelite and cassiterite). It is also used in the flotation process to separate silicate minerals containing alkaline earth metals such as calcium oxide and magnesium oxide (such as garnet, beryl, and spodumene) from other minerals (such as mica, feldspar, and quartz).

[0005] Selective separation of silicate minerals is a common challenge in mineral processing. The main drawbacks of existing technologies are: the separation of different aluminosilicate minerals is generally quite difficult, both in the modification process of the modifier and in the collection and flotation process; this is primarily limited by, firstly, the breaking of Si-O / Al-O bonds on the surface of aluminosilicate minerals, resulting in the loss of surface Si... 4+ \Al 3+ Its derivatives are readily reacted with anions (PO4). 3- / CO3 2- HS - / S 2- OH - The adsorption modification by the adjusting agent leads to enhanced surface negative charge expression of minerals across a wide pH range, resulting in more homogenized surface charge properties among different aluminosilicate minerals. This makes it difficult to use anionic collectors for flotation, while the selectivity of cationic collectors for separation becomes weaker. Secondly, metal ions (Ca) are inevitably present in the solution system. 2+ / Mg 2+ / Al 3+ / Fe 3+ / 2+ The adsorption of mineral surfaces by various factors, such as the surface of different aluminosilicate minerals and silicate minerals, makes it easy for different aluminosilicate minerals and silicate mineral surfaces to express similar reactivity, resulting in low separation and recovery efficiency when using anionic collectors for the flotation recovery of target minerals. However, current flotation reagents used to obtain -Si- / -Al- silicate mineral concentrates generally suffer from poor selectivity in their modifying effects, prominent environmental problems with fluorinated modifiers that are relatively effective in inhibiting their effects, and poor adsorption and mineralization efficiency of their collectors. These issues make it difficult to selectively separate, enrich, and recover low-grade aluminosilicate minerals, resulting in low comprehensive utilization of target metal mineral resources.

[0006] Therefore, this invention is proposed. Summary of the Invention

[0007] According to one embodiment of the present invention, the purpose is to provide a sorting method for aluminosilicate minerals, which utilizes the theory of soft and hard acids and bases to perform multiple stages of mineral surface property enhancement and modification, and then employs selective anionic collectors for adsorption and mineralization separation, so as to achieve highly selective separation and enrichment recovery of the target aluminosilicate minerals.

[0008] The above objective can be achieved through the following technical solutions: According to one aspect of the present invention, a method for sorting aluminosilicate minerals is provided, comprising: The grinding pulp is prepared by using a hard alkali modifier to obtain a first modified pulp; this includes: preparing the pulp with a first modifier, and / or preparing the pulp with a second modifier; the first modifier is selected from one or more modifiers whose active component is a carbonate or a phosphate, and the second modifier is selected from modifiers containing an active component OH. - One or more of the modifiers; The first modified slurry was prepared by using a soft alkali modifier to obtain a second modified slurry; the soft alkali modifier was selected from those containing active component S. 2- / HS - One or more of the modifiers; A metal ion activator was added to the second modified slurry for slurry conditioning to obtain a third modified slurry; An anionic collector is added to the third modified slurry for selective collection and mineralization, followed by flotation separation using a foaming flotation process to obtain the target mineral concentrate and flotation tailings.

[0009] Preferably, the first modifier is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium percarbonate, ammonium carbonate, formic acid, acetic acid, oxalic acid, ascorbic acid, citric acid, tartaric acid, succinic acid, succinic acid, disodium oxalate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, methylphosphonic acid, aminotrimethylphosphonic acid, hydroxyethylidene diphosphonic acid, polyacrylic acid, hydroxyphosphonate, and polyepoxysuccinic acid.

[0010] Preferably, the dosage of the first modifier is 20-5000 g / t relative to the dry ore feed, and the time for adjusting the slurry with the first modifier is 2-10 min.

[0011] Preferably, the second modifier is one or more of sodium hydroxide, potassium hydroxide, ammonia, and calcium hydroxide.

[0012] Preferably, the dosage of the second modifier is 50-3000 g / t based on the dry ore feed, and the time for adjusting the slurry with the second modifier is 2-10 min.

[0013] Preferably, the soft alkali modifier is one or more of sodium sulfide, potassium sulfide, sodium hydrosulfide, potassium hydrosulfide, and ammonium sulfide.

[0014] Preferably, the dosage of the soft alkali modifier is 50-3000 g / t based on the dry ore feed, and the time for adjusting the slurry with the soft alkali modifier is 2-10 min.

[0015] Preferably, the metal ions in the metal ion activator include Sn. 4+ Co 3+ Cr 3+One or more of them.

[0016] Preferably, the metal ion activator is one or more of tin tetrachloride, tin sulfate, chromium chloride, chromium sulfate, cobalt trichloride, high cobalt sulfate, and cobalt trihydroxide.

[0017] Preferably, the amount of the metal ion activator is 10-1000 g / t based on the dry ore feed, and the time for adding the metal ion activator to adjust the slurry is 2-10 min.

[0018] Preferably, the anionic collector is selected from one or more of fatty acids, organic sulfur-containing compounds, and hydroxamic acids.

[0019] Preferably, the anionic collector is one or a combination of several of the following: oxidized paraffin soap, oleic acid, sodium oleate, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium petroleum sulfonate, octyl hydroxamic acid, and benzyl sulfoxyxamic acid.

[0020] Preferably, the dosage of the anionic collector is 50-3000 g / t based on the dry ore feed, and the time for adding the anionic collector to adjust the slurry is 2-10 min.

[0021] Preferably, a foaming positive flotation process is used for flotation separation.

[0022] Preferably, the flotation process adopts a combined process of roughing-scavenging-cleaning.

[0023] Preferably, the time for a single coarse selection operation is 3 to 10 minutes, the time for a single sweeping operation is 3 to 10 minutes, and the time for a single fine selection operation is 2 to 6 minutes.

[0024] Beneficial effects: The aluminosilicate mineral sorting method provided by this invention fully utilizes the selective reaction tendency between hard and soft acids among active species. In an alkaline or weakly alkaline system, hard base modifiers, including carbonates, phosphates, and hydroxyl groups, are first used to adjust the unavoidable metal ions (Ca) in the hard acid separation system. 2+ / Mg 2+ / Fe 3+ The negative effects of components such as (etc.) and the Al-OH / Si-OH sites on the mineral surface expressing hard acid activity are reduced on the one hand, and the influence of unavoidable metal ions is reduced on the other hand, making the mineral surface more negatively charged; subsequently, soft base (or transition base) activity modifiers containing active component S are used. 2- / HS - It mainly consists of sulfides and hydrosulfides, which regulate the expression of soft acid-like active species Fe on the mineral surface. 2+ / Cr 2+ ...etc., to form Me-S colloids and then hydrolyze, enhancing the Fe content... 2+The mineral surface is hydrophilic; then, a hard alkali-based metal ion activator with oxidizing activity is used to adsorb and activate the target mineral surface, employing the metal ion Sn. 4+ / Co 3+ / Cr 3+ On the one hand, compensate S 2- On the one hand, the electrons of oxidation selectively adsorb onto the mineral surface to form positively charged centers, which facilitate subsequent collection and flotation by anionic collectors, thereby enhancing the overall mineral separation selectivity within the system.

[0025] The solution medium is ion-regulated by first using a hard base whose active component is carbonate / phosphate as a first modifier, and / or, a hard base containing the active component OH... - The second modifier is used for competitive adsorption and dissolution regulation of hydroxyl groups; then, a soft alkali modifier is used for competitive adsorption of sulfides to enhance dispersion regulation; next, a metal ion activator is used for competitive desorption regulation of soft acid oxidation; finally, a selective anion collector is used for adsorption, mineralization, and flotation separation, thus achieving highly selective separation and enrichment recovery of the target aluminosilicate minerals.

[0026] Compared with the prior art, the technical advantages of this invention are: 1) The flotation separation of aluminosilicate minerals has high selectivity, large enrichment ratio, and is easy to obtain high-quality concentrate. The modification and adjustment process is easy to control and is suitable for the separation process of low-grade aluminosilicate minerals containing the target metal.

[0027] 2) The sorting reagents are highly adaptable, making full use of the selective reaction of acids and bases in the process, and can adapt to the selective modification and mineral separation process of various complex aluminum silicate minerals.

[0028] 3) Flotation method is used to achieve highly selective separation of aluminosilicate minerals of different crystal types, with high recovery rate of target metal minerals and is beneficial to the comprehensive recovery of associated metals in materials. Detailed Implementation

[0029] The technical solution of the present invention will be clearly and completely described below with reference to embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0030] Selective separation of silicate minerals is a common challenge in mineral processing, especially since mineral surfaces have similar surface flotation properties and are easily contaminated by unavoidable metal ions (Ca). 2+ / Mg 2+ / Al3+ / Fe 3+ / 2+ Flotation separation systems for aluminosilicate minerals (including those with similar adsorption and pollution characteristics and diverse crystalline chemical structures) often face challenges in achieving high-quality flotation concentrates. Optimizing the performance of flotation agents for aluminosilicate minerals is crucial for obtaining high-quality concentrates. Currently, for flotation separation of silicate minerals containing -Si- / -Al-, the commonly used reagents suffer from poor selectivity in their modifying effects, significant environmental issues with fluorinated modifiers that are relatively effective in inhibiting their growth, and poor adsorption and mineralization efficiency of their collectors. These issues result in low-grade aluminosilicate minerals being difficult to selectively separate, enrich, and recover, leading to low overall utilization rates of the target metal mineral resources.

[0031] To address the challenges of efficient flotation enrichment and recovery of aluminosilicate minerals in existing technologies, this invention proposes a novel separation method for aluminosilicate minerals rich in Al-O and Si-O mineral surfaces. This method utilizes the synergistic properties and process transformation of various modifiers to achieve selective modification and enhanced regulation of different mineral surfaces, thereby improving the separation and sorting of silicate minerals. The method employs a selective reaction of soft and hard acids and bases to modify the aluminosilicate mineral surface, a collection and adsorption method, and a reagent administration system to solve the aforementioned technical problems.

[0032] The present invention provides a method for separating aluminosilicate minerals, comprising: adjusting the grinding pulp with a hard alkali modifier to obtain a first modified pulp; adjusting the first modified pulp with a soft alkali modifier to obtain a second modified pulp; adding a metal ion activator to the second modified pulp for further adjustment to obtain a third modified pulp; adding an anionic collector to the third modified pulp for selective collection and mineralization adjustment; and performing flotation separation using a foaming flotation process to obtain the target mineral concentrate and flotation tailings.

[0033] This invention utilizes the theory of hard and soft acids and bases to perform multiple, multi-stage modifications and enhancements to the properties of mineral surfaces. These modifications include: first, using hard base modifiers to reduce the influence of unavoidable metal ions, resulting in a more negatively charged mineral surface; then, using soft base modifiers to regulate the expression of soft acid-like active species Fe on the mineral surface. 2+ / Cr 2+ ...etc., to form Me-S colloids and then hydrolyze, enhancing the Fe content... 2+ The mineral surface is hydrophilic; then, a hard alkali-based metal ion activator with oxidizing activity is used to adsorb and activate the target mineral surface, on the one hand compensating for S 2-The electrons from oxidation, on the other hand, are redirected to soft / interfacial acid ions for reduction, selectively adsorbing onto the mineral surface to form positively charged centers, which facilitates subsequent collection and flotation by anionic collectors, thereby enhancing the overall mineral separation selectivity within the system. Finally, by using selective anionic collectors for adsorption and mineralization separation, highly selective separation and enrichment recovery of the target aluminosilicate minerals are achieved.

[0034] The method for separating aluminosilicate minerals according to the present invention includes at least one slurry modification process using a hard alkali modifier and at least one slurry modification process using a soft alkali modifier. Through the coupling / synergistic effect of the hard alkali modifier (first slurry modifier and / or second slurry modifier) ​​and the soft alkali modifier, the surface of the silicate minerals is modified and regulated. This allows the surface of silicate minerals with numerous surface defect sites to be sufficiently modified into a strongly negatively charged surface, providing a mineral surface basis for the subsequent selective competitive desorption and collection separation of different minerals.

[0035] In some embodiments, a first modifier is used to adjust the slurry after grinding to obtain a first modified slurry.

[0036] In some embodiments, a second modifier is used to adjust the post-grinding slurry to obtain a first modified slurry.

[0037] In some embodiments, the slurry after grinding is first adjusted with a first modifier to obtain modified slurry A; then, the modified slurry A is adjusted with a second modifier to obtain modified slurry B, i.e., the first modified slurry.

[0038] First, a hard alkali-based first and / or second modifier is used for ion regulation and / or hydroxyl competitive adsorption and dissolution regulation of the solution medium; then, a soft alkali-based modifier (third modifier) ​​is used for sulfide competitive adsorption and enhanced dispersion regulation; next, a metal ion activator (fourth modifier) ​​is used for soft acid oxidation and competitive desorption regulation; finally, an anionic collector is used for enhanced collection and mineralization slurry conditioning, followed by foam sorting, thereby achieving efficient flotation separation and enrichment of low-grade aluminosilicate minerals.

[0039] Taking the last embodiment described above as an example, the specific steps in the sorting method of the present invention and the working principle of each modifier are explained as follows: Step 1: Ion regulation of the solution medium using a hard base-based first modifier: This involves modifying the modifier component that can adjust the unavoidable metal ions in the sorting solution. This modifier is a water-soluble organic or inorganic modifier capable of settling or competitively adsorbing metal ions in the solution. Its main function is to reduce the amount of unavoidable metal ions (Ca) in the sorting solution. 2+ / Mg 2+ / Fe 3+ / Al 3+The effects of non-selective adsorption and activation on different silicate minerals (etc.) are investigated, while the anionic active components compete for the expression sites of positive charges on the mineral surface (Lewis hard acid active components), thereby enhancing the negative charge properties of the mineral surface.

[0040] The active component in the first modifier is one or more of carbonates and phosphates, and contains CO3. 2- / R-COO - and its hydrolysis derivatives, or PO4 3- / R-PO3 2- At least one of its hydrolysis derivatives.

[0041] Preferably, the first modifier is one or more of the following: sodium / potassium carbonate, sodium / potassium bicarbonate, sodium percarbonate, ammonium carbonate, methyl / acetic acid, oxalic acid, ascorbic acid, citric acid, tartaric acid, succinic acid, succinic acid, disodium oxalate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, methylphosphonic acid, aminotrimethylphosphonic acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), polyacrylic acid (PAA), hydroxyphosphonate (HPMA), polyepoxysuccinic acid (PESA).

[0042] Furthermore, the dosage of the first modifier, calculated relative to the dry ore feed for sorting, is 20–5000 g / t; the first modifier is stirred and adjusted with the slurry to be sorted for 2–10 min, and modified slurry A is obtained after adjustment.

[0043] The trend / preferred responses to obtain modified slurry A are: Based on Lewis' (hard and soft) acid-base theory, hard base anionic surfactants (containing the active component CO3) are used. 2- PO4 3- (and its derivatives) to regulate the unavoidable metal ions in flotation solutions: Me n+ (Mg) 2+ Ca 2+ Fe 3+ Al 3+ Cr 3+ (etc.) + CO3 2- / PO4 3- →Me x CO3(s) / Me x PO4; Adsorption modification of mineral surfaces in flotation pulp using hard alkali anionic surfactants: Me n+ (Si) 4+ Al 3+ Mg 2+ Ca 2+ Fe3+ Cr 3+ (etc.) + CO3 2- / PO4 3- →Me x -CO3(s) / Me x PO4.

[0044] Step 2: Adjusting the hydroxyl group competitive adsorption and dissolution using a hard base-based second modifier: This involves adding highly free OH groups. - To adjust the surface charge of different minerals in slurry A, and partially free OH groups. - The adsorption capping of positively charged (Lewis hard acid active components) expresses active sites, partially causing the -Si- and -Al- on the silicate mineral surface to be converted by OH-. - Dissolution and etching cause the surface to exhibit a more negative charge, while adjusting the pH of the slurry to increase the negative charge on the surface of aluminosilicate minerals.

[0045] The second modifier contains a highly free active component OH. - The modifier is preferably one or more of sodium hydroxide, potassium hydroxide, ammonia, calcium hydroxide, etc.

[0046] Furthermore, the dosage of the second modifier, calculated based on the dry ore feed, is 50–3000 g / t; after adding this type of modifier and modifying the slurry for 2–10 minutes, the modified slurry B is obtained.

[0047] Based on Lewis acid-base theory, to obtain modified slurry B, a hard base anionic surfactant (OH-) is used. - The adsorption hydroxylation reactions on the surface of modified silicate minerals include: Me n+ (Si) 4+ Al 3+ Mg 2+ Ca 2+ Fe 3+ Cr 3+ (etc.) + OH - →Me x -OH.

[0048] Step 3: Enhanced dispersion regulation through competitive adsorption of sulfurized sulfur using a soft alkali-based modifier (third modifier): Utilizing free sulfur with strong reducing properties... 2- / HS - The active sites for expressing positively charged (Lewis soft acid-like active components) adsorbed on the mineral surface are again competitively activated, further enhancing the negatively charged expression on the mineral surface. The main functions are, on the one hand, to regulate the movement of silicate mineral surfaces towards more negatively charged expression, thereby increasing the electrostatic repulsion between particles and enhancing the dispersion effect; on the other hand, to utilize anions (S...) 2- / HS - The coating on the mineral surface strengthens the active sites that occupy positively charged expression, thereby reducing the probability of aluminosilicate minerals being adsorbed and collected by anionic collectors. On the other hand, it adjusts the redox potential state of the silicate mineral flotation system, so that the entire flotation system is in a relatively reduced state.

[0049] The soft alkaline modifier contains a highly free active component S. 2- / HS - The modifier. Preferably, the soft alkali modifier (third modifier) ​​is one or more of sodium sulfide / potassium, sodium hydrosulfide / potassium, and ammonium sulfide.

[0050] Furthermore, the dosage of the soft alkali modifier is calculated based on the dry ore feed, and is 50-3000 g / t; after adding this type of modifier and modifying the slurry for 2-10 minutes, the modified slurry C is obtained.

[0051] To obtain slurry C, a soft base anionic surfactant (S) is used. 2- / HS - The potential adsorption modification reactions for strengthening and modifying silicate mineral surfaces include: Me n+ (Fe) 2+ Cr 2+ Co 2+ (etc.) + S 2- →Me x -S.

[0052] After steps one through three, involving multi-stage strengthening and modification of the mineral surface using hard and soft alkalis, the active component CO3 of the hard alkalis is utilized. 2- OH - PO4 3- and soft alkali active component S 2- / HS - Three small molecule modulators of negatively expressed properties modify the positively charged Me(Si) on mineral surfaces. 4+ \Al 3+ \Fe 3+ / 2+ \Ca 2+ \Mg 2+ The active sites of silicate minerals (such as alkali, etc.) are activated during the process. Due to electrostatic adsorption of anions, the surface of the minerals is enhanced by electrostatic force, which strengthens the negative charge of the silicate mineral surface and forms a silicate mineral surface with strong negative charge expression. At the same time, the negative charge repulsion between particles is increased, thereby enhancing the dispersion effect. Through the coupling or synergistic effect of the above-mentioned hard alkali and soft alkali slurry modification process (this embodiment is three processes), the modification and regulation of the silicate mineral surface is achieved, so that the silicate mineral surface with more surface defect sites is fully modified into a surface with strong negative charge, which provides a mineral surface basis for the subsequent selective competitive desorption and collection separation of different minerals.

[0053] It should be noted that, as mentioned above, the synergistic / coupling effect of hard alkali conditioning and soft alkali conditioning in this invention includes at least one hard alkali conditioning modification process and one soft alkali conditioning modification process, which can be composed of step one, step two, and step three. Of course, it is not limited to these, and can also be composed of step one or step two and step three.

[0054] Step Four: Soft acid oxidation competitive desorption regulation using metal ion activators (fourth modifier): A small amount of hard base active components with catalytic oxidation activity is added to the slurry C, which has undergone multiple anion-enhanced modifications. The main function of this type of modifier is that it is easily reduced to form soft acids or interface acids (Lewis acid-base theory) to modify the mineral surface. This results in a higher density of OH- ions in some silicate minerals within the system due to surface adsorption or capping of anionic components. - CO 3- S 2- The differences in the presence of these differences lead to the oxidation and desorption of some anionic active components, thereby exposing some positively charged active sites or mineral surfaces. This allows for selective modification and adjustment of the aluminosilicate mineral surfaces with different crystal structures, providing advantageous mineral surfaces for subsequent anion flotation separation.

[0055] The metal ion activator is Sn, which has oxidizing activity. 4+ / Co 3+ / Cr 3+ Metal ion activators can be reduced to soft / transitional acids and selectively competitively adsorb onto mineral surfaces.

[0056] Preferably, the metal ion activator (fourth modifier) ​​is one or more of the following: tin chloride (SnCl4), tin sulfate (Sn(SO4)2), chromium chloride (CrCl3), chromium sulfate (Cr2(SO4)3), cobalt trichloride (CoCl3), high cobalt sulfate (Co2(SO4)3), and cobalt trihydroxide (Co(OH)3).

[0057] Furthermore, the amount of the metal ion activator is calculated based on the dry ore feed, which is 10-1000 g / t. After adding this type of modifier and adjusting the slurry for 2-10 minutes, the adjusted slurry D is obtained.

[0058] To obtain slurry D, a mineral surface redox modifier is added to competitively regulate the main reaction process on the aluminosilicate mineral surface: When adjusting with tin-containing modifiers such as soft acid oxidizing agents, The main cathode reactions are: Sn 4+ +2e→Sn 2+ E 0 =0.20 V (vs. SHE) Sn 2+ +2e→Sn E 0 =-0.14V (vs. SHE) SnS + 2e → Sn + S 2- E 0 =-0.94 V (vs. SHE) When adjusting with chromium / cobalt-containing modifiers of soft acid oxidizing properties, The main cathode reactions are: Cr 3+ / Co 3+ +2e→Cr 2+ / Co 2+ E 0 =-0.41 V / 1.82 V (vs. SHE) Cr 2+ / Co 2+ +2e→Cr / Co E 0 =-0.9V / -0.277V (vs. SHE) Co(OH)3 + e → Co(OH)2 + OH - E 0 =0.20 V (vs. SHE) CoS + 2e → Co + S 2- E 0 =-0.93V (vs. SHE) During the process, the main reactions at the anode are: S+2e→S 2- E 0 =-0.58 V (vs. SHE) SO3 2- +3H₂O + 6e → S 2- +OH - E 0 =-0.61 V (vs. SHE) SO4 2- +H₂O + 3e → SO₃ 2- +2OH - E 0 =-0.90 V (vs. SHE).

[0059] Step 5: Enhanced Collection and Mineralization Foam Separation: An anionic collector is added to the modified slurry D to enhance the collection of minerals with -COO2. - -OSO3 - -SO3 - -CONHOH is electrostatically adsorbed onto the positively charged active sites on the surface of the target mineral, while still repelling the non-target mineral surface covered by anions, thus performing anion-selective collection, mineralization, and slurry conditioning.

[0060] The anionic collector is one or more of the following: fatty acid surfactants, organic sulfuric acid / sulfonic acid surfactants, and their emulsifying agents.

[0061] Preferably, the anionic collector is one or more of the following: fatty acid oxidized paraffin soap, oleic acid, sodium oleate; organic sulfur-containing sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium petroleum sulfonate; and hydroxamic acids such as octyl hydroxamic acid, benzyl hydroxamic acid, and combinations thereof.

[0062] Furthermore, the anionic collector is used at a dosage of 50–3000 g / t based on the dry ore feed. After adding this type of collector and adjusting the slurry for 2–10 minutes, the ore slurry E to be separated is obtained.

[0063] Subsequently, aeration is performed for foaming positive flotation to separate minerals. The flotation process adopts a combination of roughing-scavenging-cleaning. The time for a single roughing-scavenging operation is 3 to 10 minutes, and the time for a single cleaning operation is 2 to 6 minutes, yielding the target mineral concentrate product F and the non-target mineral tailings product G.

[0064] The technical solution and effects of the present invention will be described below with reference to specific embodiments: Example 1 Kyanite is a high-alumina silicate mineral that is widely used as a high-quality refractory material.

[0065] The main minerals in a kyanite sample from a kyanite mine in Gansu Province were kyanite, quartz, and biotite, followed by albite and garnet. Small amounts of muscovite, chlorite, apatite, and trace amounts of orthoclase, calcite, monazite, hematite / limonite, ilmenite, magnetite, monazite, talc, rutile, and pyrite were also present. The original sample contained the following components: Al₂O₃ (14.65%), SiO₂ (65.14%), CaO (0.56%), MgO (4.65%), K₂O (2.98%), Na₂O (2.51%), TiO₂ (0.46%), TFe (4.32%), and S (0.08%). The mineral with recovery value in the ore sample is kyanite. The difficulty in its flotation recovery lies in the fact that the ore contains a large amount of biotite and a small amount of iron-bearing minerals such as garnet, staurolite, hematite, magnetite and pyrite. The iron content in the kyanite concentrate is prone to exceed the standard.

[0066] The kyanite ore is processed using the sorting method of this invention through the following steps: 1) Solution medium ion control adjustment: After grinding the ore to 60% -0.074mm, add 100 g / t of sodium hexametaphosphate, a hard alkali modifier, for 3 minutes to adjust the pulp, obtaining modified pulp A. The modifier is used to adjust the unavoidable Fe in the flotation system. 3+ / Ca 2+ / Mg 2+ And so on, promoting the formation of hard base PO4 3- With the unavoidable hard acid Fe in the system 3+ / Ca 2+ / Mg 2+ Active species preferentially react to form hydrophilic complexes, thereby reducing the adverse effects of inevitable metal ion adsorption and thus reducing the buoyancy of feldspar and quartz minerals.

[0067] The main reaction process is: PO4 3- +Me(Fe 3+ / Ca 2+ / Mg 2+ )→Me(Fe 3+ / Ca 2+ / Mg 2+ ) x -PO4.

[0068] 2) Sulfide competitive adsorption enhanced dispersion regulation: 500 g / t of sodium hydrosulfide, a soft alkali third modifier, was added to the modified slurry A based on dry ore and stirred for 3 min to obtain modified slurry C. The active sites on the mineral surface were selectively adsorbed and modified by soft alkali active species, which regulated the expression of positively charged active sites on the surface of iron-bearing gangue minerals and reduced the floatability of biotite, hematite, magnetite, and iron-bearing garnet.

[0069] During the process HS - With Fe-containing minerals (Fe 2+ Selective adsorption modification of the surface of soft acids and aluminum / silicate iron minerals includes: Fe 2+ +S 2- / HS - →FeS x ; Then FeS on the mineral surface x Active species undergo hydrolysis, thus enhancing hydrophilicity; FeS x +H₂O→Fe(OH) x +H + ; Another part, due to HS - / S 2- The effect of reduction is relatively greater on hard acid-bearing iron minerals (such as hematite / magnetite). 3+ The reaction of / Fe2O3) is: HS- / S 2- +Fe 3+ +H₂O→FeS x +SO4 2- +OH - ; Then, similar to the FeS surface of minerals... x The active species are hydrolyzed and subsequently modified by hydrophilization.

[0070] 3) Soft acid oxidation competitive desorption adjustment: Add cobalt sulfate (Co2(SO4)3), the fourth modifier of hard bases, to slurry C at 50 g / t based on dry ore. Stir and adjust the slurry for 3 min to obtain slurry D. This allows the Al-O and Si-O bonds of the kyanite in the system to be broken, and the Al-OH and Si-OH mineral surfaces of the hard bases to be desorbed by hard acid Co. 3+ Selective adsorption promotes the adsorption of mineral metal ions, thereby activating the mineral surface. The main adsorption / activation reactions in this process include Co... 3+ +OH - →Co(OH)3+HS - / S 2- →CoS x +OH - ; In contrast, because the flotation system is in an alkaline environment, FeS x Hydrolysis produces H + It is easy to occur, and Co(OH)3 produces OH. - The redox reaction proceeds relatively slowly, and tends to proceed in the form of positively charged Co ions. 3+ Electrostatic adsorption onto the surface of kyanite enhances the expression of positive charge on the kyanite surface, which is also beneficial for the selective collection and flotation separation of subsequent anionic collectors.

[0071] 4) Enhanced froth flotation with enhanced collection and mineralization: Anionic collector benzyl hydroxamic acid + sodium oleate 400 + 100 g / t was added to slurry D and stirred for 3 minutes to achieve collection and mineralization of kyanite by the anionic collector. Subsequently, aeration was performed, and froth flotation separation was carried out using a two-roughing-one-scavenging-three-cleaving process to obtain kyanite concentrate and tailings. The obtained kyanite concentrate had an Al2O3 content of 60.54% and a recovery rate of 85.2%, and a TFe content of 0.32%, with a relative enrichment ratio of kyanite minerals reaching 11.0.

[0072] Example 2

[0073] The difference from Example 1 is that in step 1), the first hard base modifier added is methylphosphonic acid 150 g / t.

[0074] The obtained kyanite concentrate contained 60.15% Al2O3 with a recovery rate of 85.0%, and the obtained concentrate contained 0.33% TFe.

[0075] Example 3

[0076] The difference from Example 1 is that in step 2), the added soft alkali third modifier is potassium hydrosulfide.

[0077] The obtained kyanite concentrate contained 60.23% Al2O3 with a recovery rate of 84.8%, and the obtained concentrate contained 0.32% TFe.

[0078] Example 4

[0079] The difference from Example 1 is that in step 3), the fourth modifier added is chromium sulfate.

[0080] The obtained kyanite concentrate contained 59.98% Al2O3 with a recovery rate of 85.1%, and the obtained concentrate contained 0.33% TFe.

[0081] Comparative Example 1

[0082] The conventional flotation process using phosphate / carbonate slurry conditioning and sodium oleate (anionic collector) is adopted, excluding step 2) third conditioning agent conditioning and step 3) fourth conditioning agent conditioning in Example 1.

[0083] Comparative Example 2

[0084] The conventional flotation process using fluoride / sodium silicate conditioning and dodecylamine (cationic collector) was adopted, without the use of hard alkali conditioning agents or soft alkali conditioning agents.

[0085] Compared with Comparative Examples 1-2, it was found that the Al2O3 content of the concentrate in Examples 1-4 using the method of the present invention was increased by at least 4.5 percentage points, the recovery rate was increased by at least 5 percentage points, and the iron content in the concentrate was reduced by at least 1.5 percentage points.

[0086] Example 5

[0087] The low-grade beryllium ore contains 0.080% BeO, 0.10% Li2O, and 1.56% TFe. Beryllium is mainly found in beryl, while lithium is mainly found in spodumene. The main aluminosilicate minerals include white / black / phlogopite, albite, plagioclase, iron-bearing amphibole, and quartz. The valuable metallic minerals in this ore are mainly beryllium minerals, with a low lithium content.

[0088] The method of the present invention for processing low-grade beryllium-containing ore includes the following steps: 1) Solution medium ion regulation: Add 1000 g / t of sodium carbonate, the first hard alkali modifier, to the slurry to be separated based on dry ore, and stir for 3 minutes to obtain modified slurry A. During the process, the unavoidable hard acid Fe in the system is regulated by the hard alkali modifier. 3+ / Ca 2+ / Mg 2+ Ionic components reduce the negative impact of inevitable metal ion adsorption within the system.

[0089] 2) Hydroxyl competitive adsorption and dissolution adjustment: 200 g / t of sodium hydroxide, a hard base second modifier, was added to slurry A and stirred for 3 min to obtain modified slurry B. During the process, highly free hard base OH groups were used for adsorption and dissolution. - The modification of the mineral surface is enhanced, resulting in secondary hydroxylation of Al-O and Si-O on the mineral surface, increasing the electronegativity expression of the mineral surface, and making Al-OH and Si-OH on the mineral surface more prominent.

[0090] 3) Sulfide competitive adsorption enhanced dispersion regulation: 1000 g / t of sodium sulfide, a soft alkali third modifier, was added to slurry B based on dry ore and stirred for 3 min to obtain modified slurry C. Subsequently, the surface of iron-bearing minerals was modified with soft alkali active species to enhance the hydrophilicity of iron-bearing amphibole.

[0091] 4) Soft acid oxidation competitive desorption adjustment: Add ionic hard acids (which can be oxidized to soft acid ions for competitive adsorption) as the fourth modifier, tin sulfate (Sn(SO4)2), at a rate of 100 g / t based on dry ore, to slurry C. Stir and adjust the slurry for 3 minutes to obtain slurry D. This allows the hard base surfaces (Al-O and Si-O bonds on the target mineral surface) to be desorbed by the hard acid Sn(SO4)2, resulting in the Al-OH and Si-OH bonds on the target mineral surface being broken. 4+ Selective adsorption promotes the adsorption of mineral metal ions, thereby activating the mineral surface. The main adsorption / activation reactions in this process include Sn. 4+ +OH - →Sn 2+ +HS - / S 2- →SnS x .

[0092] 5) Enhanced froth separation for mineralization: 800 g / t of anionic collector oxidized paraffin soap (731) was added to slurry D, stirred for 3 min, followed by aeration. A two-roughing-one-scavenging-three-cleaning process was used for froth flotation separation to obtain beryl concentrate and tailings. The BeO content in the obtained beryl concentrate was 6.1%, with a recovery rate of 80.2%. The TFe content in the obtained concentrate was 0.65%, and the relative enrichment ratio of BeO was 76.5.

[0093] Example 6

[0094] The difference from Example 5 is that in step 1), the first hard base modifier added is formic acid 1500 g / t.

[0095] The obtained beryl concentrate contained 5.9% BeO with a recovery rate of 80.0% and 0.67% TFe.

[0096] Example 7

[0097] The difference from Example 5 is that in step 2), potassium hydroxide, a hard base second modifier, is added.

[0098] The obtained beryl concentrate contained 6.0% BeO with a recovery rate of 80.2% and 0.64% TFe.

[0099] Example 8

[0100] The difference from Example 5 is that in step 3), potassium hydrosulfide, a soft alkali third modifier, is used.

[0101] The obtained beryl concentrate contained 6.0% BeO with a recovery rate of 79.9%, and the obtained concentrate contained 0.65% TFe.

[0102] Example 9

[0103] The difference from Example 5 is that in step 4), tin chloride, a soft alkali-based fourth modifier, is used.

[0104] The obtained beryl concentrate contained 6.1% BeO with a recovery rate of 80.0% and 0.66% TFe.

[0105] Comparative Example 3

[0106] A flotation method using a commonly used Na₂CO₃-NaOH-Na₂S-FeCl₃ modifier-oxidized paraffin soap collector flotation system was employed. Results showed that Comparative Example 3 exhibited little selectivity for separating Fe-containing gangue minerals (amphibole, tremolite, etc.). Compared to Comparative Example 3, the BeO content in the beryllium concentrate obtained using the method of this invention in Examples 5-9 was increased by at least 1.6 percentage points, and the BeO recovery rate was increased by at least 5 percentage points.

[0107] The description of this invention is given for illustrative and descriptive purposes only and is not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of the invention and to enable those skilled in the art to understand the invention and to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A method for sorting aluminosilicate minerals, characterized in that, include: The grinding pulp is prepared by using a hard alkali modifier to obtain a first modified pulp; this includes: preparing the pulp with a first modifier, and / or preparing the pulp with a second modifier; the first modifier is selected from one or more modifiers whose active component is a carbonate or a phosphate, and the second modifier is selected from modifiers containing an active component OH. - One or more of the modifiers; The first modified slurry was prepared by using a soft alkali modifier to obtain a second modified slurry; the soft alkali modifier was selected from those containing active component S. 2- / HS - One or more of the modifiers; A metal ion activator was added to the second modified slurry for slurry conditioning to obtain a third modified slurry; An anionic collector is added to the third modified slurry for selective collection and mineralization, followed by flotation separation using a foaming flotation process to obtain the target mineral concentrate and flotation tailings.

2. The method for sorting aluminosilicate minerals according to claim 1, characterized in that, The first modifier is one or more of the following: sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium percarbonate, ammonium carbonate, formic acid, acetic acid, oxalic acid, ascorbic acid, citric acid, tartaric acid, succinic acid, succinic acid, disodium oxalate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, methylphosphonic acid, aminotrimethylphosphonic acid, hydroxyethylidene diphosphonic acid, polyacrylic acid, hydroxyphosphonate, and polyepoxysuccinic acid. And / or, the amount of the first modifier is calculated to be 20 to 5000 g / t relative to the dry ore of the sorting feed, and the time for adjusting the slurry with the first modifier is 2 to 10 min.

3. The method for sorting aluminosilicate minerals according to claim 1, characterized in that, The second modifier is one or more of sodium hydroxide, potassium hydroxide, ammonia, and calcium hydroxide; And / or, the dosage of the second modifier is 50-3000 g / t based on the dry ore feed, and the time for adjusting the slurry with the second modifier is 2-10 min.

4. The method for sorting aluminosilicate minerals according to claim 1, characterized in that, The soft alkali modifier is one or more of sodium sulfide, potassium sulfide, sodium hydrosulfide, potassium hydrosulfide, and ammonium sulfide. And / or, the dosage of the soft alkali modifier is 50-3000 g / t based on the dry ore feed, and the time for adjusting the slurry with the soft alkali modifier is 2-10 min.

5. The method for sorting aluminosilicate minerals according to claim 1, characterized in that, The metal ions in the metal ion activator include Sn. 4+ Co 3+ Cr 3+ One or more of them.

6. The method for sorting aluminosilicate minerals according to claim 5, characterized in that, The metal ion activator is one or more of tin tetrachloride, tin sulfate, chromium chloride, chromium sulfate, cobalt trichloride, high cobalt sulfate, and cobalt trihydroxide.

7. The method for sorting aluminosilicate minerals according to claim 5, characterized in that, The dosage of the metal ion activator is calculated based on the dry ore feed at 10–1000 g / t, and the time for adding the metal ion activator to adjust the slurry is 2–10 min.

8. The method for sorting aluminosilicate minerals according to claim 1, characterized in that, The anionic collector is selected from one or more of fatty acids, organic sulfur-containing compounds, and hydroxyoxime acids.

9. The method for sorting aluminosilicate minerals according to claim 8, characterized in that, The anionic collector is one or more of the following: oxidized paraffin soap, oleic acid, sodium oleate, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium petroleum sulfonate, octyl hydroxamic acid, and benzyl sulfoxyxamic acid. And / or, the amount of the anionic collector is calculated based on the dry ore feed as 50-3000 g / t, and the time for adding the anionic collector to adjust the slurry is 2-10 min.

10. The method for sorting aluminosilicate minerals according to claim 1, characterized in that, Flotation separation is performed using a foamed positive flotation process, employing a combined process of roughing-scavenging-cleaning. The time for a single coarse selection operation is 3 to 10 minutes, the time for a single sweeping operation is 3 to 10 minutes, and the time for a single fine selection operation is 2 to 6 minutes.