A flotation collector and its preparation method and application

Abstract

The present invention discloses a flotation collector, a preparation method, and an application thereof, and relates to the field of mineral processing technology. The flotation collector comprises carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol, and sulfate in a mass ratio of (3-6): (1-12): (2-3): (3-8). During the flotation treatment of cassiterite ore, the composite flotation agent prepared thereby reduces the loss of easily muddied fine and micro-grained cassiterite in tailings after one roughing, three scavenging, and three cleaning steps. The agent accurately adsorbs and reduces the cassiterite content in the cassiterite ore, achieves efficient recovery of fine and micro-grained cassiterite, improves the effective recovery of cassiterite, and significantly improves the tin grade and recovery rate in the tin concentrate.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a flotation collector and a preparation method and application thereof. Background Art

[0002] Tin (Sn) is widely used in electronic solders, semiconductors, batteries, solder alloys, and other fields, and is particularly indispensable in the electronics and solder industries. Cassiterite (primarily composed of SnO2) is the primary mineral raw material for extracting tin. With technological advancements, the demand for tin continues to grow, and cassiterite, as a primary source, is of undeniable importance. However, the properties of cassiterite present numerous challenges in its beneficiation process. Common issues are as follows:

[0003] (1) Cassiterite often coexists with other sulfide minerals such as copper, lead, zinc, and silver. Due to the significant differences in the properties of these minerals, the grinding and separation process can easily lead to an increase in the content of fine and micro-particle cassiterite, which reduces the recovery rate of cassiterite. (2) Cassiterite also often coexists with gangue minerals such as calcite, quartz, and fluorite. This symbiotic relationship reduces the grade and precision of cassiterite. (3) Micro-particle cassiterite and gangue minerals are easily muddied during the grinding process, forming a mud cover on the mineral surface, which further affects the precise targeted adsorption of flotation reagents on the mineral surface, thereby affecting the beneficiation efficiency and recovery rate of cassiterite.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a flotation collector and its preparation method and application to solve the above technical problems.

[0006] The present invention is achieved in that:

[0007] In a first aspect, an embodiment of the present invention provides a flotation collector comprising carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol, and sulfate in a mass ratio of (3-6): (1-12): (2-3): (3-8).

[0008] In a second aspect, an embodiment of the present invention provides a method for preparing the flotation collector as described above, the preparation method comprising:

[0009] The flotation collector is prepared by mixing carbonized methyl carbamate, zinc diethyldithiocarbamate, octanol and sulfate in proportion, reacting them at normal pressure and a temperature of 50-100° C. for 120-200 minutes.

[0010] In a third aspect, an embodiment of the present invention provides a composite flotation reagent, which comprises the flotation collector as described above or the flotation collector prepared by the preparation method as described above, and at least one of an activator, a foaming agent, and a defoaming agent;

[0011] Wherein, the activator is selected from any one of the following components:

[0012] Component 1: lead nitrate, alkylsulfonic acid and oxalic acid in a mass ratio of (0.5-1.5):(0.5-1.5):(0.5-1.5);

[0013] Component 2: lead nitrate and alkyl sulfonic acid in a mass ratio of 4:(2-5);

[0014] The foaming agent is selected from at least one of camphor oil, pine needle oil and cresol acid;

[0015] The defoaming agent is selected from at least one of palmitic acid, cottonseed oil and castor oil.

[0016] In a fourth aspect, embodiments of the present invention provide a use of the aforementioned flotation collector, or the flotation collector prepared by the aforementioned preparation method, or the aforementioned composite flotation reagent in cassiterite ore flotation.

[0017] The present invention has the following beneficial effects:

[0018] The flotation collector provided in the embodiments of the present invention is a new type of organic collector, which is prepared by mixing carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sulfate; the amino group (-NH2) and methyl formate (-COO) in the flotation collector selectively adsorb to the exposed cassiterite crystal faces and form stable chemical bonds, thereby improving the floatability of the cassiterite.

[0019] A flotation collector is combined with at least one of an activator, a foaming agent and a defoaming agent to prepare a composite flotation agent. During the flotation treatment of cassiterite ore, after one roughing selection, three scavenging selections and three cleaning selections, the loss of easily muddied fine and micro-grained cassiterite in the tailings is reduced, and efficient recovery of fine and micro-grained cassiterite is achieved, thereby improving the effective recovery of cassiterite and significantly improving the tin grade and recovery rate in the tin concentrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0021] Figure 1 Schematic diagram of the process flow of cassiterite flotation treatment in an embodiment of the present invention;

[0022] Figure 2 This is the infrared test spectrum of the flotation collector. DETAILED DESCRIPTION

[0023] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0024] In a first aspect, an embodiment of the present invention provides a flotation collector comprising carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol, and sulfate in a mass ratio of (3-6): (1-12): (2-3): (3-8).

[0025] It should be noted that during the ore flotation process, the collector is adsorbed on the surface of the mineral, forming a hydrophobic film, which enhances the hydrophobicity of the target mineral, allowing it to adhere to the bubbles and float out with the foam layer. Traditional collectors have the following shortcomings:

[0026] (1) Traditional collectors (such as xanthate, black medicine or fatty acids) have an adsorption effect on a variety of minerals, making it difficult to effectively separate the target minerals from the gangue minerals, resulting in a decrease in the concentrate grade and an increase in the subsequent smelting cost; (2) Traditional collectors (such as thiophosphates or cyanides) are toxic and may pollute water or soil, which does not meet the requirements of green mines; for example, hydrocarbon sulfonates have poor biodegradability and long-term accumulation may damage the ecological environment; (3) Traditional collectors have weak collection capabilities for extremely fine particles or oxidized ores, which can easily cause metal loss; (4) Mineral mud in complex ores (such as kaolin or montmorillonite) will adsorb collectors, resulting in poor collector adaptability, increased drug consumption and deterioration of flotation indicators; (5) Collectors (such as dodecylamine) can easily cause the foam to be too sticky or fragile, affecting the stability of flotation operations.

[0027] The flotation collector provided in the embodiment of the present invention is a novel organic collector, which is prepared by mixing carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sulfate.

[0028] Among them, carbonized methyl carbamate has the following characteristics: after being modified with carboxylic acid-phosphonic acid bipolar groups, the carboxyl group (-COOH) and phosphonic acid group (-PO3H2) in its molecule can selectively chelate Sn on the surface of cassiterite. 4+ (Binding energy increased by 3.8 times), forming a hydrophobic metal complex, while the mesoporous structure (specific surface area> 800m 2 / g) to enhance the physical adsorption capacity of fine-grained cassiterite.

[0029] Zinc diethyldithiocarbamate has the following characteristics: controlled release is achieved through thermosensitive microencapsulation technology (PNIPAM coating), and its thiocarbamate group (-N-CSS - ) is quickly exposed in the 35°C slurry, bonding with the oxygen vacancies on the SnO2 surface to form a stable chemical adsorption layer, significantly reducing the thickness of the hydration film on the mineral surface.

[0030] Butyl octanol acts as an amphiphilic co-adsorbent, and its long carbon chain (C8) is inserted into the carbonized methyl carbamate adsorption layer, enhancing the mineral hydrophobicity through hydrophobic association.

[0031] Sulfate (such as Na2SO4) is converted to SO4 2- Ion exchange with hydroxyl groups (-OH) on the surface of cassiterite exposes more Sn active sites, while adjusting the slurry potential to optimize the adsorption kinetics of the collector.

[0032] The synergistic mechanism of the use of new organic collectors is as follows: carbonized methyl carbamate provides specific chelating anchor points, zinc diethyldithiocarbamate dynamically supplements adsorption sites, butyl octanol enhances the ductility of hydrophobic chains, and sulfate activates the mineral surface. The four work through the triple effects of chemical bonding-hydrophobic assembly-potential regulation, increasing the contact angle of cassiterite from 35° to 78° and the flotation rate constant by 2.3 times. In particular, the recovery rate of -20μm fine-particle cassiterite is increased to more than 85%.

[0033] The amino groups (-NH2) and methyl formate (-COO) in the flotation collector selectively adsorb to the exposed cassiterite crystal faces and form stable chemical bonds, thereby improving the floatability of the cassiterite. The details are as follows:

[0034] The amino groups (-NH2) and methyl formate (-COO) in the flotation collector selectively adsorb on the exposed cassiterite crystal faces (such as (110), (101), (200) and (211)). Among them, the OC=O group acts as an electron donor and establishes a Sn-...O=C spatial interaction with the surface cations (Sn) on the cassiterite, inducing significant chemical bonding and forming a stable chemical bond with the electron pairs provided by the -NH2 group, thereby improving the floatability of the cassiterite.

[0035] It should be noted that when the dosage of the components of the flotation collector is within the above-set ratio range, a better tin collection effect is achieved, but this does not mean that the dosage of the components of the flotation collector has and is only limited to the above-mentioned ratio selection; the mass ratio of carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sulfate can be selected from any one of 3:5:2:4, 4:8:2:6, 5:10:3:7, 5:12:3:5 and 6:12:3:8, or other values ​​within the range of (3-6): (1-12): (2-3): (3-8).

[0036] In other embodiments of the present invention, one or a combination of two components can be selected for ore flotation according to actual needs, such as achieving the effect of copper capture in the flotation process of chalcopyrite and pyrite.

[0037] In an optional embodiment of the present invention, the sulfate is selected from at least one of sodium sulfate, zinc sulfate, ferrous sulfate, sulfated soap, alkyl sulfate and petroleum sulfonate.

[0038] It should be noted that the sulfate reagent used in the present invention is low-cost and widely available, but the dosage must be controlled according to the characteristics of the ore to avoid excessive inhibition or interference with the flotation system. Its main effects are reflected in the following aspects:

[0039] Sodium sulfate, which focuses on physical adjustments (dispersion, pH, and ionic strength), is suitable for oxide ores with high levels of ore slime. It inhibits fine mud agglomeration, reduces interference from ore slime on the flotation process (e.g., clay encapsulating useful minerals), and prevents clay minerals (e.g., kaolinite) from affecting concentrate grade. It also helps increase ionic strength in the slurry, improves bubble stability, and enhances flotation efficiency. However, excessive use may interfere with foam stability.

[0040] Zinc sulfate: Specifically used to suppress zinc minerals, it is a key agent in lead-zinc / copper-zinc separations. During copper-zinc separation, zinc sulfate suppresses zinc minerals and improves the purity of copper concentrate. It must be used in conjunction with cyanide or sulfite.

[0041] Ferrous sulfate: It mainly inhibits pyrite, has both reduction and environmental protection functions, and reduces the pollution of sulfur to concentrate; when flotating sulfide ores (such as galena and chalcopyrite), ferrous sulfate can reduce the oxide film (such as PbSO4) on the surface of the mineral and restore its floatability; in flotation tailings, Fe 2+ Can precipitate heavy metal ions (such as Cu 2+ 、Zn 2+ ), reduce environmental pollution. Fe(OH)3 precipitation is easily generated in an alkaline environment.

[0042] Sulfated soap: It is derived from natural raw materials and has better biodegradability than synthetic agents; it can maintain good capture performance under hard water conditions.

[0043] Alkyl sulfate: can significantly reduce the surface tension of water and generate a stable foam layer, which is suitable for flotation systems that require high foam stability.

[0044] Petroleum sulfonates: They have good effects on sulfide ores (such as chalcopyrite and galena) and partially oxidized ores (such as hematite); they have both collecting and emulsifying properties, which can inhibit the interference of ore slime on flotation and improve the dispersion of ore pulp.

[0045] In a second aspect, an embodiment of the present invention provides a method for preparing the flotation collector as described above, the preparation method comprising:

[0046] After carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sulfate are mixed in proportion, the mixture is reacted for 120 minutes to 200 minutes under normal pressure and a temperature of 50-100 degrees Celsius to prepare a flotation collector.

[0047] It should be noted that increasing temperature generally accelerates reaction kinetics, but excessively high temperatures may lead to side reactions, while excessively low temperatures may result in incomplete reactions. Reaction temperature directly affects the configuration and degree of branching of the molecular hydrophobic chains in the flotation collector. Reaction time can be adjusted appropriately based on the actual amount of material being processed. Insufficient reaction time can result in incomplete reaction, while excessively long reaction times may trigger hydrolysis or oxidation, hindering the control of side reactions.

[0048] During the preparation process, in order to avoid local overheating, product deposition and other problems, and to ensure that the flotation collector is more uniform and the reaction is more thorough, appropriate stirring treatment can be carried out.

[0049] In a third aspect, an embodiment of the present invention provides a composite flotation reagent, which comprises the flotation collector as described above or the flotation collector prepared by the preparation method as described above, and at least one of an activator, a foaming agent, and a defoaming agent;

[0050] Wherein, the activator is selected from any one of the following components:

[0051] Component 1: lead nitrate, alkylsulfonic acid and oxalic acid in a mass ratio of (0.5-1.5):(0.5-1.5):(0.5-1.5);

[0052] Component 2: lead nitrate and alkyl sulfonic acid in a mass ratio of 4:(2-5);

[0053] The foaming agent is selected from at least one of camphor oil, pine needle oil and cresol acid;

[0054] The defoaming agent is selected from at least one of palmitic acid, cottonseed oil and castor oil.

[0055] It should be noted that collectors determine mineral floatability, activators broaden the range of mineral floatability, frothers ensure bubble transport, and defoamers optimize foam structure. Their rational combination can reduce the number and dosage of reagents, achieving high selectivity, high recovery, and low reagent consumption for flotation, which is particularly crucial for complex paragenetic minerals. The specific role of each substance in the flotation process is as follows:

[0056] Among them, the activator forms an active film on the mineral surface (such as Cu 2+ Substitution of Zn 2+ Forming CuS film) is used to change the surface properties of minerals, enhance the adsorption of collectors or release the inhibition state; in addition, it has the effect of removing the oxide layer. Among them, lead nitrate has the characteristics of selective activation, which can reduce the activation of gangue; through Pb 2+ It adsorbs on the mineral surface to form active sites, significantly enhancing the adsorption capacity of the collector.

[0057] Alkyl sulfonic acid has both activation and capture functions. Specifically, the sulfonic acid group (-SO3H) can react with metal ions (such as Ca 2+ 、Fe 3+ ) binds to the surface of the alkyl sulfonic acid, exposing the hydrophobic alkyl chain (R-), improving mineral floatability. It can also be used directly as an anionic collector. It effectively adsorbs even in slurries with high calcium and magnesium ion concentrations, overcoming the precipitation problem of traditional fatty acid collectors. Compared to traditional activators (such as dichromates), alkyl sulfonic acids are less toxic and more compliant with green mineral processing requirements.

[0058] The strong complexing ability of oxalic acid can dissolve the oxide and hydroxide films (such as PbSO4, Fe(OH)3) on the surface of minerals and restore the natural floatability of minerals. It also has the function of pH adjustment and can complex Ca in the slurry. 2+ 、Fe 3+ In addition, oxalic acid is inexpensive and its degradation products are CO2 and H2O, which is environmentally friendly.

[0059] When component 1 is selected as the activator, the mass ratio of lead nitrate, alkyl sulfonic acid and oxalic acid can be selected from any one of 0.5:1.0:1.2, 1.0:1.5:1.2, 1.0:1.0:1.0, 1.2:1.3:1.2 and 1.5:1.0:1.3 according to actual needs, or other values ​​within the range of (0.5-1.5):(0.5-1.5):(0.5-1.5);

[0060] When component 2 is selected as the activator, the mass ratio of lead nitrate to alkyl sulfonic acid can be selected from any one of 4:2, 4:3, 4:4 and 4:5, or other values ​​within the range of 4:(2-5) according to actual needs.

[0061] Frothers are used to reduce interfacial tension between the gas and liquid, forming a stable bubble layer that carries hydrophobic minerals to the surface. The mechanism of action of frothers is that their polar groups are hydrophilic, while their non-polar groups are aerobic, forming a bubble structure that in turn forms a stable bubble layer that carries hydrophobic minerals to the surface.

[0062] Camphor oil, pine needle oil, and cresol acid used in optional embodiments of the present invention as natural or semi-synthetic frothers exhibit irreplaceable advantages in specific flotation scenarios due to their unique chemical structures and physical properties. Specific advantages are as follows:

[0063] Among them, camphor oil is a by-product of camphor extraction. It contains natural ingredients such as camphorene, eucalyptol, and terpene alcohol. It has both foaming and moderate capturing properties, and is especially suitable for the flotation of fine-particle minerals. It can still maintain the characteristics of stable foam in low-temperature slurry.

[0064] Pine needle oil contains terpenes such as α-pinene and β-pinene, forming a dense foam layer that effectively carries coarse mineral particles (such as apatite and feldspar). Its polar components, such as terpineol, adsorb on the surface of mineral sludge, reducing its damage to the foam. When combined with alkyl sulfonates, pine needle oil extends the life of the foam and is suitable for high-salinity slurries. Its strong anti-interference ability and coarse particle carrying properties make it irreplaceable in saline minerals. Combining camphor oil and pine needle oil creates a foaming agent that not only maintains low-temperature activity but also enhances foam stability.

[0065] The benzene ring structure and hydroxyl group in cresol can reduce the surface tension and bind to the metal ions (such as Cu 2+ , Pb 2+ ) weakly binds, making it particularly suitable for mixed systems of sulfide and oxide ores. Its dual-functionality ensures its robustness in complex sulfide ore flotation, but toxicity must be balanced. It easily controls foam fluidity and provides strong foaming properties. The resulting foam exhibits moderate brittleness, facilitating rapid foam scraping in the concentrating stage and reducing retained impurities.

[0066] Defoamers are used when the foam in the concentration section or scavenging section is too sticky. They are helpful in destroying overly stable foam, controlling the thickness of the foam layer, and preventing impurities from being carried over into the concentrate.

[0067] It should be noted that different combinations of the components in the composite flotation reagent have different effects. Specifically in the implementation method, reasonable combinations can be made according to actual needs to achieve the final effect: for example, the combination of collector and activator can significantly improve the recovery rate of difficult-to-float minerals; the combination of collector and frother can balance the mineral flotation speed and foam stability; the combination of frother and defoamer can accurately control the foam layer and improve the concentrate grade. The main application is to add a small amount of defoamer in the concentration section to reduce the entrainment of fine gangue. If the activator is used in combination with the inhibitor, the paragenetic minerals can be selectively separated.

[0068] In addition, the following aspects should be noted during the use of composite flotation reagents: the activator must be added before the collector, and the inhibitor is usually added before the collector; the use of excessive activator may cause non-target minerals to float (such as Cu 2+ Too much frother will activate the gangue), while too much frother will reduce the selectivity of the composite flotation reagent.

[0069] In a fourth aspect, embodiments of the present invention provide a use of the aforementioned flotation collector, or the flotation collector prepared by the aforementioned preparation method, or the aforementioned composite flotation reagent in cassiterite ore flotation.

[0070] In an optional embodiment of the present invention, cassiterite flotation comprises the following steps:

[0071] The tin polymetallic ore is subjected to grinding and classification treatment to prepare a mixed ore pulp for standby use;

[0072] The mixed pulp is subjected to flotation treatment to obtain tin concentrate;

[0073] The flotation process includes one roughing, three scavenging and three concentrating operations in sequence; the roughing process obtains roughing pulp, each scavenging process obtains scavenging pulp, and each concentrating process obtains concentrating pulp.

[0074] It should be noted that the cassiterite ore in the embodiment of the present invention is a tin polymetallic ore, which is a low-grade complex ore (the average grade of cassiterite is below 0.21%-0.35%). The main metal minerals in the ore are cassiterite, galena and sphalerite, and the gangue minerals are mainly quartz, muscovite and fluorite. The tin content in the ore is 0.61%-0.70%, the average grade of the main valuable element copper is 0.66%-2.36%, and the average sulfur grade is 5.52%-25.00%. In view of the many challenges faced by cassiterite in the mineral processing process, the present invention, in an optional embodiment, optimizes its flotation process. The specific process is as follows:

[0075] The low-grade complex tin polymetallic ore mixed material is subjected to grinding and classification treatment to prepare a mixed ore slurry for standby use.

[0076] It should be noted that grinding has the following characteristics: (1) By mechanically destroying the ore structure, useful minerals (such as copper, iron, gold, etc.) are fully dissociated from gangue (useless minerals), creating the necessary conditions for subsequent separation (such as flotation and magnetic separation), and improving the efficiency and recovery rate of mineral processing. (2) After grinding, the particle size of the mineral particles is reduced, and the specific surface area is significantly increased, which accelerates the contact between the chemical reagents and the target minerals, and improves the reaction rate and recovery rate. (3) Optimizing the particle size of the mineral can avoid over-grinding or under-grinding, and can prevent the mineral particles from being too coarse or too fine, which affects the effect of the subsequent separation process. (4) Through sufficient dissociation, the loss of useful minerals (such as residues in tailings) can be reduced. (5) The fine particles after grinding are easy to transport or stir and mix, which helps to reduce transportation and smelting costs.

[0077] Grinding can be performed by dry grinding, wet grinding, or other methods depending on actual needs, and grinding media or additives can also be added to assist grinding. In an optional embodiment of the present invention, wet grinding is used, in which ore is mixed with water and added to a grinding mill, and the ore is ground by stirring and grinding to produce a prefabricated mixed slurry.

[0078] The prefabricated mixed ore pulp is subjected to classification treatment to obtain a mixed ore pulp, wherein the proportion of the mixed ore pulp satisfying that the ore particle size is less than 0.074 mm is 75%-82%.

[0079] It should be noted that grading slurry minerals after grinding can avoid uneven particle sizes during the grinding process. For example, coarse particles (under-grinding) result in insufficient dissociation of useful minerals, while fine particles (over-grinding) increase energy consumption and the risk of mudification. This improves grinding efficiency and reduces energy and ball consumption. Furthermore, the sludge present in the ground minerals can encapsulate useful mineral particles, hindering reagent adsorption (e.g., in flotation), increasing solution viscosity, and affecting sedimentation or magnetic separation efficiency. After grading, separate treatment or desliming of the sludge can improve concentrate grade and recovery.

[0080] Before flotation, the mixed pulp needs to be diluted with water, wherein the concentration of the ore particles less than 0.074mm is 20%-25%.

[0081] The mixed pulp is subjected to flotation treatment to obtain tin concentrate; wherein the flotation treatment includes one roughing, three scavenging and three concentrating processes in sequence; the roughing process obtains roughing pulp, each scavenging process obtains scavenging pulp, and each concentrating process obtains concentrating pulp.

[0082] It should be noted that each stage of flotation processing has different functions and characteristics, primarily balancing concentrate recovery and quality. The actual flotation process varies depending on ore properties (such as particle size and mineral symbiosis) and may include multiple scavenging or concentrating stages. In the embodiments of the present invention, a flotation process with three scavenging stages and three concentrating stages is used.

[0083] Roughing is used for preliminary separation of raw ore, quickly separating most of the useful minerals and some gangue, to obtain roughing pulp and some tin concentrate. It has the characteristics of large processing capacity, but the concentrate grade is low and may contain more impurities.

[0084] Scavenging is used to reprocess pulp after roughing or scavenging to recover useful minerals and reduce metal loss. It focuses on improving recovery rates. Scavenged pulp is usually returned to roughing or treated separately.

[0085] Concentration is used to further purify slurry after scavenging or concentrating. Multiple flotation steps are used to remove impurities and improve the final concentrate grade. Multi-stage concentrating ensures the concentrate meets smelting or marketing standards.

[0086] It should be noted that the roughing, scavenging and cleaning mentioned above all refer to one flotation operation, that is, a total of seven flotation steps are performed in the flotation process of the present invention; and the roughing pulp obtained in the roughing process, that is, the roughing tailings pulp, is used as the pulp raw material for the first scavenging, and the scavenged pulp obtained in the first scavenging, that is, the scavenging tailings pulp, is used as the pulp raw material for the second scavenging, and so on.

[0087] In each flotation operation, there should be corresponding stirring and aeration methods. In the embodiments of the present invention, any conventional or unconventional stirring method such as mechanical impeller stirring, rotor stirring, erosion method such as gas precipitation method or pressure dissolved gas method can be adopted.

[0088] The present invention does not impose any particular limitation on the setting of flotation parameters or types, which can be reasonably adjusted according to actual needs to achieve mineral separation.

[0089] In an optional embodiment of the present invention, the flotation process includes at least one of the following features:

[0090] Feature 1: Roughing includes adding the first composite flotation agent to the mixed pulp for flotation treatment to obtain part of the tin concentrate and roughing pulp.

[0091] It should be noted that the tin concentrate is uniformly recovered and processed, and the pulp after roughing is used as the raw material for scavenging and further flotation treatment.

[0092] Feature 2: Each scavenging includes adding a second composite flotation agent to the pulp after roughing or scavenging for flotation treatment to obtain part of the tin concentrate and the pulp after scavenging.

[0093] It should be noted that there are three scavenging processes. The tin concentrate obtained from each scavenging process is uniformly recovered and processed. The pulp after the first scavenging process is used as the raw material for the second scavenging process for flotation; the pulp after the second scavenging process is used as the raw material for the third scavenging process for flotation; and the pulp after the third scavenging process is used as the selected raw material for flotation.

[0094] Feature 3: Each concentration includes flotation treatment of the scavenged pulp or the concentrated pulp, during which no reagents are added, to obtain partial tin concentrate and concentrated pulp.

[0095] It should be noted that there are three rounds of beneficiation. The tin concentrate obtained in each round is uniformly recovered and processed. The pulp after the first round of beneficiation is used as the raw material for the second round of beneficiation for flotation; the pulp after the second round of beneficiation is used as the raw material for the third round of beneficiation for flotation; and the pulp after the third round of beneficiation is recovered and processed.

[0096] In an optional embodiment of the present invention, the first composite flotation reagent added during the roughing process includes, based on the mass of the slurry, 50g / t-1000g / t of a flotation collector, 50g / t-80g / t of an activator, 10g / t-20g / t of a defoamer, and 10g / t-20g / t of a frother.

[0097] In an optional embodiment of the present invention, based on the mass of the slurry, the second composite flotation reagent added during the scavenging process includes: 30g / t-1000g / t of flotation collector; 30g / t-50g / t of activator.

[0098] It should be noted that the different composite flotation reagents used in roughing and scavenging are primarily designed to optimize separation targets at different stages, improving the recovery rate of useful minerals and the concentrate grade. Roughing is designed to quickly float out the majority of useful minerals, preventing them from being lost to the tailings. Scavenging, on the other hand, is designed to recover remaining useful minerals in the roughing tailings, further reducing the tailings grade. Excessive addition of collectors in scavenging can cause gangue to float, increasing the burden on the concentrate.

[0099] In an optional embodiment of the present invention, during the flotation treatment, the flotation collector and the activator are both added in the form of solutions;

[0100] The mass concentration of the flotation collector solution is 1%-3%; the mass concentration of the activator solution is 3%-5%.

[0101] It should be noted that adding flotation collectors and activators in the form of aqueous solutions has the following characteristics compared to directly adding reagents:

[0102] (1) It helps to make the flotation collector evenly adsorbed on the surface of the target mineral, reducing the waste of reagents; the activator fully contacts the mineral to be activated, avoiding the "dead zone" effect. (2) It reduces the loss of reagents adhering to the inner wall of equipment or pipelines, reducing the collection efficiency and increasing operating costs.

[0103] The setting of mass concentration can be reasonably adjusted according to actual needs, wherein the mass concentration of the flotation collector solution can be selected from any one of 1%, 1.5%, 2%, 2.5% and 3%, or other values ​​within the range of 1%-3%; the mass concentration of the activator solution can be selected from any one of 3%, 3.5%, 4%, 4.5% and 5%, or other values ​​within the range of 3%-5%.

[0104] The features and performance of the present invention are further described in detail below with reference to the embodiments.

[0105] Example 1

[0106] This embodiment provides a flotation collector, and the preparation steps thereof are as follows:

[0107] Carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sodium sulfate were mixed in proportion, and reacted for 120 minutes under normal pressure and 50° C. to prepare a flotation collector.

[0108] The mass ratio of carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sodium sulfate is 3:1:2:3.

[0109] This embodiment also provides a composite flotation reagent, the specific components of which include: the above-mentioned flotation collector, an activator, a foaming agent and a defoaming agent, which is recorded as a first composite flotation reagent.

[0110] Among them, the activator is lead nitrate, alkyl sulfonic acid and oxalic acid in a mass ratio of 1:1:1; the foaming agent is pine oil, and the defoaming agent is P86.

[0111] Example 2

[0112] This embodiment provides a composite flotation reagent, the specific components of which differ from those of Example 1 only in that:

[0113] The specific components of the activator in the composite flotation reagent are different: lead nitrate and alkyl sulfonic acid with a mass ratio of 4:3, which is recorded as the second composite flotation reagent.

[0114] Example 3

[0115] This embodiment provides a composite flotation reagent, the specific components of which differ from those of Example 1 only in that:

[0116] In the first composite flotation collector, the mass ratio of carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sodium sulfate is 6:12:3:8.

[0117] Example 4

[0118] This embodiment provides a composite flotation reagent, the specific components of which differ from those of Example 1 only in that:

[0119] In the first composite flotation collector, the mass ratio of carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sodium sulfate is 3:5:2:8.

[0120] Application Example 1

[0121] This application example uses the composite flotation reagent of Example 1 to flotate cassiterite. The specific flotation process includes the following steps:

[0122] (1) Grinding and classifying the raw ore to obtain a mixed ore pulp for later use;

[0123] Among them, the raw materials come from a tin-containing mine in Jiangxi Province, with a tin grade of 0.35% and a sulfur grade of 23.25%.

[0124] (2) flotation treatment of the mixed pulp to obtain tin concentrate;

[0125] Among them, flotation treatment includes one roughing, three sweeping and three cleaning processes;

[0126] The roughing process is to add a first composite flotation reagent to the mixed pulp for roughing treatment to obtain a portion of tin concentrate and roughing pulp; wherein the first composite flotation reagent includes 100g / t of a flotation collector, 50g / t of an activator, 10g / t of a defoamer, and 10g / t of a frother; wherein the mass concentration of the flotation collector is 1%, and the mass concentration of the activator is 3%; and the activator includes lead nitrate, alkyl sulfonic acid, and oxalic acid in a mass ratio of 1:1:1.

[0127] A second composite flotation reagent is added to the roughing pulp for scavenging, producing a portion of tin concentrate and a first scavenged pulp. The second composite flotation reagent is added to the first scavenged pulp for flotation, producing a portion of tin concentrate and a second scavenged pulp. The second scavenged pulp is subjected to flotation without adding any reagents, producing a portion of tin concentrate and a beneficiated pulp. The second composite flotation reagent comprises 30g / t of a flotation collector and 30g / t of an activator. The mass concentration of the flotation collector is 2%, and the mass concentration of the activator is 4%. The activator comprises lead nitrate and an alkyl sulfonic acid in a 4:3 mass ratio.

[0128] The tin concentrate obtained from the roughing is subjected to a concentration treatment without adding any reagents, thereby obtaining a portion of the tin concentrate and a first concentrated pulp; a second composite flotation agent is added to the first concentrated pulp for flotation treatment, thereby obtaining a portion of the tin concentrate and a second concentrated pulp; and the second concentrated pulp is subjected to a flotation treatment without adding any reagents, thereby obtaining a portion of the tin concentrate and a concentrated pulp.

[0129] After chemical titration, the tin grade in the concentrated ore pulp was 4.21%, and the tin recovery rate was 55.68%.

[0130] Application Example 2

[0131] This application example provides a cassiterite flotation method. The specific flotation process is the same as that of Application Example 1. The only difference is that the second composite flotation agent used is the second composite flotation agent prepared in Example 2 for cassiterite flotation.

[0132] After chemical titration, the tin grade in the concentrated ore pulp was 5.98%, and the tin recovery rate was 85.02%.

[0133] Application Example 3

[0134] This application example provides a cassiterite flotation method. The specific flotation process is the same as that of Application Example 1. The only difference is that the first composite flotation agent used is the first composite flotation agent prepared in Example 3 for cassiterite flotation.

[0135] After chemical titration, the tin grade in the concentrated ore pulp was 5.45%, and the tin recovery rate was 84.21%.

[0136] Application Example 4

[0137] This application example provides a cassiterite flotation method. The specific flotation process is the same as that of Application Example 1. The only difference is that the first composite flotation agent used is the first composite flotation agent prepared in Example 4 for cassiterite flotation.

[0138] After chemical titration, the tin grade in the concentrated ore pulp was 5.68%, and the tin recovery rate was 84.84%.

[0139] Comparative Example 1

[0140] This comparative example provides a cassiterite flotation method. The specific flotation process is consistent with that of Application Example 1, with the only difference being that this comparative example uses a traditional reagent (benzohydroxamic acid) for cassiterite flotation.

[0141] Among them, the raw materials come from a tin-containing mine in Guangxi. The ore grade contains 0.58% tin and 12.25% sulfur. After chemical titration, the tin grade in the selected ore pulp is 5.01%, and the tin recovery rate is 70.24%.

[0142] Comparative Example 2

[0143] This comparative example provides a cassiterite flotation method. The specific flotation process is different from that of Application Example 1 in that:

[0144] The process is one roughing selection, two sweeping selections, and two fine selections.

[0145] After chemical titration, the tin grade in the concentrated ore pulp was 4.34%, and the tin recovery rate was 65.24%.

[0146] Test Example 1

[0147] This test example conducts infrared absorption test on the flotation collector prepared in Example 1. The schematic diagram of the relevant test results is shown in Figure 2 .

[0148] from Figure 2 It can be seen that 1500.14 cm -1 The peak at 1427.62 cm-1 is attributed to the stretching vibration of CN in the molecule. -1 、1353.94 cm -1 and 1144.22 cm -1 The peaks at are typically associated with CH and CO stretching vibrations. This suggests that the C=O groups and NH bonds in the reagent molecules enhance adsorption on the Sn(IV) surface. This interaction suggests that Sn and C=O bonds chemically adsorb through weak interactions, thereby enhancing the role of these functional groups in improving cassiterite floatability.

[0149] In summary, the flotation collector provided by the present invention overcomes the drawbacks of conventional flotation agents in the flotation of fine and micro-grained cassiterite, such as poor recovery efficiency and high cassiterite content in tailings due to poor adsorption accuracy. It also effectively addresses the challenge of efficiently recovering low-grade tin and polymetallic complex coexistence of fine and micro-grained cassiterite. In the flotation of cassiterite ore, a specific flotation agent and flotation process are employed to efficiently recover tin concentrate through grinding, classification, primary roughing, tertiary scavenging, and tertiary concentrating.

[0150] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A flotation collector, characterized in that: The flotation collector comprises carbonized methyl carbamate, zinc diethyldithiocarbamate, butyl octanol and sulfate in a mass ratio of (3-6): (1-12): (2-3): (3-8).

2. The flotation collector according to claim 1, characterized in that The sulfate is selected from at least one of sodium sulfate, zinc sulfate, ferrous sulfate, sulfated soap and alkyl sulfate.

3. A method for preparing a flotation collector according to claim 1 or 2, characterized in that: The preparation method comprises: The flotation collector is prepared by mixing carbonized methyl carbamate, zinc diethyldithiocarbamate, octanol and sulfate in proportion, reacting them at normal pressure and a temperature of 50-100° C. for 120-200 minutes.

4. A composite flotation reagent, characterized in that: The composite flotation reagent comprises the flotation collector according to any one of claims 1 to 2 or the flotation collector prepared by the preparation method according to claim 3, and at least one of an activator, a foaming agent and a defoaming agent; Wherein, the activator is selected from any one of the following components: Component 1: lead nitrate, alkylsulfonic acid and oxalic acid in a mass ratio of (0.5-1.5):(0.5-1.5):(0.5-1.5); Component 2: lead nitrate and alkyl sulfonic acid in a mass ratio of 4:(2-5); The foaming agent is selected from at least one of camphor oil, pine needle oil and cresol acid; The defoaming agent is selected from at least one of palmitic acid, cottonseed oil and castor oil.

5. Use of the flotation collector according to any one of claims 1 to 2, or the flotation collector prepared by the preparation method according to claim 3, or the composite flotation reagent according to claim 4 in cassiterite flotation.

6. The use according to claim 5, characterized in that Cassiterite flotation includes the following steps: The tin polymetallic ore is subjected to grinding and classification treatment to prepare a mixed ore pulp for standby use; The mixed pulp is subjected to flotation treatment to obtain tin concentrate; The flotation process includes one roughing, three scavenging and three concentrating processes performed sequentially; the roughing process obtains roughing pulp, each scavenging process obtains scavenging pulp, and each concentrating process obtains concentrating pulp.

7. The use according to claim 6, characterized in that The flotation process includes at least one of the following features: Feature 1: The roughing includes adding a first composite flotation agent to the mixed pulp for flotation treatment to obtain a portion of tin concentrate and roughing pulp; Calculated by slurry mass, the first composite flotation reagent includes: 50g / t-1000g / t of flotation collector, 50g / t-80g / t of activator, 10g / t-20g / t of defoamer and 10g / t-20g / t of frother; Feature 2: Each scavenging step includes adding a second composite flotation agent to the roughing pulp or the scavenging pulp for flotation treatment to obtain a portion of tin concentrate and the scavenging pulp; based on the mass of the pulp, the second composite flotation agent includes: 30g / t-1000g / t of flotation collector; 30g / t-50g / t of activator; Feature 3: Each time the concentration includes flotation treatment of the scavenged pulp or the concentrated pulp, no reagent is added during the process, and a portion of tin concentrate and concentrated pulp is obtained; Wherein, the flotation collector is the flotation collector according to claim 1 or 2; The activator is selected from any one of the following components: Component 1: lead nitrate, alkylsulfonic acid and oxalic acid in a mass ratio of (0.5-1.5):(0.5-1.5):(0.5-1.5); Component 2: lead nitrate and alkyl sulfonic acid in a mass ratio of 4:(2-5); The foaming agent is selected from at least one of camphor oil, pine needle oil and cresol acid; The defoaming agent is selected from at least one of palmitic acid, cottonseed oil and castor oil.

8. The use according to claim 7, characterized in that During the flotation treatment, the flotation collector and the activator are both added in the form of solutions; Wherein, the mass concentration of the flotation collector solution is 1%-3%; The mass concentration of the activator solution is 3%-5%.

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