Flotation separation collecting agent for associated ultrafine particle apatite in vanadium titano-magnetite, preparation method of flotation separation collecting agent and direct flotation process

Abstract

The invention discloses a flotation separation collecting agent for associated ultrafine particle apatite in vanadium titano-magnetite and a preparation method and a direct flotation process of the flotation separation collecting agent, and relates to the technical field of mineral separation. The flotation separation collecting agent comprises oxidized paraffin soap, salicylhydroxamic acid, soya bean lecithin and dodecyl sulfopropyl betaine. The preparation method comprises the following steps: independently dissolving the components, and sequentially mixing. The flotation separation collecting agent for the superfine apatite has the characteristic of synergistic interaction of multiple agents, the agent cost is low, the collecting capacity and the separation selectivity of the collecting agent for the superfine apatite are remarkably improved, the phosphorus resource recovery rate exceeds 80%, the loss of the phosphorus resource in tailings is effectively reduced, and the flotation separation collecting agent for the superfine apatite is suitable for industrial production. And efficient recycling of Panxi vanadium titano-magnetite associated phosphorus resources is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a flotation separation collector for associated ultra-fine apatite in vanadium-titanium magnetite and a preparation method and positive flotation process thereof. BACKGROUND

[0002] The Panxi region is an important vanadium-titanium magnetite resource base in China. In addition to being rich in strategic metal elements such as iron, vanadium, and titanium, the ore in this region is also associated with apatite resources of important industrial value. However, the apatite in this region is generally in the form of ultra-fine particles and is closely associated with titanium magnetite, ilmenite, and other main metal minerals, forming a complex intergrowth structure. This special occurrence state makes it difficult for apatite to achieve single liberation during separation and easily intergrow with gangue minerals, significantly increasing the technical difficulty of flotation separation.

[0003] Currently, traditional collectors such as fatty acids, phosphate esters, amines, etc. perform well in the flotation of coarse-grained apatite, but face many challenges when dealing with ultra-fine-grained apatite. First, ultra-fine-grained apatite has a large specific surface area and high surface energy, which easily leads to non-selective agglomeration or excessive dispersion, resulting in a decrease in collector adsorption efficiency. Second, the "entrainment effect" is significant during the flotation of ultra-fine-grained minerals, and the lack of selectivity of conventional collectors makes it easy for gangue minerals to enter the concentrate with the foam, affecting product quality. In addition, higher concentrations of collectors are needed to achieve full surface coverage of ultra-fine-grained apatite, but excessive reagents not only increase costs but also can worsen the flotation environment and reduce separation efficiency.

[0004] In order to solve the above problems, beneficiation researchers have carried out a series of research and practice. Patent CN103831171A discloses a phosphate rock flotation collector and its preparation method, which is mixed by sodium stearate, sulfonate and water, has the characteristics of good selectivity, low temperature resistance, moderate dosage and moderate price, etc.; the low temperature positive flotation of phosphorus iron ore with very low P2O5 grade can obtain high quality phosphate concentrate and has high P2O5 recovery rate. Although this method can effectively float and recover apatite, it has poor flotation effect on ultra-fine apatite. Patent CN109876928B discloses a low-temperature flotation collector for apatite, which can effectively float at low temperature through the synergistic effect of oxidized paraffin soap, soybean oil fatty acid soap and fatty acid methyl ester sodium sulfonate, but has insufficient selectivity for high-impurity or complex ores, and cannot effectively separate apatite from impurity minerals when dealing with apatite ores associated with multiple other minerals and complex components, affecting the quality of concentrate. Patent CN101602031A discloses a combined collector for apatite, which is designed for phosphorus ore with high mud content and is composed of oxidized paraffin soap, salt and sodium oleate, mainly optimizing foam effect and reducing soda ash consumption. However, it is not optimized for the high specific surface area, easy agglomeration and "entrainment effect" of ultra-fine apatite, the dispersibility of fatty acid components is limited, it is difficult to efficiently cover ultra-fine particles, and it lacks means to enhance selectivity, which is not suitable for ultra-fine apatite flotation.

[0005] In view of this, the present application is proposed. SUMMARY

[0006] The present application provides a flotation separation collector for associated ultra-fine particle apatite in vanadium-titanium magnetite, which is suitable for the positive flotation process of associated ultra-fine particle apatite in vanadium-titanium magnetite, has high selective collecting capacity, good adaptability to ultra-fine particle minerals and high concentrate recovery rate, etc.

[0007] The present application is implemented as follows: In the first aspect, the present application provides a flotation separation collector for associated ultra-fine particle apatite in vanadium-titanium magnetite, which comprises the following raw materials in mass percentage: oxidized paraffin soap 40%-80%, salicylhydroxamic acid 10%-40%, soybean lecithin 5%-20% and dodecylsulfopropyl betaine 2%-10%.

[0008] In some preferred embodiments, the collector comprises the following raw materials in mass percentage: oxidized paraffin soap 50%-70%, salicylhydroxamic acid 15%-30%, soybean lecithin 8%-15% and dodecylsulfopropyl betaine 3%-8%.

[0009] In the second aspect, the application provides a preparation method of a flotation separation collector for associated superfine particle apatite in vanadium-titanium magnetite, which comprises the following steps: adding oxidized paraffin soap into water to stir and heat to dissolve to form a first solution; adding salicylhydroxamic acid into lye to stir and dissolve to form a second solution; adding soybean lecithin into an ethanol solution to stir and dissolve to form a third solution; adding dodecyl sulfopropyl betaine into water to stir and dissolve to form a fourth solution; then adding the third solution into the second solution, adding the first solution, and finally adding the fourth solution to mix and stir uniformly, so that the flotation separation collector is prepared.

[0010] In some preferable embodiments, the dissolving temperature of the first solution is 60-90 DEG C, and the stirring time is 5-10 min.

[0011] In some preferable embodiments, the dissolving temperature of the second solution is 15-30 DEG C, the concentration of the lye is 2%-5%, and the dissolving time is 10-30 min.

[0012] In some preferable embodiments, the dissolving temperature of the third solution is 15-30 DEG C, the concentration of the ethanol solution is 2%-10%, and the dissolving time is 10-60 min.

[0013] In some preferable embodiments, the dissolving temperature of the fourth solution is 15-30 DEG C, and the stirring time is 5-10 min.

[0014] In some preferable embodiments, the mixing temperature is 60-90 DEG C, and the mixing and stirring time is 5-10 min.

[0015] In the third aspect, the application further provides a positive flotation process for associated superfine particle apatite in vanadium-titanium magnetite, which adopts the above-mentioned flotation separation collector, and comprises the following steps: first, grinding the phosphate-containing raw ore to 80%-95% of-0.018 mm, and screening by adopting a vertical ring high-intensity magnetic process with a magnetic field strength of 0.4-0.8 T, then adding a pH adjusting agent, a gangue inhibitor and the flotation separation collector in sequence to perform positive flotation, and obtaining phosphate concentrate after one roughing and three cleaning.

[0016] In some preferable embodiments, the adding amount of the pH adjusting agent is 100-1000 g / t, the adding amount of the gangue inhibitor is 1000-3000 g / t, and the adding amount of the flotation separation collector is 100-2000 g / t.

[0017] The application has the following beneficial effects: (1) The four kinds of component medicaments of the flotation separation collector proposed in the application are all conventional medicaments, and have the characteristics of low cost, and are easy to popularize and apply in industrial production.

[0018] (2) The four components of the flotation separation collector of the present application are combined in a certain proportion to form a synergistic mechanism, which significantly improves the collecting ability and selectivity of the collector for ultra-fine particle apatite, and has good flotation effect on ultra-fine particle apatite with complex ore properties, and the grade of the flotation phosphate concentrate is more than 35%, and the recovery rate is more than 80%. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0020] Figure 1 The present application provides a vanadium-titanium magnetite associated with ultra-fine particle apatite positive flotation process flow chart. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be described clearly and completely. The specific conditions in the embodiments are not specified, and are carried out according to conventional conditions or manufacturer's recommended conditions. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased on the market.

[0022] The present application provides a vanadium-titanium magnetite associated with ultra-fine particle apatite positive flotation process flow chart.

[0023] The present application is aimed at the problem of difficult recovery of vanadium-titanium magnetite associated with ultra-fine particle apatite in Panxi, and innovatively uses oxidized paraffin soap, salicylhydroxamic acid, soybean lecithin and dodecyl sulfopropyl betaine in combination. Among them, the soybean lecithin and dodecyl sulfopropyl betaine in the collector are amphoteric surfactants, which have good compatibility with anionic surfactants such as oxidized paraffin soap and salicylhydroxamic acid. The polar groups of oxidized paraffin soap, salicylhydroxamic acid, soybean lecithin and dodecyl sulfopropyl betaine are -COO - , -CONO - , -SO3 - , -PO3 - , which greatly enhances the adsorption effect of the collector on the surface of ultra-fine particle apatite, and the dodecyl sulfopropyl betaine has good calcium soap dispersibility and excellent foam performance, providing excellent dispersibility and foaming property for the collector.

[0024] The flotation separation collector proposed in the application effectively improves the flotation behavior of micro-fine particle minerals and significantly improves the flotation recovery rate through the synergistic effect between components, electrostatic adsorption, hydrogen bonding and hydrophobic association and other multiple action mechanisms; and the reagent selectively adsorbs on the surface of apatite, reduces the entrainment of gangue minerals, and significantly enhances the collection capacity and selectivity of ultra-fine particle apatite. Meanwhile, the components in the composite collector complement each other under different pH conditions, so that the reagent system maintains stable collection performance in a wide pH range, and adapts to the complex ore slurry environment. In addition, the use of natural degradable ingredients such as soybean lecithin, combined with low-toxicity dodecylsulfopropyl betaine, not only improves the flotation efficiency, but also reduces the risk of environmental pollution, which meets the development trend of green beneficiation.

[0025] Preferably, the flotation separation collector comprises the following raw materials in mass percentage: oxidized paraffin soap 50%-70%, salicylhydroxamic acid 15%-30%, soybean lecithin 8%-15% and dodecylsulfopropyl betaine 3%-8%.

[0026] The second aspect of the application provides a preparation method of a flotation separation collector for associated ultra-fine particle apatite in vanadium-titanium magnetite, which comprises the following steps: oxidized paraffin soap is heated and stirred to dissolve in water to form a first solution, the dissolution temperature is 60-90℃, and the dissolution time is 5-10 min; salicylhydroxamic acid is stirred and dissolved in lye to form a second solution, the dissolution temperature is 15-30℃, the lye concentration is 2%-5%, and the dissolution time is 10-30 min; soybean lecithin is stirred and dissolved in an ethanol solution to form a third solution, the dissolution temperature is 15-30℃, the ethanol solution concentration is 2%-10%, and the dissolution time is 10-60 min; dodecylsulfopropyl betaine is stirred and dissolved in water to form a fourth solution, the dissolution temperature is 15-30℃, and the dissolution time is 5-10 min. Finally, the solutions after dissolving the components are mixed by heating and stirring according to the following method: first, the soybean lecithin solution is added to the salicylhydroxamic acid solution, then the oxidized paraffin soap solution is added, and finally the dodecylsulfopropyl betaine solution is added, the mixing temperature is 60-90℃, and the mixing and stirring time is 5-10 min.

[0027] In some embodiments of the application, the lye is sodium hydroxide solution.

[0028] The third aspect of the present application provides a positive flotation process of vanadium-titanium magnetite associated with superfine particle apatite, which adopts the flotation separation collector described above, and includes the following steps: first, grinding the phosphate-containing raw ore to 80-95% of -0.018 mm, screening by using a vertical ring high-intensity magnetic process with a magnetic field strength of 0.4-0.8 T, then sequentially adding a pH regulator 100-1000 g / t, a gangue inhibitor 1000-3000 g / t and a flotation separation collector 100-2000 g / t for positive flotation, and obtaining a phosphate concentrate after one roughing and three cleaning.

[0029] In some embodiments of the present application, the pH regulator is sodium carbonate, and the gangue inhibitor is water glass.

[0030] The features and performances of the present application are further described in detail below in combination with embodiments.

[0031] Embodiment 1 The present embodiment provides a flotation separation collector for superfine particle apatite associated with vanadium-titanium magnetite, which includes the following raw materials in mass percentage: oxidized paraffin soap 60%, salicylhydroxamic acid 25%, soybean lecithin 10% and dodecyl sulfopropyl betaine 5%.

[0032] The preparation method thereof includes the following steps: The oxidized paraffin soap is dissolved in water by heating and stirring, the dissolution temperature is 75°C, and the dissolution time is 8 minutes; the salicylhydroxamic acid is dissolved in a sodium hydroxide solution by stirring at 25°C, the alkali concentration is 4%, and the dissolution time is 15 minutes; the soybean lecithin is dissolved in an ethanol solution by stirring, the ethanol solution concentration is 6%, and the dissolution time is 45 minutes; and the dodecyl sulfopropyl betaine is dissolved in water by stirring, and the dissolution time is 8 minutes. Finally, the solutions after dissolving each component are mixed by heating and stirring according to the following method: first, the soybean lecithin solution is added into the salicylhydroxamic acid solution, then the oxidized paraffin soap solution is added, and finally the dodecyl sulfopropyl betaine solution is added, the mixing temperature is 75°C, and the mixing and stirring time is 8 minutes.

[0033] The present embodiment also provides a positive flotation process of vanadium-titanium magnetite associated with superfine particle apatite, and a process flow chart is shown in Figure 1 The mineral raw material in the present embodiment ranges from a vanadium-titanium magnetite iron tailings in the Panxi region, with a P2O5 content of 3.24%, and the gangue minerals mainly include quartz, ilmenite, chlorite, calcium feldspar and potassium feldspar, as well as a small amount of magnetite, titanic augite, muscovite and kaolinite, etc. The process mainly includes the following steps: The phosphate-containing crude ore is ground to 90% of -0.018 mm, and the magnetite and ilmenite and other magnetic minerals in the crude ore are removed by a vertical ring high-intensity magnetic process with a magnetic field strength of 0.6 T. Under the condition of a 50 wt% ore slurry concentration, 500 g / t of sodium carbonate as a pH regulator, 2000 g / t of water glass as a gangue inhibitor, and 1000 g / t of the collector described in the application are added, and a phosphate concentrate is obtained after one roughing and three cleaning flotation.

[0034] Example 2 The present example provides a flotation separation collector for associated ultrafine-grained apatite in vanadium-titanium magnetite, and the preparation method thereof is different from that of Example 1 only in that the mass concentration of the raw materials for preparing the ultrafine-grained apatite flotation collector is: oxidized paraffin soap 50%, salicylhydroxamic acid 30%, soybean lecithin 15%, and dodecyl sulfopropyl betaine 5%.

[0035] Example 3 The present example provides a flotation separation collector for associated ultrafine-grained apatite in vanadium-titanium magnetite, and the preparation method thereof is different from that of Example 1 only in that the mass concentration of the raw materials for preparing the ultrafine-grained apatite flotation collector is: oxidized paraffin soap 70%, salicylhydroxamic acid 15%, soybean lecithin 10%, and dodecyl sulfopropyl betaine 5%.

[0036] Example 4 The present example provides a flotation separation collector for associated ultrafine-grained apatite in vanadium-titanium magnetite, and the preparation method thereof is different from that of Example 1 only in that the mass concentration of the raw materials for preparing the ultrafine-grained apatite flotation collector is: oxidized paraffin soap 57%, salicylhydroxamic acid 20%, soybean lecithin 15%, and dodecyl sulfopropyl betaine 8%.

[0037] Example 5 The present example provides a flotation separation collector for associated ultrafine-grained apatite in vanadium-titanium magnetite, and the preparation method thereof is different from that of Example 1 only in that the mass concentration of the raw materials for preparing the ultrafine-grained apatite flotation collector is: oxidized paraffin soap 65%, salicylhydroxamic acid 24%, soybean lecithin 8%, and dodecyl sulfopropyl betaine 3%.

[0038] Comparative Example 1 The present comparative example provides a flotation separation collector for associated ultrafine-grained apatite in vanadium-titanium magnetite, and the comparative example 1 is the same as the example 1 in other conditions, and the difference is only that only oxidized paraffin soap is used as the separation flotation collector.

[0039] Comparative Example 2 The present comparative example provides a flotation separation collector for associated ultrafine-grained apatite in vanadium-titanium magnetite, and the comparative example 2 is the same as the example 1 in other conditions, and the difference is only that only salicylhydroxamic acid is used as the separation flotation collector.

[0040] Comparative Example 3 The present comparative example provides a flotation separation collector for associated ultra-fine particle apatite in vanadium-titanium magnetite. The comparative example 3 is identical to the rest of example 1, the only difference is that only soybean lecithin is used as a separation flotation collector.

[0041] Comparative Example 4 The present comparative example provides a flotation separation collector for associated ultra-fine particle apatite in vanadium-titanium magnetite. The comparative example 4 is identical to the rest of example 1, the only difference is that only dodecyl sulfopropyl betaine is used as a separation flotation collector.

[0042] The performance of the phosphate concentrate product produced by the above examples and each comparative example is detected, and the specific results are shown in Table 1.

[0043] Table 1. Performance detection of phosphate concentrate

[0044] According to the experimental results, the composite collector (oxidized paraffin soap 60%, salicylhydroxamic acid 25%, soybean lecithin 10% and dodecyl sulfopropyl betaine 5%) in example 1 shows the best comprehensive performance in apatite flotation separation. The phosphorus grade of the phosphate concentrate reaches 37.62%, and the recovery rate is 81.26%, which takes into account high grade and high recovery rate. In contrast, the single collector of the comparative example has obvious defects: comparative example 1 (only oxidized paraffin soap) has a recovery rate (80.01%) close to example 1, but the phosphorus grade (31.54%) is significantly reduced, indicating poor selectivity; comparative example 2 (only salicylhydroxamic acid) has a high phosphorus grade (37.87%), but the recovery rate (60.32%) is significantly reduced, indicating insufficient collecting ability; comparative example 3 (only soybean lecithin) has the highest phosphorus grade (38.02%), but the recovery rate (26.11%) is extremely low, indicating that it has excellent selectivity but extremely weak collecting efficiency; comparative example 4 (only dodecyl sulfopropyl betaine) has a recovery rate (80.43%) slightly higher than example 1, but the phosphorus grade (24.16%) is the lowest, indicating the worst selectivity. Therefore, the composite collector maintains the high recovery characteristics of oxidized paraffin soap and betaine, and combines the high selectivity of salicylhydroxamic acid and soybean lecithin, achieving balanced optimization of grade and recovery rate.

[0045] In summary, the flotation separation collector for associated ultra-fine particle apatite in vanadium-titanium magnetite provided by the present application has the following characteristics: (1) Multi-agent synergistic cost reduction and efficiency improvement: By optimizing the combination of agent ratios, reducing agent consumption, and improving concentrate grade and recovery rate, cost reduction and efficiency improvement are effectively achieved.

[0046] (2) Strong collecting ability enhancement: Designed for ultra-fine particle apatite, significantly improves the recovery rate of phosphate minerals, with a recovery rate of more than 80%, especially suitable for the complex system of Panxi vanadium-titanium magnetite associated ore.

[0047] (3) High selectivity separation: Enhances the selective collection of apatite, effectively inhibits gangue minerals, and the concentrate grade is greater than 35%.

[0048] (4) Efficient use of resources: Through efficient recovery of ultra-fine particle apatite, improve the comprehensive utilization rate of mineral resources, reduce tailings discharge and environmental burden.

[0049] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A flotation collector for separating ultrafine apatite associated with vanadium-titanium magnetite, characterized in that, The raw materials include the following percentages by weight: 40%-80% oxidized paraffin soap, 10%-40% salicylic acid, 5%-20% soybean lecithin, and 2%-10% dodecyl sulfopropyl betaine.

2. The flotation collector for the associated ultrafine apatite in vanadium-titanium magnetite according to claim 1, characterized in that, The raw materials include the following percentages by weight: 50%-70% oxidized paraffin soap, 15%-30% salicylic acid hydroxamic acid, 8%-15% soybean lecithin, and 3%-8% dodecyl sulfopropyl betaine.

3. A method for preparing a flotation collector for the separation of associated ultrafine apatite in vanadium-titanium magnetite as described in claim 1 or 2, characterized in that, Includes the following steps: Oxidized paraffin soap is added to water and stirred and heated to dissolve, forming the first solution; salicylic acid is added to alkaline solution and stirred to dissolve, forming the second solution; Soybean lecithin was added to an ethanol solution and stirred to dissolve, forming a third solution. Dodecyl sulfopropyl betaine was added to water and stirred to dissolve, forming a fourth solution; Then, add the third solution to the second solution, then add the first solution, and finally add the fourth solution and mix thoroughly to obtain the flotation separation collector.

4. The method for preparing a flotation collector for the separation of associated ultrafine apatite in vanadium-titanium magnetite according to claim 3, characterized in that, The dissolution temperature of the first solution is 60-90℃, and the stirring time is 5-10 min.

5. The method for preparing a flotation collector for associated ultrafine apatite in vanadium-titanium magnetite according to claim 3, characterized in that, The second solution has a dissolution temperature of 15-30℃, an alkaline concentration of 2%-5%, and a dissolution time of 10-30 min.

6. The method for preparing a flotation collector for the separation of associated ultrafine apatite in vanadium-titanium magnetite according to claim 3, characterized in that, The dissolution temperature of the third solution is 15-30℃, the concentration of the ethanol solution is 2%-10%, and the dissolution time is 10-60 min.

7. The method for preparing a flotation collector for associated ultrafine apatite in vanadium-titanium magnetite according to claim 3, characterized in that, The dissolution temperature of the fourth solution is 15-30℃, and the stirring time is 5-10 min.

8. The method for preparing a flotation collector for the separation of associated ultrafine apatite in vanadium-titanium magnetite according to claim 3, characterized in that, The mixing temperature is 60-90℃, and the mixing time is 5-10 minutes.

9. A positive flotation process for vanadium-titanium magnetite associated with ultrafine-grained apatite, characterized in that, The flotation separation collector described in claim 1 or 2 is used to perform the following steps: first, the phosphorus-containing raw ore is ground to -0.018mm with 80%-95% particle size, and then screened using a vertical ring strong magnetic process with a magnetic field strength of 0.4-0.8T. Then, a pH adjuster, gangue inhibitor and flotation separation collector are added in sequence for positive flotation. After one roughing and three cleaning processes, the phosphorus concentrate is obtained.

10. The positive flotation process for vanadium-titanium magnetite associated with ultrafine apatite according to claim 9, characterized in that, The pH adjuster is added at a rate of 100-1000 g / t, the gangue inhibitor is added at a rate of 1000-3000 g / t, and the flotation separation collector is added at a rate of 100-2000 g / t.

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