Vanadium titano-magnetite floating phosphorus inhibitor and application thereof

Abstract

The invention discloses a vanadium titano-magnetite floating phosphorus inhibitor and application thereof, and relates to the technical field of mineral processing. The floating phosphorus inhibitor comprises the following components in percentage by mass: 30%-50% of low-polymerization-degree polysaccharide, 30%-50% of high-polymerization-degree polysaccharide and 0%-40% of an organic dispersing agent. Gangue minerals can be accurately inhibited through good selectivity and stability, and flotation of phosphorite is not affected; and the method is environment-friendly, does not pollute the environment, meets the current requirements on green and environment-friendly production, and is beneficial to promoting the sustainable development of the mining industry. The grade of raw ore P2O5 is 3% or below, phosphorus resources in the vanadium titano-magnetite tailings can be effectively recycled, and the comprehensive utilization rate of the resources is increased; meanwhile, the production cost is effectively reduced, and good economic benefits and social benefits are achieved. In addition, the preparation method of the inhibitor is simple, convenient and feasible, and is convenient to popularize and use in actual production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a vanadium-titanium magnetite phosphorus flotation inhibitor and application thereof. BACKGROUND

[0002] Vanadium-titanium magnetite is an important component of black metal mineral resources in China. The mineral composition of vanadium-titanium magnetite is complex and contains many associated elements. In addition to iron, it also contains economically valuable elements such as phosphorus. With the gradual depletion of high-grade phosphate resources, the recovery of phosphorus resources from low-grade minerals and tailings has become a research hotspot. At present, vanadium-titanium magnetite concentrators mainly use magnetic separation process to recover magnetite and ilmenite. However, for low-grade and phosphorus-containing iron tailings, the existing technology lacks mature flotation process and supporting reagent system, resulting in a large amount of waste of these tailings and serious waste of phosphorus resources.

[0003] Panxi region is the main production area of vanadium-titanium magnetite in China. The occurrence state of phosphorus in the ore is complex, mainly existing in the form of isomorphism in the titanium magnetite lattice or as an independent mineral apatite. The phosphorus content is generally low and unevenly distributed, making it difficult to effectively enrich and recover in the beneficiation process. The existing flotation process faces multiple technical bottlenecks in recovering phosphorus: the flotation recovery rate is generally lower than 75%, and the useful minerals are lost with the tailings; titanium magnetite, vanadium-titanium magnetite, and associated minerals such as ilmenite, sulfide, and silicate interfere with each other, resulting in unstable flotation separation effect; the surface properties of phosphorus minerals and calcareous gangue minerals such as calcite and dolomite are similar, causing a decrease in the selectivity of flotation reagents; traditional inhibitors such as water glass have poor stability, are prone to react with reagents, and leave residues on the mineral surface, which not only affects the separation effect but also may cause environmental pollution.

[0004] To address the above problems, the existing technology explores phosphorus recovery processes such as acid leaching and bioleaching. Acid leaching can extract phosphorus, but it requires high corrosion resistance of equipment and has defects such as difficulty in acid treatment and long time consumption; bioleaching technology is limited by the sensitivity of microorganisms to the environment and the complexity of operation, making it difficult to achieve industrial-scale application. In terms of reagent development, traditional inhibitors generally have poor selectivity, high dosage, and heavy environmental burden, which cannot meet the needs of efficient and environmentally friendly flotation.

[0005] As disclosed in Chinese patent CN110935560A, a method for recovering phosphorus by grinding and screening and flotation process is disclosed, which uses water glass as a phosphorus inhibitor, and finally a qualified phosphate concentrate with P2O5 content of 31.78% can be obtained; however, the phosphorus recovery rate of this method is relatively low, which limits the comprehensive utilization rate of tailings resources. Chinese patent CN117920465A discloses an apatite inhibitor based on the combination of L-malic acid, hypochlorous acid and ammonium sulfate, and apatite is inhibited into tailings by reverse flotation, and finally a phosphate concentrate with P2O5 grade of 29.59% and P2O5 recovery rate of 93.11% is obtained; this method has a higher requirement for the content of apatite in the raw ore for flotation, and the beneficiation efficiency is not ideal for minerals with low phosphorus grade. Chinese patent CN112474065A discloses a method for recovering phosphorus from low-grade vanadium-titanium magnetite tailings, which uses a combination inhibitor HQ-P1 and is processed by magnetic separation and flotation process, and finally a qualified phosphate concentrate with P2O5 content of 35.24% is obtained; although this method can recover most of the phosphorus resources, the flotation recovery rate is low, and the P2O5 grade in the tailings reaches 0.58%, resulting in waste of part of the resources; in addition, the cost of the combination inhibitor HQ-P1 is high, which further increases the economic burden of the beneficiation process.

[0006] Therefore, it is of great practical application value and significance to develop a new type of flotation separation inhibitor with high efficiency, good selectivity and stability for improving the recovery rate and utilization efficiency of phosphorus resources in vanadium-titanium magnetite.

[0007] In view of this, the present application is proposed. SUMMARY

[0008] The present application aims to provide a vanadium-titanium magnetite phosphorus flotation inhibitor and its application, to solve the above technical problems.

[0009] The present application is implemented as follows: In a first aspect, the embodiments of the present application provide a vanadium-titanium magnetite phosphorus flotation inhibitor, which comprises the following components in terms of mass percentage: 30%-50% of low degree of polymerization polysaccharide, 30%-50% of high degree of polymerization polysaccharide and 0%-40% of organic dispersing agent.

[0010] In a second aspect, the embodiments of the present application provide an application of the aforementioned phosphorus flotation inhibitor in the flotation separation of associated phosphorus resources in vanadium-titanium magnetite.

[0011] The present application has the following beneficial effects: The vanadium-titanium magnetite phosphorus floating inhibitor provided by the embodiment of the present application is suitable for low-grade vanadium-titanium magnetite flotation and low-grade phosphorus resource mineral flotation associated with vanadium-titanium magnetite, has good selectivity and stability, can accurately inhibit gangue minerals without affecting the flotation of phosphorus minerals, is environmentally friendly and does not pollute the environment, meets the current requirements for green and environmentally friendly production, and is conducive to promoting the sustainable development of the mining industry. In the case that the P2O5 grade of the raw ore is only 1%-3%, a concentrate product with a P2O5 grade of more than 30% and a recovery rate of more than 85% is selected, and the P2O5 grade of the flotation tailings is less than 0.3%. The comprehensive utilization rate of resources is improved, the production cost is reduced, and good economic and social benefits are achieved. In addition, the preparation method of the inhibitor is simple and easy to implement, and is convenient for popularization and use in actual production. BRIEF DESCRIPTION OF DRAWINGS

[0012] 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.

[0013] Figure 1 The figure is a schematic diagram of the flotation process of the associated phosphorus resources in the vanadium-titanium magnetite. DETAILED DESCRIPTION

[0014] 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 below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0015] In recent years, the research on phosphorus floating inhibitors is relatively less. The development of many inhibitors is mainly based on apatite inhibitors, and the recovery of phosphorus resources is realized through reverse flotation technology, but this flotation technology has a high requirement for the phosphorus content of the raw ore. For the recovery of low-grade tailings phosphorus, the current mainstream solution still uses water glass as the inhibitor, but its selectivity is limited and the stability is poor, which is difficult to meet the efficient and environmentally friendly flotation separation standard. The present inventors have developed a high-efficiency phosphorus floating inhibitor with good selectivity and stability, which is applied to the flotation separation process of the associated phosphorus resources in the vanadium-titanium magnetite, can recover a large amount of phosphorus resources, greatly reduces the loss of resources in the tailings, and has important economic value. The specific implementation process is as follows: In the first aspect, the embodiments of the present application provide a vanadium-titanium magnetite phosphorus floating inhibitor, which comprises the following components in terms of mass percentage: 30%-50% of the low degree of polymerization polysaccharide, 30%-50% of the high degree of polymerization polysaccharide and 0%-40% of the organic dispersant.

[0016] It should be noted that the phosphorus flotation inhibitor of the present application has good stability, which can effectively overcome the problem of insufficient stability of traditional inhibitors in a complex ore slurry system, and ensure stable inhibition under various conditions, thereby improving the controllability and reliability of the flotation process, and is especially suitable for low-grade vanadium-titanium magnetite and vanadium-titanium magnetite associated with low-grade phosphorus resource minerals. The formula is simple and low in cost, does not pollute the environment, meets the current requirements for green and environmentally friendly production, and is conducive to promoting the sustainable development of the mining industry.

[0017] The phosphorus flotation inhibitor of the present application significantly improves the selective inhibition ability of gangue in the apatite mineral flotation system, realizes the recovery of phosphorus from low-grade vanadium-titanium magnetite tailings in the Panxi region, and under the condition that the P2O5 grade of the raw ore is only 1%-3%, a concentrate product with a P2O5 grade of more than 30% is selected, and the P2O5 grade of the flotation tailings is less than 0.3%. In comparison, the P2O5 grade of the raw ore required by other related patents is generally higher than 3%, and the tailings grade is more than 0.5%, making it difficult to effectively recover and utilize useful minerals, further highlighting the significant advantage of the present application in improving resource recovery efficiency. This significantly improved recovery rate not only effectively recovers a large amount of phosphorus resources, but also significantly reduces resource loss in the tailings, significantly improving the level of resource comprehensive utilization.

[0018] In an optional embodiment, the phosphorus flotation inhibitor includes the following components in terms of mass percentage: 40%-50% of the low degree of polymerization polysaccharide, 40%-50% of the high degree of polymerization polysaccharide and 0%-20% of the organic dispersant.

[0019] It should be noted that the low degree of polymerization polysaccharide used in the flotation separation process of the vanadium-titanium magnetite associated with phosphorus resources has a polymerization degree of less than 20, a small molecular weight, good water solubility and low viscosity. In the flotation process, it can be adsorbed on the surface of fine particles to prevent mud agglomeration and improve the flowability of the ore slurry; the hydroxyl groups in its structural formula can interact weakly with the mineral surface to selectively inhibit certain gangue minerals (such as silicates); and it is beneficial to the dispersion of non-polar collectors (such as kerosene) to improve the collection efficiency of hydrophobic target minerals.

[0020] The high degree of polymerization polysaccharide has a polymerization degree of hundreds to thousands, a large molecular weight, and a large difference in water solubility (some need to be heated to dissolve), and a high viscosity. In the flotation process, the high degree of polymerization polysaccharide with a large molecular chain selectively inhibits oxidized minerals (such as hematite and quartz) or sulfide minerals (such as pyrite) through multi-point adsorption or chelation, especially under high pH conditions; it makes fine particles flocculate and settle through bridging, reducing metal loss; and it also has the characteristics of improving the stability of the foam layer.

[0021] It should be noted that the organic dispersant selectively adsorbs a specific mineral surface through its specific molecular structure, forms electrostatic repulsion or steric hindrance, and can effectively prevent the heterogeneous coagulation of fine particle size slime (such as clay and silicate); it is beneficial to improve the fluidity of the ore slurry and reduce the negative impact of the "slime cover" on the floatability of the target mineral; it meets the requirements of green beneficiation and is beneficial to reduce the pressure of wastewater treatment.

[0022] In an optional embodiment, the polysaccharide with low degree of polymerization is at least one of maltodextrin, cyclodextrin, fructooligosaccharide, galactooligosaccharide, and chitooligosaccharide.

[0023] In the optimal embodiment, the polysaccharide with low degree of polymerization is maltodextrin; in other embodiments of the present application, reasonable adjustments can be made according to actual needs.

[0024] It should be noted that maltodextrin, as a polysaccharide inhibitor, adsorbs on the surface of silicate and other gangue minerals to form a hydrophilic covering layer, preventing the adsorption of collectors such as fatty acids; it has a significant selective inhibition effect on apatite and silicate-containing gangue (such as feldspar and quartz), which is beneficial to improve the grade of phosphate concentrate.

[0025] In an optional embodiment, the polysaccharide with high degree of polymerization is at least one of soluble starch, cellulose, pectin, xanthan gum, hyaluronic acid, carboxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

[0026] In the optimal embodiment, the polysaccharide with high degree of polymerization is soluble starch; in other embodiments of the present application, reasonable adjustments can be made according to actual needs.

[0027] It should be noted that soluble starch forms a hydration film on the surface of the mineral by adsorption, inhibiting calcite, quartz, and other gangue minerals; it has less interference with the flotation of apatite and has the characteristics of low cost.

[0028] In an optional embodiment, the organic dispersant is at least one of humic acid sodium, polyaspartic acid sodium, sodium gluconate, tannic acid, oxalic acid, and urea.

[0029] In the optimal embodiment, the organic dispersant is humic acid sodium; in other embodiments of the present application, reasonable adjustments can be made according to actual needs.

[0030] It should be noted that humic acid sodium is widely available and has low cost and good environmental protection; it has both dispersing and inhibiting functions, and it inhibits impurity minerals such as iron and aluminum oxides by chelating calcium, magnesium, iron, and other metal ions; it is beneficial to disperse slime and reduce the negative impact of fine particle agglomeration on flotation.

[0031] In an optional embodiment, the phosphorus floating inhibitor is prepared by the following method: The low degree of polymerization polysaccharide, the high degree of polymerization polysaccharide and water are mixed in a water bath with a temperature of 30-60 DEG C in proportion, and then the organic dispersing agent is added after stirring uniformly, and the phosphorus floating inhibitor is prepared by continuing to stir.

[0032] It should be noted that the preparation method of the phosphorus floating inhibitor is simple and easy to use, and is convenient for popularization and use in actual production.

[0033] Among them, because there are a large number of hydrogen bonds (-OH…O-) in the molecular structure of polysaccharide substances, hydrogen bond is the key force for the substance to dissolve in water, and since there are a large number of hydrogen bonds, why is it difficult to dissolve, and recheck. Form a tight three-dimensional network structure (such as the crystalline region of starch), which makes it difficult to dissolve in cold water. Therefore, appropriate heating can provide energy to destroy the hydrogen bonds between molecules, so that the crystalline region is depolymerized into an amorphous structure, reducing the energy barrier required for dissolution, and accelerating the contact between polysaccharide molecules and water molecules. The increase of temperature will reduce the viscosity and surface tension of water, and increase the kinetic energy of water molecules, so that they are more easily penetrated into the internal gap of the polysaccharide molecular chain, forming a hydration layer, and accelerating the dissolution rate of the polysaccharide. If the temperature is too high, the polysaccharide will be gelatinized, which will reduce the inhibitory effect.

[0034] Stirring is mainly to solve the problem of uneven mass transfer and agglomeration blockage, to ensure uniform dispersion of polysaccharide and to shorten the total time.

[0035] In a second aspect, the embodiments of the present application provide a use of the phosphorus floating inhibitor as described above in the flotation separation of vanadium-titanium magnetite associated phosphorus resources.

[0036] In an optional embodiment, in the flotation operation process, the mass concentration of the phosphorus floating inhibitor is 0.1%-10%.

[0037] It should be noted that in the flotation process, the ore pulp is usually a complex system with high solid content and multiple components, and the mineral particles (especially the ultra-fine particles) are easy to agglomerate to form a "slime cover", which causes the reagent to be unable to uniformly contact the surface of the target mineral. The phosphorus floating inhibitor is added in the form of a solution, which can quickly penetrate into the gap between the mineral particles, avoiding the "local concentration too high" or "agglomeration settlement" phenomenon when dry powder is added. The reagent molecules in the solution can quickly diffuse through Brownian motion and fully mix with the collector and the frother to form a "inhibition-collector-frothing" synergistic system, which optimizes the flotation process and improves the flotation efficiency.

[0038] In an optional embodiment, the flotation separation of vanadium-titanium magnetite associated phosphorus resources adopts a "one roughing and three cleaning" operation process, and the operation process schematic diagram is shown in Figure 1 ; specifically, the raw ore is treated by strong magnetic iron and titanium removal, and then subjected to a flotation beneficiation process of one roughing and three cleaning to obtain a phosphorus concentrate.

[0039] In an optional embodiment, the dosage of the phosphorus floating inhibitor is 360 g / t-640 g / t, which is added in stages, and the dosage in the roughing stage is 45%-55% by mass percentage; the dosage in the first cleaning stage is 20%-30%; the dosage in the second cleaning stage is 10%-20%; and the dosage in the third cleaning stage is 5%-15%.

[0040] It should be noted that the roughing is the “enrichment” stage of flotation, and the goal is to quickly separate most of the useful minerals (apatite) while minimizing the loss of useful minerals. The addition of the phosphorus floating inhibitor in this stage is beneficial to the inhibition of gangue and the promotion of the preferential floating of apatite; the dosage needs to be strictly controlled, and if it is excessive, it may cause the hydroxylation of the surface of apatite, reducing the hydrophobicity; if it is insufficient, too much gangue will float, reducing the grade of the rough concentrate; it is beneficial to reduce the subsequent cleaning load, reduce the total consumption of reagents, and ensure the recovery rate.

[0041] The cleaning is the “purification” stage of flotation, and the goal is to further improve the concentrate grade while removing residual fine-grained gangue or “difficult-to-inhibit gangue” (such as colloidal clay and micro-fine quartz). The addition of the phosphorus floating inhibitor in this stage can destroy the gangue aggregation and inhibit the flotation of the gangue by using its strong dispersibility or chelating ability; it can wash off the impurities on the surface of apatite, while inhibiting the secondary floating of residual gangue, improving the “cleanliness” of the concentrate; it can adjust the pH or ionic strength of the ore slurry by adding the inhibitor, optimize the surface electrical difference between apatite and gangue, and further improve the selective adsorption of the collector.

[0042] In an optional embodiment, the P2O5 grade of the ore entering the flotation is 1%-3%, and the proportion of the -38 μm particle size is greater than 45%.

[0043] The P2O5 grade of the concentrate obtained by flotation is greater than 30%, and the phosphorus recovery rate is greater than 80%.

[0044] It should be noted that the raw ore of the present application is a vanadium-titanium magnetite tailing with a P2O5 grade of 3% or less, which is difficult to recover and has low beneficiation economic benefits; the use of the phosphorus floating inhibitor of the present application can effectively recover and utilize the vanadium-titanium magnetite tailing, increasing the utilization rate of phosphorus resources.

[0045] The features and performance of the present application are further described in detail below in conjunction with the embodiments.

[0046] Embodiment 1 The present embodiment provides a vanadium-titanium magnetite phosphorus floating inhibitor, which is prepared by the following method: The low-polymerization-degree polysaccharide, the high-polymerization-degree polysaccharide, and the organic dispersant are added in a ratio of 9:9:2 for reaction, and the specific process is as follows: Add 4.5 kg of malt dextrin (low degree of polymerization polysaccharide) to the stirring barrel, then add 4.5 kg of soluble starch (high degree of polymerization polysaccharide), add 500 kg of water, and after water bath to 50℃, start stirring, stirring speed is 1800 r / min, stirring time is 15 min; Then add 1 kg of sodium humate (organic dispersant) to the stirring barrel, then add water to a total weight of 1000 kg, and continue stirring for 10 min. After completing the stirring, a mass concentration of 1% of the phosphorus floatation inhibitor is prepared.

[0047] This embodiment also provides a test of using the phosphorus floatation inhibitor in a vanadium-titanium magnetite tailing floatation process in the Panxi region. The relevant data are shown in Table 1. Table 1 Size composition and distribution of vanadium-titanium magnetite tailings

[0048] The difference between each particle size in the raw ore is significant, and is mainly concentrated in the-38 μm particle size interval, and the yield reaches 47.21%. From the distribution of P2O5, the distribution in other particle size intervals is relatively uniform, except that the content of +300 μm particle size is low.

[0049] Under the condition that the P2O5 grade of the raw ore is 2.626%, through the strong magnetic iron and titanium removal treatment, and then through the “one roughing and three cleaning” floatation beneficiation process, in the floatation process, the foaming speed is general, and the foam is relatively more.

[0050] Among them, the total amount of the phosphorus floatation inhibitor added is 480 g / t, specifically, the phosphorus floatation inhibitor is added in the roughing stage at 240 g / t, the regulator (NaCO3) is added at 720 g / t, and the phosphorus collecting agent (sodium oleate) is added at 600 g / t; the amount of the phosphorus floatation inhibitor added in the first cleaning stage is 120 g / t; the amount of the phosphorus floatation inhibitor added in the second cleaning stage is 80 g / t; and the amount of the phosphorus floatation inhibitor added in the third cleaning stage is 40 g / t.

[0051] The P2O5 grade of the phosphorus concentrate can reach 32.15%, the P2O5 recovery rate reaches 86.08%, and the P2O5 grade of the floatation tailings is 0.21%.

[0052] Embodiment 2 This embodiment provides a vanadium-titanium magnetite phosphorus floatation inhibitor, which is different from the embodiment 1 only in that: The low degree of polymerization polysaccharide (malt dextrin), the high degree of polymerization polysaccharide (soluble starch) and the organic dispersant (sodium humate) are added in a ratio of 2:2:1 for reaction, and a mass concentration of 1% of the phosphorus floatation inhibitor is prepared.

[0053] The prepared phosphorus floatation inhibitor is used in a test of a vanadium-titanium magnetite tailing floatation process in the Panxi region, and the relevant result data are shown in Table 2.

[0054] Example 3 This example provides a vanadium-titanium magnetite phosphorus flotation inhibitor, which is only different from example 1 in that: The low degree of polymerization polysaccharide (malt dextrin) and the high degree of polymerization polysaccharide (soluble starch) are added in a ratio of 1:1 for reaction to prepare a phosphorus flotation inhibitor with a mass concentration of 1%.

[0055] The prepared phosphorus flotation inhibitor is used for the test of the vanadium-titanium magnetite tailings flotation process in the Panxi region, and the relevant result data are shown in Table 2.

[0056] Comparative Example 1 This comparative example provides a vanadium-titanium magnetite phosphorus flotation inhibitor, which is only different from example 1 in that: The low degree of polymerization polysaccharide (malt dextrin) and the organic dispersant (sodium humate) are added in a ratio of 2:1 for reaction to prepare a phosphorus flotation inhibitor with a mass concentration of 1%.

[0057] The prepared phosphorus flotation inhibitor is used for the test of the vanadium-titanium magnetite tailings flotation process in the Panxi region, and the relevant result data are shown in Table 2.

[0058] Comparative Example 2 This comparative example provides a vanadium-titanium magnetite phosphorus flotation inhibitor, which is only different from example 1 in that: The high degree of polymerization polysaccharide (soluble starch) and the organic dispersant (sodium humate) are added in a ratio of 2:1 for reaction to prepare a phosphorus flotation inhibitor with a mass concentration of 1%.

[0059] The prepared phosphorus flotation inhibitor is used for the test of the vanadium-titanium magnetite tailings flotation process in the Panxi region, and the relevant result data are shown in Table 2.

[0060] Comparative Example 3 This comparative example provides a vanadium-titanium magnetite phosphorus flotation inhibitor, which is only different from example 1 in that: The low degree of polymerization polysaccharide (malt dextrin) and the organic dispersant (tannic acid) are added in a ratio of 1:1 for reaction to prepare a phosphorus flotation inhibitor with a mass concentration of 1%.

[0061] The prepared phosphorus flotation inhibitor is used for the test of the vanadium-titanium magnetite tailings flotation process in the Panxi region, and the relevant result data are shown in Table 2.

[0062] Comparative Example 4 This comparative example provides a vanadium-titanium magnetite phosphorus flotation inhibitor, which is only different from example 1 in that: The low degree of polymerization polysaccharide (malt dextrin) and the organic dispersant (hydroxyethyl cellulose) are added in a ratio of 1:1 for reaction to prepare a phosphorus flotation inhibitor with a mass concentration of 1%.

[0063] The prepared phosphorus floating inhibitor was used in the flotation process test of vanadium-titanium magnetite tailings in Panxi region, and the relevant result data are shown in Table 2.

[0064] Comparative Example 5-17 The comparative example 5-17 provides a vanadium-titanium magnetite phosphorus floating inhibitor, which is only different from the example 1 in that a single component phosphorus floating inhibitor is used, and is used in the flotation process test of vanadium-titanium magnetite tailings in Panxi region, and the relevant result data are shown in Table 2.

[0065] In the comparative example 5, the mass concentration of water glass is 5%, and the total addition amount is 1440g / t.

[0066] In the comparative example 6, the mass concentration of high polymerization degree polysaccharide (hydroxypropyl methyl cellulose) is 0.5%.

[0067] In the comparative example 7, the mass concentration of low polymerization degree polysaccharide (malt dextrin) is 0.5%.

[0068] In the comparative example 8, the mass concentration of organic dispersant (oxalic acid) is 2%.

[0069] In the comparative example 9, the mass concentration of high polymerization degree polysaccharide (soluble starch) is 2%.

[0070] In the comparative example 10, the mass concentration of organic dispersant (sodium humate) is 2%.

[0071] In the comparative example 11, the mass concentration of high polymerization degree polysaccharide (hydroxyethyl cellulose) is 0.5%.

[0072] In the comparative example 12, the mass concentration of sodium tripolyphosphate is 2%.

[0073] In the comparative example 13, the mass concentration of organic dispersant (sodium polyaspartate) is 2%.

[0074] In the comparative example 14, the mass concentration of organic dispersant (sodium gluconate) is 2%.

[0075] In the comparative example 15, the mass concentration of organic dispersant (tannic acid) is 2%.

[0076] In the comparative example 16, the mass concentration of sodium hexametaphosphate is 2%.

[0077] In the comparative example 17, the mass concentration of organic dispersant (urea) is 2%.

[0078] Table 2: Flotation results of different phosphorus floating inhibitors

[0079] As can be seen from Table 2, the float phosphorus inhibitors provided in Examples 1 and 2 can significantly improve the grade and recovery rate of the phosphorus concentrate under the same flotation conditions compared with the float phosphorus inhibitors in the comparative examples. In particular, in the case of the raw ore P2O5 grade of 3.10%, the P2O5 grade of the phosphorus concentrate obtained in Example 1 is as high as 32.15%, the recovery rate is as high as 86.08%, and the P2O5 grade of the tailings is as low as 0.21%, which shows excellent flotation performance and selectivity. The float phosphorus inhibitor in Example 3 is slightly worse than Examples 1-2 in the flotation results due to the absence of an organic dispersant, and the phenomenon of fast foaming, large amount of foaming and viscous foaming occurs during the flotation process.

[0080] The float phosphorus inhibitors in the comparative examples, whether single-component or composite components in Comparative Examples 1-4 but with improper proportions, have poorer flotation effects than Examples 1 and 2. For example, the single-component inhibitors in Comparative Examples 5-17, although some components such as high-polymer polysaccharides and organic dispersants have certain effects in flotation, single components often cannot achieve ideal flotation effects, and the concentrate grade and recovery rate are generally low. The composite-component inhibitors in Comparative Examples 1-4 have improper component proportions, resulting in that the flotation performance cannot be fully exerted, and the concentrate grade and recovery rate are also lower than Examples.

[0081] In addition, it can also be seen from Table 2 that the foaming speed and foam state are relatively stable during the flotation process of Examples 1 and 2, which is conducive to the flotation process and the collection of the concentrate. However, some inhibitors in the comparative examples, such as Comparative Example 3 and Comparative Example 4, have problems such as difficult preparation of the reagent, slow dissolution rate and the like, resulting in the phenomenon of ore loss during the flotation process, which seriously affects the flotation effect.

[0082] In summary, the vanadium-titanium magnetite float phosphorus inhibitor provided in the examples of the present application has the following characteristics: (1) The float phosphorus inhibitor has good selectivity and is suitable for low-grade vanadium-titanium magnetite and low-grade phosphorus resource minerals associated with vanadium-titanium magnetite. The present application significantly improves the selective inhibition ability of apatite minerals, realizes the recovery of low-grade vanadium-titanium magnetite tailings in the Panxi region, and selects a concentrate product with a P2O5 grade of more than 30% from a raw ore with a P2O5 grade of only 1%-3%, and the P2O5 grade of the flotation tailings is less than 0.3%. In comparison, the P2O5 grade of the raw ore required by other related patents is generally higher than 3%, and the tailings grade is more than 0.5%, which makes it difficult to effectively recover and utilize useful minerals, further highlighting the significant advantages of the present application in improving resource recovery efficiency.

[0083] (2) The phosphorus flotation inhibitor is applied to the flotation separation of associated phosphorus resources in vanadium-titanium magnetite, and the phosphorus recovery effect is particularly prominent. Through the application of the flotation separation inhibitor and its unique preparation process, in the flotation test of low-grade vanadium-titanium magnetite tailings in Panxi region, the P2O5 recovery rate is more than 85%, which significantly exceeds the recovery level of the traditional method. This significantly improved recovery rate not only effectively recovers a large amount of phosphorus resources, but also greatly reduces the resource loss in the tailings, and significantly improves the comprehensive utilization level of resources.

[0084] (3) The phosphorus flotation inhibitor has good stability, can effectively overcome the stability problem of traditional inhibitors in complex slurry system, ensures stable inhibition under various conditions, and improves the controllability and reliability of the flotation process.

[0085] (4) The phosphorus flotation inhibitor is environmentally friendly and will not pollute the environment, meeting the current requirements for green and environmentally friendly production, and being conducive to promoting the sustainable development of mining industry.

[0086] (5) The formula of the phosphorus flotation inhibitor is simple, the cost is low, and the raw materials are easy to purchase, thereby reducing the cost of mineral processing and improving the economic benefit. In addition, the dosage of the inhibitor is relatively small, and the reagent consumption is only 480g / t, which effectively reduces the amount of reagent used, further reduces the production cost, and is convenient for operation and popularization in actual production process.

[0087] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various changes and variations. 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 vanadium-titanium magnetite floating phosphorus inhibitor, characterized in that: The floating phosphorus inhibitor comprises the following components by mass percentage: 30%-50% of low-polymerization degree polysaccharide, 30%-50% of high-polymerization degree polysaccharide and 0%-40% of organic dispersant.

2. The floating phosphorus inhibitor according to claim 1, characterized in that The floating phosphorus inhibitor comprises the following components by mass percentage: 40%-50% of low-polymerization degree polysaccharide, 40%-50% of high-polymerization degree polysaccharide and 0%-20% of organic dispersant.

3. The floating phosphorus inhibitor according to claim 1, characterized in that The low-polymerization polysaccharide is selected from at least one of maltodextrin, cyclodextrin, oligofructose, oligogalactose and chitosan oligosaccharide.

4. The floating phosphorus inhibitor according to claim 1, characterized in that The high polymerization degree polysaccharide is selected from at least one of soluble starch, cellulose, pectin, xanthan gum, hyaluronic acid, carboxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.

5. The floating phosphorus inhibitor according to claim 1, characterized in that The organic dispersant is selected from at least one of sodium humate, sodium polyaspartate, sodium gluconate, tannic acid, oxalic acid and urea.

6. The floating phosphorus inhibitor according to any one of claims 1 to 5, characterized in that The floating phosphorus inhibitor is prepared by the following method: The low-polymerization degree polysaccharide, the high-polymerization degree polysaccharide and water are mixed in a water bath at a temperature of 30-60° C. in proportion, stirred evenly, and then an organic dispersant is added and stirred continuously to prepare a floating phosphorus inhibitor.

7. Use of the floating phosphorus inhibitor according to any one of claims 1 to 6 in the flotation separation of associated phosphorus resources in vanadium-titanium magnetite.

8. The use according to claim 7, characterized in that In the flotation process, the mass concentration of the floating phosphorus inhibitor is 0.1%-10%.

9. The use according to claim 7, characterized in that The flotation separation of associated phosphorus resources in vanadium-titanium magnetite adopts a "one coarse and three fine" operation process; And / or, the amount of the floating phosphorus inhibitor is 360g / t-640g / t, added in stages, and calculated by mass percentage, the amount added in the roughing stage is 45%-55%; the amount added in the first refining stage is 20%-30%; the amount added in the second refining stage is 10%-20%; and the amount added in the third refining stage is 5%-15%.

10. The use according to claim 7, characterized in that The P2O5 grade of the float ore is 1%-3%, and the -38μm particle size accounts for more than 45%; The P2O5 grade of the concentrate obtained by flotation is greater than 30%, and the phosphorus recovery rate is greater than 80%.

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