A kind of micro-fine oxide ore flotation inhibitor and its preparation method and application

Abstract

The invention discloses a micro-fine oxide ore flotation inhibitor and a preparation method and application thereof. The micro-fine oxide ore flotation inhibitor is a complex formed by divalent or higher metal ions and macromolecules such as starch, dextrin, guar gum, polyolefin amide, etc. The micro-fine oxide ore flotation inhibitor is used in the flotation process of micro-fine oxide ore to achieve selective flocculation and inhibition of gangue minerals such as calcite and dolomite, thereby achieving the enrichment of useful minerals such as micro-fine scheelite, wolframite, cassiterite, etc., and achieving the purpose of effectively recovering valuable components of micro-fine oxide ore.

Description

Technical Field

[0001] The invention relates to a micro-fine oxide ore flotation inhibitor, and also relates to a preparation method and application thereof as a gangue mineral inhibitor in the flotation enrichment process of micro-fine oxide ore, belonging to the field of ore dressing technology utilization. Background Art

[0002] In the prior art, due to their brittleness, scheelite and wolframite are easily over-crushed and muddied in the process of wind, mining, crushing and grinding, forming fine tungsten ore mud. With the long-term mining and utilization of tungsten ore, rich ore and coarse-grained mineral resources are becoming increasingly scarce, and the situation of poor and fine tungsten ore resources has become very prominent, and fine particles, especially fine tungsten ore, are difficult to effectively sort and recycle, resulting in a large waste of mineral resources. For example, weathered tungsten ore and colloidal tin ore in the Nanling mineralization belt have long been defined as "dead ore". According to statistics, the weathered tungsten resources of Yuanjing Tungsten Industry, Yaogangxian Tungsten Mine and Xintianling Tungsten Mine under China Minmetals Group are equivalent to 1.2 million tons of WO3 metal, with a total value of more than 100 billion yuan. According to surveys, 20% of the world's tungsten-containing minerals are lost in fine particles, which has caused a large waste of mineral resources and economic losses. In addition, the production practices of multi-metal concentrators such as Shizhuyuan and Huangshaping and related process mineralogy studies have shown that tungsten flotation is mostly present in the fine-grained WO3 of -400 mesh in the concentrating section, while gangue minerals such as calcite, chlorite, and mica are mostly present in the particle size of -800 mesh. These fine-grained gangue minerals either consume collectors, cover the surface of useful minerals, or are mechanically entrained, which has a great impact on the recovery rate and grade of tungsten flotation. As an important part of my country's mineral resources, the large amount of tungsten metal contained in fine particles urgently needs mature technology recovery.

[0003] The flotation of fine-grained and micro-fine-grained minerals is mainly solved from two aspects: equipment and reagents. In terms of equipment, the flotation equipment is mainly modified around strong shear flocculation, micron or nano bubbles, etc. Its main disadvantages are high cost, limited processing capacity, and poor adaptability. In terms of reagents, the scope is relatively wide, involving many flotation reagents such as collectors, inhibitors, dispersants, flocculants, and bubble regulators. In the flotation process of fine-grained minerals, dispersants are usually used to disperse different fine-grained minerals, and then macromolecular reagents are used to form large flocs. These macromolecular reagents, such as starch, dextrin, guar gum, etc., have long molecular chains and poor selectivity, making it difficult to separate fine-grained useful minerals from gangue minerals. Summary of the invention

[0004] In view of the difficulty in flotation enrichment of valuable components in existing fine-grained oxide ores, the first object of the present invention is to provide a fine-grained oxide ore flotation inhibitor, which can act on fine-grained gangue minerals with high selectivity, and has the functions of flocculating and inhibiting fine-grained gangue minerals, and can effectively improve the enrichment ratio of fine-grained useful minerals and realize effective recovery of valuable components.

[0005] The second object of the present invention is to provide a method for preparing a micro-particle oxide ore flotation inhibitor, which is simple, has low raw material cost, mild reaction conditions, and is conducive to large-scale production.

[0006] The third object of the present invention is to provide an application of a flotation inhibitor for fine-grained oxide ores, which is applied to the flotation of fine-grained oxide ores and can efficiently and selectively act on fine-grained calcite, dolomite, siderite, magnesite, feldspar, kaolinite, quartz, talc, mica, illite, montmorillonite, nepheline and other gangue minerals, and achieve their aggregation and hydrophilic modification, inhibit their flotation, and greatly improve the flotation enrichment of useful minerals such as tungsten ore, cassiterite, fluorite, apatite, barite, rutile and so on.

[0007] In order to achieve the above technical objectives, the present invention provides a micro-particle oxide ore flotation inhibitor, which is a complex formed by divalent or higher metal ions and macromolecules; the macromolecules include at least one of starch, dextrin, polyacrylamide, and guar gum.

[0008] The micro-fine oxide ore flotation inhibitor of the present invention is a complex formed by the coordination of divalent or higher metal ions and hydroxyl-rich macromolecules, so that the -CH2-OH hydroxyl group on the polymer chain of the macromolecule is converted into -CH2-O-Me. On the basis of ensuring the flocculation ability of the macromolecule itself, the introduced metal-based -Me greatly improves the adsorption selectivity of the macromolecule to the mineral. Therefore, the complex formed by the divalent or higher metal ions and the macromolecule has both flocculation ability and selective adsorption ability, so that specific micro-fine gangue minerals can be selectively combined, and flocculated and surface hydrophilic modified, and the flotation of micro-fine gangue minerals can be inhibited.

[0009] As a preferred embodiment, starches include starch or starch derivatives (starch modifications), such as soluble starch, potato starch or caustic starch; dextrins include dextrin or dextrin derivatives (dextrin modifications) such as white dextrin, yellow dextrin, cyclodextrin or maltodextrin; polyacrylamides include nonionic polyacrylamide, anionic polyacrylamide or cationic polyacrylamide.

[0010] As a preferred solution, the divalent or higher metal ions include Mn 2+ Mg 2+ , Ca 2+, Fe 3+ 、Al 3+ , Pb 2+ The most preferred is Al 3+ or Pb 2+ The complex formed by it and macromolecules has a better inhibitory effect on fine-grained gangue minerals than the complex formed by other metal ion macromolecules.

[0011] As a preferred solution, the mass ratio of the divalent or higher metal ion to the macromolecule is 1:5 to 4:1. When the divalent or higher metal ion is Mn 2+ and / or Fe 3+ When the divalent or higher metal ion is Mg, the mass ratio of the divalent or higher metal ion to the macromolecule is further preferably 1:1 to 4:1. 2+ and / or Ca 2+ When the divalent or higher metal ion is Al 3+ and / or Pb 2+ When the molecular weight is 2:1, the mass ratio of the molecular weight to the macromolecule is more preferably 1:5 to 2:1.

[0012] The present invention also provides a method for preparing a micro-particle oxide ore flotation inhibitor, which comprises reacting divalent or higher metal ions with macromolecules under alkaline conditions to obtain the inhibitor.

[0013] As a preferred solution, the pH value of the alkaline condition is 9.0 to 12.0. When the pH is less than 9, it is difficult for divalent or higher metal ions to form complexes with macromolecules that have high efficiency in inhibiting the activity of fine-grained gangue minerals.

[0014] As a preferred solution, the reaction conditions are: temperature of 60-95° C. and time of 20-60 min.

[0015] As a preferred solution, the divalent or higher metal ions are provided by water-soluble divalent or higher metal salts, such as nitrates.

[0016] The present invention also provides an application of a micro-fine oxide ore flotation inhibitor, which is used as a gangue mineral inhibitor in the flotation of micro-fine oxide ore.

[0017] As a preferred solution, the gangue mineral includes at least one of calcite, dolomite, siderite, magnesite, feldspar, kaolinite, quartz, talc, mica, illite, montmorillonite and nepheline.

[0018] As a preferred solution, the useful minerals in the fine-grained oxide ore include at least one of tungsten ore, cassiterite, fluorite, apatite, barite and rutile.

[0019] As a preferred solution, the particle size of the fine oxide ore is less than 15 microns.

[0020] As a preferred solution, the amount of the gangue mineral inhibitor relative to the fine oxide ore is 5 to 50 g / t, and the effect is particularly significant when the amount is 10 to 20 g / t.

[0021] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects:

[0022] The micro-fine oxide ore flotation inhibitor of the present invention is mainly aimed at the flotation process of micro-fine oxide minerals. It is difficult to selectively act on micro-fine gangue minerals in the process of flocculating micro-fine gangue minerals by using conventional macromolecules, so it is difficult to separate micro-fine gangue minerals from useful minerals. However, high-valent metal ions and macromolecules form complexes, and the complexes have both flocculation ability and selective adsorption ability, so that specific micro-fine gangue minerals can be selectively combined, and flocculated and surface hydrophilic modified at the same time, so as to improve the dispersibility of gangue minerals, enhance the inhibitory effect of gangue minerals, and achieve the purpose of recovering micro-fine useful minerals.

[0023] The preparation method of the micro-fine oxide ore flotation inhibitor of the invention is simple, the raw material cost is low, the reaction conditions are mild, and it is conducive to large-scale production.

[0024] The micro-fine oxide ore flotation inhibitor of the present invention is applied to the flotation of micro-fine oxide ore, and can efficiently and selectively act on fine-grained calcite, dolomite, siderite, magnesite, feldspar, kaolinite, quartz, talc, mica, illite, montmorillonite, nepheline and other gangue minerals, and realize their aggregation and hydrophilic modification, inhibit their flotation, and greatly improve the flotation enrichment of useful minerals such as micro-fine tungsten ore, cassiterite, fluorite, apatite, barite, rutile and the like with a particle size of less than 15 microns. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 These are the infrared spectrum analysis and XPS analysis results of the Al-starch colloid collector prepared in Example 1.

[0026] Figure 2 The figure shows the effects of Al-starch colloid inhibitor and Pb-starch colloid inhibitor prepared with different ratios of metal ions to macromolecules in Example 4 on calcite flotation.

[0027] Figure 3 The flotation results of scheelite-chlorite artificial mixed ore using Mg-starch inhibitor prepared with different ratios of metal ions to macromolecules in Example 5 are shown.

[0028] Figure 4 Effect of Ca-polyacrylamide complex on selective flocculation of fine-particle tin resources in Example 6.

[0029] Figure 5 This is a flow chart of the open circuit test of the Pb-dextrin colloidal complex and other flotation agents in Example 8. DETAILED DESCRIPTION

[0030] The following examples are provided to further illustrate the present invention, but are not intended to limit the scope of protection of the claims of the present invention.

[0031] Example 1

[0032] Prepare 20 mg / L soluble starch solution and 100 mg / L aluminum ion solution (added in the form of aluminum sulfate) respectively. Take 20 mL of soluble starch solution, place it in a constant temperature magnetic stirring water bath, and stir it at a constant temperature and uniform speed at 90°C. Slowly add 20 mL of aluminum ion solution to the soluble starch solution, adjust the solution pH to 10.5 with sodium hydroxide solution, react at 90°C for 30 minutes, and obtain Al-starch colloid inhibitor after cooling.

[0033] The reaction formula is as follows:

[0034]

[0035] Infrared spectroscopy and XPS analysis of Al-starch colloid inhibitor Figure 1 As shown in the figure, it can be seen that aluminum reacts successfully with soluble starch and Al-starch colloid inhibitor is obtained through chemical bonding.

[0036] Example 2

[0037] 40 mg / L soluble starch solution and a series of aluminum ion solutions of different concentrations (10 mg / L, 20 mg / L, 40 mg / L and 80 mg / L) (added in the form of aluminum sulfate) were prepared respectively. 20 mL of the above four aluminum ion solutions of different concentrations were slowly added to 20 mL of the soluble starch solution, and a series of Al-starch colloid inhibitors with different metal ion ratios were prepared according to the reaction conditions of Example 1.

[0038] Example 3

[0039] 40 mg / L soluble starch solution and a series of lead ion solutions of different concentrations (10 mg / L, 20 mg / L, 40 mg / L and 80 mg / L) (added in the form of lead nitrate) were prepared respectively. 20 mL of the above four lead ion solutions of different concentrations were slowly added to 20 mL of the soluble starch solution, and a series of Pb-starch colloid inhibitors with different metal ion ratios were prepared according to the reaction conditions of Example 1.

[0040] Example 4

[0041] Weigh 2g of pure calcite mineral with a particle size of less than 15μm, add it to the flotation cell of the XFG hanging trough flotation machine, add 29mL of deionized water, set the flotation machine speed to 1800r / min, mix the slurry for 1min, add 10ml of Al-starch colloid inhibitor and Pb-starch colloid inhibitor with different metal ion ratios in Example 2 and Example 3 respectively, act for 3min, adjust the pH to 10 with sodium hydroxide solution, add 1mL4×10 -3 mol / L sodium oleate solution, react for 3 minutes and then scrape the foam. The scraping time is controlled within 3 minutes. Dry the flotation product, weigh it, and calculate the recovery rate. The flotation results are as follows: Figure 2 shown.

[0042] from Figure 2 It can be seen that with the increase of aluminum ion ratio, the inhibitory effect of Al-starch colloid inhibitor on calcite gradually increases. With the increase of lead ion dosage, the inhibitory effect of Pb-starch colloid inhibitor on calcite first increases and then weakens. This shows that the mass ratios of Al-starch colloid inhibitor and Pb-starch colloid inhibitor for the best inhibitory effect on calcite are 2:1 and 1:2 respectively, at which time the calcite recovery rate is reduced by 20.37% and 14.8% respectively.

[0043] Example 5

[0044] A 40 mg / L soluble starch solution and a series of magnesium ion solutions of different concentrations (20 mg / L, 40 mg / L and 80 mg / L) (added in the form of magnesium chloride) were used. 20 mL of the above four magnesium ion solutions of different concentrations were slowly added to 20 mL of the soluble starch solution, respectively, and a series of Mg-starch colloid inhibitors with different metal ion ratios were prepared according to the reaction conditions of Example 1.

[0045] Weigh 20g of each pure scheelite and chlorite mineral and mix them evenly with a particle size of less than 15μm to obtain an artificial scheelite-chlorite mixed ore with a mass ratio of 1:1, and carry out a flotation experiment: weigh 3g of the artificial mixed ore and use an XFG hanging trough flotation machine to add Mg-starch colloid inhibitor and other corresponding agents and adjust the slurry according to the flotation experiment process in Example 4. The flotation time is 4min. The flotation product is dried and weighed, and the grade of each product is obtained by XRF fluorescence analysis, and the recovery rate is calculated. Flotation experiments without inhibitors and with the addition of an equal amount of soluble starch inhibitor were carried out under the same experimental steps as a blank group control. The final concentrate results are as follows Figure 3 shown.

[0046] The use of Mg-starch colloid inhibitor can significantly reduce the recovery rate of gangue mineral chlorite without compromising the recovery rate of scheelite. When using Mg-starch colloid inhibitor, the recovery rate of scheelite fluctuates slightly and is always above 57%. As the proportion of magnesium ions gradually increases, the recovery rate of scheelite concentrate shows a slight trend of first rising and then falling, while the recovery rate of chlorite first decreases and then increases. The Mg-starch colloid inhibitor achieves the best effect at a mass ratio of 1:1, at which time the recovery rate of scheelite concentrate reaches 60%, while the recovery rate of chlorite is reduced to 30%.

[0047] Example 6

[0048] The sulfur tailings slurry from a multi-metal concentrator was taken as an experimental sample to recover the tin resources therein. The slurry concentration was about 40%, and the distribution rate of tin in the range of particle size less than 15μm was 71%. 50mg / L polyacrylamide solution and 100mg / L calcium ion solution (added in the form of calcium chloride) were respectively prepared. According to the experimental steps of Example 1, a Ca-polyacrylamide complex with a mass ratio of 2:1 was prepared under the conditions of pH=9.5, temperature 90°C and reaction time 45min. Take 450ml of sulfur tailings slurry in a beaker, use a mechanical stirrer to make the slurry fully uniform, slowly add different amounts of Ca-polyacrylamide complex and deionized water, keep the total volume at 500mL, and continue stirring for 20 minutes to allow it to fully react. Pour the completely reacted slurry into a 500mL measuring cylinder, let it stand for 5 minutes, then suck out the upper liquid product and the bottom product respectively, filter, dry, weigh, calculate the yield, and use XRF fluorescence analysis to obtain the grade of each product. The results are as follows Figure 4 As shown in the figure, with the increase of the dosage of Ca-polyacrylamide complex, the yield of tin in the upper product shows a downward trend, and an inflection point appears when the dosage is 13g / t; with the increase of the dosage of Ca-polyacrylamide complex, the grade of tin in the upper product shows a downward trend, and an obvious inflection point appears when the dosage is 13g / t. Comprehensively judging, the best effect is achieved when the dosage of Ca-polyacrylamide complex is 13g / t.

[0049] Example 7

[0050] The coarse concentrate of a tungsten concentrator contains a large amount of fine-grained gangue minerals (the proportion of particles less than 15μm accounts for 76%), especially fine-grained calcite and chlorite, which seriously affect the improvement of WO3 grade in subsequent concentration. In this example, the coarse concentrate produced on-site in the tungsten concentrator was taken, and the upper fine mud was extracted as a sample for experiment after standing and settling for 15 minutes. A Pb-caustic starch colloid inhibitor with a mass ratio of 1:1 was prepared according to the method in Example 1 using lead ion solution and caustic starch solution. Take an appropriate amount of fine mud slurry and add it to the flotation tank of a 1.5L XFD laboratory single-tank flotation machine, set the flotation machine speed to 2000r / min, adjust the slurry for 3min, add Pb-caustic starch colloid inhibitor, add 400g / t Pb-BHA collector after 3min of action, react for 3min, add a frother, aerate and scrape the foam, and control the scraping time to 5min. The flotation products were filtered, dried, and weighed, and the grades of each product were obtained by XRF fluorescence analysis, and the recovery rate was calculated. The results are shown in Table 1. The results show that the use of a small amount of Pb-caustic starch colloid inhibitor can significantly improve the recovery rate of tungsten in the fine mud of the coarse concentrate, and at the same time improve the WO3 grade of the concentrate product to a certain extent.

[0051] Table 1 Experimental results of flotation conditions for coarse concentrate and fine mud

[0052]

[0053]

[0054] Example 8

[0055] Tungsten from the sulfur tailings of a certain beneficiation plant in Chenzhou, Hunan, is closely interwoven with gangue minerals such as calcite, mica, feldspar, and quartz, and the interwoven particle size is relatively fine. After grinding, there are a large number of fine-grained scheelite and gangue minerals such as calcite and quartz, which are difficult to separate and utilize efficiently. In this embodiment, the sulfur tailings are used as samples to recover the fine-grained tungsten resources therein, and the slurry concentration is about 45%, and the distribution rate of tungsten in the range of particle size less than 15 μm is 67%. 75 mg / L dextrin solution and 150 mg / L lead ion solution (added in the form of lead nitrate) are respectively prepared. According to the experimental steps of Example 1, a Pb-dextrin colloidal complex is prepared under the conditions of pH=10, temperature 90°C and reaction time 40 min. 3.0L, 1.5L and 0.5L XFD laboratory single-slot flotation machines are used respectively according to the experimental process of one coarse, five fine and one sweep ( Figure 5) Pb-dextrin colloid complex and other flotation reagents were added in sequence to conduct long process open circuit experiments, and compared with blank experiments without Pb-dextrin colloid complex. The experimental results are shown in Table 2. The analysis results show that when no inhibitor is added, the WO3 grade and recovery rate of the concentrate product are 30.293% and 36.72% respectively. After adding 20g / t Pb-dextrin colloid inhibitor in the roughing, the WO3 grade of the concentrate product is significantly increased to 40.135%. This shows that the Pb-dextrin colloid complex has a selective inhibitory effect on fine-grained calcite, quartz and other gangue minerals.

[0056] Table 2 Pb-dextrin colloid inhibitor long process open circuit test results

[0057]

Claims

1. An application of a flotation inhibitor for fine-grained oxide ores, characterized in that: Used as a gangue mineral inhibitor in the flotation of fine oxide ores; The micro-particle oxide ore flotation inhibitor is a complex formed by divalent or higher metal ions and macromolecules; The macromolecules include at least one of starch, dextrin, polyacrylamide and guar gum; The gangue minerals in the fine-grained oxide ore include at least one of calcite, dolomite, siderite, magnesite, feldspar, kaolinite, quartz, talc, mica, illite, montmorillonite and nepheline; The particle size of the fine oxide ore is less than 15 microns; The amount of the gangue mineral inhibitor relative to the fine oxide ore is 5-50 g / t.

2. The use of a flotation inhibitor for fine-grained oxide ores according to claim 1, characterized in that: The useful minerals in the fine-grained oxide ore include at least one of tungsten ore, cassiterite, fluorite, apatite, barite and rutile.

3. The use of a flotation inhibitor for fine-grained oxide ores according to claim 1, characterized in that: The divalent or higher metal ions include Mn 2+ Mg 2+ , Ca 2+ , Fe 3+ 、Al 3+ , Pb 2+ One of them.

4. The use of a flotation inhibitor for fine-grained oxide ores according to claim 1 or 3, characterized in that: The mass ratio of the divalent or higher metal ions to the macromolecule is 1:5 to 4:1.

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