Fluoroapatite phosphorite reverse flotation magnesium removal collecting agent and application thereof

Abstract

The invention provides a fluorapatite phosphorite reverse flotation magnesium removal collecting agent and application thereof.The fluorapatite phosphorite reverse flotation magnesium removal collecting agent comprises basic substances and water, and the basic substances comprise fatty acid soap, a surfactant and an auxiliary agent according to the mass ratio of 11: 3: 2; the fatty acid soap is one or a mixture of sodium oleate and oxidized paraffin soap; the surfactant is one or any ratio of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, lauryl sodium sulfate, sodium citrate, sodium acetate and sodium benzoate; according to the fluorapatite phosphorite reverse flotation magnesium removal collecting agent, apatite and dolomite can be effectively separated, the collecting capacity and selectivity of the fluorapatite phosphorite reverse flotation magnesium removal collecting agent are remarkably improved by adding the surface active agent and the auxiliary agent, and meanwhile the influence of Fe < 3 + > introduced in the ore grinding process on a flotation system is weakened through the surface active agent component.

Description

Technical Field

[0001] The invention relates to the technical field of ore flotation reagents, in particular to a fluorapatite phosphate ore reverse flotation magnesium removal collector and application thereof. Background Art

[0002] Fluorapatite is a phosphate mineral. In the beneficiation of fluorapatite, flotation is used to separate the collected ore. It can separate solid mineral powder and impurities, thereby effectively improving the purity of the ore. Collectors are needed in the flotation process, which can change the hydrophobicity of the mineral surface and make the floating mineral particles adhere to the bubbles. Most collectors are heteropolar organic compounds, such as xanthates, carboxylic acids, fatty amines, etc. Their molecular structures generally contain two groups: polar groups and non-polar groups, which have an important influence on the flotation performance of the entire molecule. The composition and structure of the collector's polar group determine the collector's chemical properties and dissociation properties in water.

[0003] For high-magnesium, low-grade phosphate ore, the use of conventional flotation collectors has problems such as difficulty in flotation separation, low grade of phosphate concentrate and phosphorus recovery rate, and low dolomite removal rate, which makes it difficult for the quality of phosphate concentrate to meet the requirements of wet phosphoric acid.

[0004] In order to solve the problem of difficult flotation separation of high-magnesium and low-grade phosphate ore, an efficient reverse flotation magnesium removal collector is needed to obtain high-quality phosphate concentrate.

[0005] At present, there are some documents and patent applications in the disclosed prior art. The Chinese patent document "202310441774.7 A reverse flotation collector for fluoroapatite-type phosphate ore" discloses a reverse flotation collector for fluoroapatite-type phosphate ore.

[0006] However, the above technology still has certain shortcomings. For example, although the polyoxyethylene ether mentioned in this scheme is widely used in industry and chemical products, the storage conditions of polyoxyethylene ether are strict and have certain risks. Therefore, the preparation of collectors with good selectivity, strong capture ability, environmental friendliness and high economic benefits is the main development direction. Summary of the invention

[0007] In order to solve the above technical problems, the present invention provides a fluorapatite phosphate ore reverse flotation magnesium removal collector and its application. The fluorapatite phosphate ore reverse flotation magnesium removal collector comprises a basic substance and water, and the mass ratio of fatty acid soap: surfactant: auxiliary agent is 11:3:2; The fatty acid soap is one of sodium oleate and oxidized paraffin soap or a mixture of the two; The surfactant is one of sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium citrate, sodium acetate, and sodium benzoate, or any combination thereof; The auxiliary agent is sodium cyclopentaneate.

[0008] The amount of basic substances and water can be mixed in any proportion according to needs.

[0009] Furthermore, the preparation method of the reverse flotation magnesium removal collector is as follows: Step 1: prepare the fatty acid soap into a 1%-3% fatty acid soap aqueous solution; prepare the surfactant into a 1%-3% surfactant aqueous solution; Step 2: Add the fatty acid soap aqueous solution and the surfactant aqueous solution into a reaction container and stir and mix; Step 3: While stirring and mixing, adding an auxiliary agent dropwise to the reaction container during the stirring process; Step 4: After the addition of the auxiliary agent is completed, the stirring is stopped and the liquid is allowed to stand until the liquid surface is calm to obtain the finished collector.

[0010] Furthermore, the reaction container has a capacity of 500-1000 ml, and the stirring and mixing is performed by a magnetic stirring bar at a rotation speed of 300 r / min.

[0011] On the other hand, the present invention provides an application of the above-mentioned fluorapatite phosphate ore reverse flotation magnesium removal collector, and the specific method is as follows: S1. Crushing, screening and ball milling the fluorapatite phosphate ore to obtain fine-grained raw ore; S2, using reverse flotation roughing to enrich the fine-grained ore, and adding the reverse flotation demagnesium collector to the reverse flotation roughing to obtain an intermediate product; S3, performing reverse flotation scavenging and enrichment on the intermediate product to obtain a phosphate concentrate product after magnesium removal.

[0012] Furthermore, the specific method of step S2 is: S51, slurrying the fine-grained ore with water and stirring it evenly; S52, adjusting the pH of the slurry to 4-5 and stirring for 1 min; S53, adding dispersant in an amount of 400 g / t and stirring for 2 min; then adding inhibitor in an amount of 4 kg / t and stirring for 2 min; finally adding the reverse flotation magnesium removal collector in an amount of 2.7 kg / t, stirring for 3 min, and scraping to generate an intermediate product.

[0013] Furthermore, in the step S3, the specific method for obtaining the phosphate concentrate is as follows: water is added to the intermediate product, after being fully stirred, 0.9 kg / t of the reverse flotation demagnesium collector is added, stirred for 2 minutes, aerated and bubbling, and scraped for 3 minutes to obtain the demagnesiumized phosphate concentrate product.

[0014] Furthermore, in the fine-grained raw ore, the feed particle size of -200 mesh is not less than 80%.

[0015] Furthermore, the pH adjuster is sulfuric acid, and the concentration of the sulfuric acid is 40%.

[0016] Furthermore, the dispersant is sodium hexametaphosphate.

[0017] Furthermore, the inhibitor is phosphoric acid.

[0018] Furthermore, the main components of the fluorapatite phosphate rock are apatite and dolomite.

[0019] Compared with the prior art, the present invention has the following beneficial effects: 1. The fluorapatite phosphate ore reverse flotation magnesium removal collector provided by the present invention can effectively separate apatite and dolomite. The collection capacity and selectivity are significantly improved by adding surfactants and additives. At the same time, the surfactant component weakens the Fe introduced during the grinding process. 3+ Impact on flotation system.

[0020] 2. The fluoroapatite phosphate ore reverse flotation magnesium removal collector provided by the present invention is based on the co-adsorption mechanism of fatty acid soap, surfactant and auxiliary agent on the mineral surface. After the introduction of surfactant and auxiliary agent, the surface activity of the agent is significantly improved, the interaction between the collector and the localized ions on the mineral surface is enhanced, and the various components of the mixed collector show good synergy, thereby obtaining an excellent mineral processing effect.

[0021] 3. The magnesium removal collector for reverse flotation of fluoroapatite phosphate ore provided by the present invention has good selectivity, strong magnesium collection ability (from Examples 2 to 5, most of the magnesium in the feed ore is captured in the tailings, and the magnesium content in the obtained phosphate concentrate is greatly reduced), good flotation separation indicators, and at the same time, in view of the differences in the properties of the original ore and the grinding fineness, the magnesium removal collector provided by the present invention has extremely strong adaptability and stability, and can stably obtain high-quality phosphate concentrate products under the condition that its dosage remains unchanged. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a flow chart of flotation using a de-magnesium collector in Example 1 of the present invention; Figure 2 This is the effect of different proportions of surfactants and additives on flotation indicators in Experiment 2 of the present invention. DETAILED DESCRIPTION

[0023] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] In the beneficiation operation of high-magnesium low-grade phosphate ore produced in Guizhou, for the actual mineral system in which apatite is a useful mineral and dolomite is a gangue mineral, the present invention enables the reverse flotation demagnesium collector provided by the present invention to have excellent selectivity and collection capacity for dolomite, greatly improving the sorting effect of such phosphate ore, thereby improving the concentrate P2O5 grade and P2O5 recovery rate. The following are the contents of multiple embodiments of the present invention.

[0025] Embodiment 1 A collector for reverse flotation and magnesium removal of fluorapatite phosphate ore, wherein the raw materials and components thereof are composed of the following parts by weight: fatty acid soap: 11 parts; surfactant: 3 parts; auxiliary agent: 2 parts.

[0026] In the collector compounding method of this example, fatty acid soap and surfactant are respectively prepared into 2% aqueous solution, and each component reagent is placed in a 500 ml beaker according to the mass ratio. A magnetic stirrer is used for mixing, and the rotor speed is 300 r / min. During the stirring process, a 2% auxiliary agent solution is added dropwise, and the input amount matches the amount of original ore. After all the auxiliary agent solution has been added, the demagnesium collector is prepared, and four portions are taken, code-named CYS-1, CYS-2, CYS-3, and CYS-4.

[0027] Embodiment 2 The collector code-named CYS-1 was obtained by the compounding method of Example 1. The one-rough-one-sweep reverse flotation process was adopted to flotate the Guizhou high-magnesium low-grade phosphate ore. The ore has a high dolomite content and a low apatite content, and is a typical difficult ore. The ore sample was subjected to a one-rough-one-sweep reverse flotation process using CYS-1. Figure 1 shown.

[0028] CYS-1 was used to carry out one roughing and one sweeping reverse flotation on the ore sample. The flotation process conditions were as follows: (1) Ore pre-treatment: crushing, screening and ball milling of the raw ore, with the grinding particle size of -200 mesh accounting for 83.45%; (2) Reverse flotation roughing enrichment: Add 500 g of raw ore to a 1.5 L flotation cell, slurry it with tap water, stir it thoroughly, then add 30 kg / t of sulfuric acid (40%) as a pH adjuster, stir it for 1 min, then add 400 g / t of sodium hexametaphosphate as a dispersant, stir it for 2 min, then add 4 kg / t of phosphoric acid (10%) as an inhibitor, stir it for 2 min, finally add 2.7 kg / t of the collector prepared above, stir it for 3 min, aerate and bubbling it, and float it for 5 min.

[0029] (3) Reverse flotation scavenging and enrichment: Take the product in the tank obtained in step (2), add tap water to the flotation tank, and the total volume of water in the tank is the same as that in step (2). After fully stirring, add 0.9 kg / t of the above-prepared collector, stir for 2 min, aerate and bubble, and float for 3 min.

[0030] Embodiment 3 The compounding method of Example 1 was used to obtain a collector code-named CYS-2, and then the demagnesium collector of this example was also used to adopt a one-rough-one-sweep reverse flotation process to flotate a high-magnesium, low-grade phosphate ore in Guizhou. In this example, the demagnesium collector was used to adopt a one-rough-one-sweep reverse flotation process to flotate a high-magnesium, low-grade phosphate ore in Guizhou. CYS-2 was used to carry out one roughing and one sweeping reverse flotation on the ore sample. The flotation process conditions were as follows: (1) Ore pre-treatment: The raw ore is crushed, screened and ball-milled, with the grinding particle size of -200 mesh accounting for 86.57%.

[0031] (2) Reverse flotation roughing enrichment: Add 500 g of raw ore to a 1.5 L flotation cell, slurry it with tap water, stir it thoroughly, then add 30 kg / t of sulfuric acid (40%) as a pH adjuster, stir it for 1 min, then add 400 g / t of sodium hexametaphosphate as a dispersant, stir it for 2 min, then add 4 kg / t of phosphoric acid (10%) as an inhibitor, stir it for 2 min, finally add 2.7 kg / t of the collector prepared above, stir it for 3 min, aerate and bubbling it, and float it for 5 min.

[0032] (3) Reverse flotation scavenging and enrichment: Take the product in the tank obtained in step (2), add tap water to the flotation tank, and the total volume of water in the tank is the same as that in step (2). After fully stirring, add 0.9 kg / t of the above-prepared collector, stir for 2 min, aerate and bubble, and float for 3 min.

[0033] Embodiment 4 The compounding method of Example 1 was used to obtain a collector code-named CYS-3, and then the demagnesium collector of this example was also used to adopt a one-roughing-one-sweeping reverse flotation process condition to flotate a high-magnesium, low-grade phosphate ore in Guizhou.

[0034] CYS-3 was used to carry out one roughing and one sweeping reverse flotation on the ore sample. The flotation process conditions were as follows: (1) Ore pre-treatment: The raw ore is crushed, screened and ball-milled, with the grinding particle size of -200 mesh accounting for 89.31%.

[0035] (2) Reverse flotation roughing enrichment: Add 500 g of raw ore to a 1.5 L flotation cell, slurry it with tap water, stir it thoroughly, then add 30 kg / t of sulfuric acid (40%) as a pH adjuster, stir it for 1 min, then add 400 g / t of sodium hexametaphosphate as a dispersant, stir it for 2 min, then add 4 kg / t of phosphoric acid (10%) as an inhibitor, stir it for 2 min, finally add 2.7 kg / t of the collector prepared above, stir it for 3 min, aerate and bubbling it, and float it for 5 min.

[0036] (3) Reverse flotation scavenging and enrichment: Take the product in the tank obtained in step (2), add tap water to the flotation tank, and the total volume of water in the tank is the same as that in step (2). After fully stirring, add 0.9 kg / t of the above-prepared collector, stir for 2 min, aerate and bubble, and float for 3 min.

[0037] Embodiment 5 The compounding method of Example 1 was used to obtain a magnesium-removing collector code-named CYS-4, and then the collector of this example was also used to adopt a one-roughing-one-sweeping reverse flotation process condition to flotate a high-magnesium, low-grade phosphate ore in Guizhou.

[0038] CYS-4 was used to carry out one roughing and one sweeping reverse flotation on the ore sample. The flotation process conditions were as follows: (1) Ore pre-treatment: The raw ore is crushed, screened and ball-milled, with the grinding particle size of -200 mesh accounting for 80.19%.

[0039] (2) Reverse flotation roughing enrichment: Add 500 g of raw ore to a 1.5 L flotation cell, slurry it with tap water, stir it thoroughly, then add 30 kg / t of sulfuric acid (40%) as a pH adjuster, stir it for 1 min, then add 400 g / t of sodium hexametaphosphate as a dispersant, stir it for 2 min, then add 4 kg / t of phosphoric acid (10%) as an inhibitor, stir it for 2 min, finally add 2.7 kg / t of the collector prepared above, stir it for 3 min, aerate and bubbling it, and float it for 5 min.

[0040] (3) Reverse flotation scavenging and enrichment: Take the product in the tank obtained in step (2), add tap water to the flotation tank, and the total volume of water in the tank is the same as that in step (2). After fully stirring, add 0.9 kg / t of the above-prepared collector, stir for 2 min, aerate and bubble, and float for 3 min.

[0041] Comparative Example 1 The difference between this comparative example and Example 1 is that in the magnesium removal collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:0:5.

[0042] Comparative Example 2 The difference between this comparative example and Example 1 is that in the magnesium removal collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:1:4.

[0043] Comparative Example 3 The difference between this comparative example and Example 1 is that in the magnesium removal collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:2:3.

[0044] Comparative Example 4 The difference between this comparative example and Example 1 is that in the magnesium removal collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:4:1.

[0045] Comparative Example 5 The difference between this comparative example and Example 1 is that in the magnesium removal collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:5:0.

[0046] Experimental Section Experiment 1 Chemical tests were performed on the concentrates and tailings obtained in Examples 2-5. The test results are shown in Table 1. The original ore in the table is a high-magnesium, low-grade phosphate ore. The collector of the present invention was used to flotation separate the phosphate ore. Under the same collector dosage per unit phosphate ore, in Examples 2-5, the collector dosage was 2700 g / t.

[0047] Table 1 Chemical test results

[0048] As can be seen from Table 1, in Example 2, the feed particle size of -200 mesh accounts for 83.45%. From the raw ore with a P2O5 grade of 20.61% and a MgO grade of 8.62%, a phosphate concentrate with a P2O5 grade of 33.97% and a MgO grade of 0.98% is obtained through a coarse and sweep reverse flotation process, and the P2O5 recovery rate is 92.27%.

[0049] In Example 3, the feed particle size is -200 mesh, accounting for 86.57%. From the raw ore with a P2O5 grade of 25.94% and a MgO grade of 5.14%, a phosphate concentrate with a P2O5 grade of 32.64% and a MgO grade of 1.04% is obtained through a coarse and sweep reverse flotation process, and the P2O5 recovery rate is 91.78%.

[0050] In Example 4, the feed particle size is -200 mesh, accounting for 89.31%. From the raw ore with a P2O5 grade of 23.58% and a MgO grade of 7.54%, a phosphate concentrate with a P2O5 grade of 34.68% and a MgO grade of 1.01% is obtained through a coarse and sweep reverse flotation process, and the P2O5 recovery rate is 87.14%.

[0051] In Example 5, the feed particle size is -200 mesh, accounting for 80.19%. From the raw ore with a P2O5 grade of 26.54% and a MgO grade of 4.80%, a phosphate concentrate with a P2O5 grade of 33.35% and a MgO grade of 0.72% is obtained through a coarse and sweep reverse flotation process, and the P2O5 recovery rate is 86.41%.

[0052] The results show that, for high-magnesium low-grade phosphate ore, the phosphate ore reverse flotation magnesium removal collector of the present invention has good reagent selectivity, strong magnesium collection ability (from Examples 2 to 5, most of the magnesium in the feed ore is captured in the tailings, and the magnesium content in the obtained phosphate concentrate is greatly reduced), and good flotation separation indicators. At the same time, in view of the differences in the properties of the original ore and the grinding fineness, the magnesium removal collector provided by the present invention has extremely strong adaptability and stability, and under the condition of unchanged dosage, high-quality phosphate concentrate products can be stably obtained.

[0053] Experiment 2 The demagnesium collectors obtained in Example 1 and Comparative Examples 1 to 5 were used to flot a high-magnesium, low-grade phosphate ore in Guizhou using the technical solution of Example 2. The concentrate obtained was chemically tested to test its P2O5 grade, and the P2O5 recovery rate was calculated based on the concentrate yield and P2O5 grade. The results are as follows: Figure 2 As shown, when the ratio of surfactant to auxiliary agent is 3:2 (Example 1), a phosphate concentrate with a P2O5 grade of 34.12% is obtained, and the P2O5 recovery rate is 90.48%. The P2O5 grades of the concentrates of Comparative Examples 1 to 5 are all lower than that of Example 1; the P2O5 recovery rates of Comparative Examples 1 to 4 are also worse than that of Example 1. Although the P2O5 recovery rate of Comparative Example 5 is higher than that of Example 1, the P2O5 grade of its concentrate is poor. In summary, the best effect is achieved when the ratio of surfactant to auxiliary agent is 3:2.

Claims

1. A collector for reverse flotation of fluorapatite phosphate ore, comprising a basic substance and water, characterized in that: According to the mass ratio, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:3:2; The fatty acid soap is one of sodium oleate and oxidized paraffin soap or a mixture of the two; The surfactant is one of sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium citrate, sodium acetate, and sodium benzoate, or any combination thereof; The auxiliary agent is sodium cyclopentaneate.

2. A fluoroapatite phosphate ore reverse flotation magnesium removal collector as claimed in claim 1, characterized in that: The preparation method of the reverse flotation magnesium removal collector is as follows: Step 1: prepare the fatty acid soap into a 1%-3% fatty acid soap aqueous solution, and prepare the surfactant into a 1%-3% surfactant aqueous solution; Step 2: adding the fatty acid soap aqueous solution and the surfactant aqueous solution into a reaction container and stirring and mixing; Step 3: While stirring and mixing, adding an auxiliary agent dropwise to the reaction container during the stirring process; Step 4: After the addition of the auxiliary agent is completed, the stirring is stopped and the liquid is allowed to stand until the liquid surface is calm to obtain the finished collector.

3. A fluoroapatite phosphate ore reverse flotation magnesium removal collector as claimed in claim 2, characterized in that: The reaction container has a capacity of 500-1000 ml, and the stirring and mixing is performed by a magnetic stirring bar at a rotation speed of 300 r / min.

4. The use of a fluoroapatite phosphate ore reverse flotation magnesium removal collector as claimed in any one of claims 1 to 3, characterized in that: The specific method is as follows: S1. Crushing, screening and ball milling the fluorapatite phosphate ore to obtain fine-grained raw ore; S2, using reverse flotation roughing to enrich the fine-grained ore, and adding the reverse flotation demagnesium collector to the reverse flotation roughing enrichment to obtain an intermediate product; S3, performing reverse flotation scavenging and enrichment on the intermediate product to obtain a phosphate concentrate product after magnesium removal.

5. The use of a fluoroapatite phosphate ore reverse flotation magnesium removal collector as claimed in claim 4, characterized in that: The specific method of step S2 is: S51, slurrying the fine-grained ore with water and stirring it evenly; S52, adjusting the pH of the slurry to 4-5 and stirring for 1 min; S53, adding dispersant in an amount of 400 g / t and stirring for 2 min; then adding inhibitor in an amount of 4 kg / t and stirring for 2 min; finally adding the reverse flotation magnesium removal collector in an amount of 2.7 kg / t, stirring for 3 min, and scraping to generate an intermediate product.

6. The use of a fluorapatite phosphate ore reverse flotation magnesium removal collector as claimed in claim 5, characterized in that: In the step S3, the specific method for obtaining the phosphate concentrate is as follows: water is added to the intermediate product, after being fully stirred, 0.9 kg / t of the reverse flotation demagnesium collector is added, stirred for 2 minutes, aerated and bubbling, and scraped for 3 minutes to obtain the demagnesiumized phosphate concentrate product.

7. The use of a collector for reverse flotation and magnesium removal of fluorapatite phosphate ore as claimed in claim 4, characterized in that: Among the fine-grained raw ore, the feed particle size of -200 mesh is not less than 80%.

8. The use of a collector for reverse flotation and magnesium removal of fluorapatite phosphate ore as claimed in claim 5, characterized in that: The pH adjuster is sulfuric acid; the concentration of the sulfuric acid is 40%; and the dispersant is sodium hexametaphosphate.

9. The use of a collector for reverse flotation and magnesium removal of fluorapatite phosphate ore as claimed in claim 5, characterized in that: The inhibitor is phosphoric acid, and the concentration of the phosphoric acid is 10%.

10. The use of a collector for reverse flotation and magnesium removal of fluorapatite phosphate ore as claimed in claim 5, characterized in that: Used to separate apatite and dolomite.

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