Fluorapatite phosphate ore reverse flotation magnesium removal collector and application thereof

Abstract

The application provides a fluorapatite phosphate ore reverse flotation magnesium removal collector and application thereof, which comprises basic substances and water, and the basic substances are mixed according to the mass ratio, wherein the ratio of fatty acid soap, surfactant and additive is 11:3:2; the fatty acid soap is one or a mixture of two of sodium oleate, oxidized paraffin soap; the surfactant is one or any ratio of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium citrate, sodium acetate and sodium benzoate; and the additive is sodium naphthenate. The fluorapatite phosphate ore reverse flotation magnesium removal collector provided by the application can effectively separate apatite and dolomite, significantly improve the collecting capacity and selectivity by adding surfactants and additives, and the surfactant composition weakens the influence of Fe 3+ on the flotation system.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore flotation reagents, in particular to a fluorapatite phosphate ore reverse flotation magnesium removal collector and its application. BACKGROUND

[0002] Fluorapatite is a phosphate mineral, and flotation is used in the beneficiation of fluorapatite to separate the collected ore, which can separate solid ore powder and impurities, thereby effectively improving the purity of the ore. In the process of flotation, collectors are needed, which can change the hydrophobicity of the mineral surface, making the floating mineral particles adhere to the bubbles. Most collectors are heteropolar organic compounds, such as xanthate, carboxylic acid, and fatty amine. The structure of the molecule generally contains two groups: polar group and non-polar group, which have important influence on the overall flotation performance of the molecule. The composition and structure of the polar group of the collector determine the chemical properties and dissociation properties in water.

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

[0004] To solve the problem of difficult flotation separation of high-magnesium low-grade phosphate ore, a high-efficiency reverse flotation magnesium removal collector is needed to obtain high-quality phosphate concentrate.

[0005] Currently, there are some documents and patent applications in the existing technology. The Chinese patent document "202310441774.7 A reverse flotation collector for fluorapatite type phosphate ore" discloses a reverse flotation collector for fluorapatite type phosphate ore.

[0006] However, the above technology still has some deficiencies, such as the polyoxyethylene ether mentioned in the scheme, which is widely used in industry and chemical products, but the storage conditions of polyoxyethylene ether are strict and have certain risks. Therefore, the main development direction is to prepare a collector with good selectivity, strong collecting ability, environmental friendliness, and high economic benefit. SUMMARY

[0007] To solve the above technical problems, the present application provides a fluorapatite phosphate ore reverse flotation magnesium removal collector and its application. The fluorapatite phosphate ore reverse flotation magnesium removal collector comprises basic substances and water, and the mass ratio of fatty acid soap, surfactant and additive is 11:3:2.

[0008] The fatty acid soap is one of sodium oleate and oxidized paraffin soap or a mixture of the two;

[0009] The surface active agent is one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium citrate, sodium acetate, sodium benzoate or any ratio;

[0010] The assistant is sodium naphthenate.

[0011] The basic substance and water are arbitrarily matched according to needs.

[0012] Further, the preparation method of the reverse flotation demagnetizing collector is as follows:

[0013] Step one: configure the fatty acid soap into 1%-3% fatty acid soap aqueous solution; configure the surface active agent into 1%-3% surface active agent aqueous solution;

[0014] Step two: add the fatty acid soap aqueous solution and the surface active agent aqueous solution into the reaction container and mix by stirring;

[0015] Step three: while mixing by stirring, add the assistant into the reaction container and drop during the stirring process;

[0016] Step four: after the assistant dropping is completed, end the stirring, and after the liquid surface is calm, the collector finished product is obtained.

[0017] Further, the capacity of the reaction container is 500-1000 ml, and the mixing by stirring is performed by a magnetic stirring rod with a rotating speed of 300 r / min.

[0018] On the other hand, the application provides the application of the reverse flotation demagnetizing collector for fluorapatite phosphate rock, and the specific method is as follows:

[0019] S1, crush, screen and ball mill the fluorapatite phosphate rock to obtain fine-grained raw ore;

[0020] S2, use the reverse flotation roughing enrichment on the fine-grained raw ore, and add the reverse flotation demagnetizing collector in the reverse flotation roughing enrichment to obtain an intermediate product;

[0021] S3, use the reverse flotation scavenging enrichment on the intermediate product to obtain a demagnetized phosphate concentrate product.

[0022] Further, the specific method of the step S2 is as follows:

[0023] S51, use water to adjust the slurry of the fine-grained raw ore and fully stir to be uniform;

[0024] S52, adjust the pH of the ore slurry to 4-5 and stir for 1 min;

[0025] S53, the dispersing agent is added in an amount of 400 g / t, stirring for 2 min; then the inhibitor is added in an amount of 4 kg / t, stirring for 2 min; finally the reverse flotation demagnetizing collector is added in an amount of 2.7 kg / t, stirring for 3 min, and the intermediate product is scraped.

[0026] Further, in the step S3, the specific method for obtaining the phosphate concentrate is: water is supplemented to the intermediate product, and after uniform stirring, the reverse flotation demagnetizing collector is added in an amount of 0.9 kg / t, stirring for 2 min, and after air bubbling, the demagnetized phosphate concentrate product is obtained by scraping for 3 min.

[0027] Further, in the fine-grained raw ore, the particle size of the feed ore is not less than 80% of -200 mesh.

[0028] Further, the pH adjusting agent is sulfuric acid, and the concentration of the sulfuric acid is 40%.

[0029] Further, the dispersing agent is sodium hexametaphosphate.

[0030] Further, the inhibitor is phosphoric acid.

[0031] Further, the main components of the fluorapatite phosphate ore are apatite and dolomite.

[0032] Compared with the prior art, the beneficial effects of the present application are:

[0033] 1. The fluorapatite phosphate ore reverse flotation demagnetizing collector provided by the present application can effectively separate apatite and dolomite, and significantly improve the collecting capacity and selectivity by adding a surfactant and an auxiliary agent, and the surfactant component weakens the influence of Fe 3+ on the flotation system.

[0034] 2. The fluorapatite phosphate ore reverse flotation demagnetizing collector provided by the present application, based on the common adsorption mechanism of fatty acid soap, surfactant and auxiliary agent on the mineral surface, significantly improves the surface activity of the reagent after the introduction of the surfactant and the auxiliary agent, enhances the interaction between the collector and the mineral surface positioning ion, and the components of the mixed collector show good synergy, thereby obtaining excellent beneficiation effect.

[0035] 3. The fluorapatite phosphate ore reverse flotation demagnetizing collector provided by the present application has good selectivity and strong collecting capacity for magnesium (from examples two to five, most of the magnesium in the feed ore is captured into the tailings, and the content of magnesium in the obtained phosphate concentrate is greatly reduced), and the flotation separation index is good. Meanwhile, in view of the difference in the nature and grinding fineness of the raw ore, the demagnetizing collector provided by the present application has strong adaptability and stability, and under the condition that the amount is unchanged, high-quality phosphate concentrate products can be stably obtained. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 Flow chart for the flotation process using the demagnetizing collector in the first embodiment of the present application;

[0037] Figure 2 Effect of different proportions of surfactants and additives on the flotation index in the second experiment of the present application. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be described clearly and completely below in combination with the drawings. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0039] In the beneficiation operation of the high-magnesium low-grade phosphate ore produced in Guizhou, aiming at the actual mineral system in which apatite is the useful mineral and dolomite is the gangue mineral, the reverse flotation demagnetizing collector provided by the present application has excellent selectivity and collecting capacity for dolomite, greatly improves the separation effect of this type of phosphate ore, thereby improving the concentrate P2O5 grade and P2O5 recovery rate. The following are contents of multiple embodiments of the present application.

[0040] Embodiment one

[0041] A fluorapatite type phosphate ore reverse flotation demagnetizing collector, each raw material and each component thereof consists of the following weight fractions: fatty acid soap: 11 parts; surfactant: 3 parts; additive: 2 parts.

[0042] The compounding method of the collector of the present example is to configure the fatty acid soap and the surfactant into 2% aqueous solutions respectively, place each component reagent in a 500 ml beaker according to the mass ratio, mix using a magnetic stirrer with a rotor speed of 300 r / min, drop in a 2% additive solution during the stirring process, the amount of which is matched with the amount of the raw ore, after the additive solution is completely added, the demagnetizing collector is configured, and four portions are taken respectively, coded as CYS-1, CYS-2, CYS-3, and CYS-4.

[0043] Embodiment two

[0044] The collector coded as CYS-1 is obtained by using the compounding method of embodiment one, and a one-roughing one-scavenging reverse flotation process condition is adopted to carry out flotation on the Guizhou high-magnesium low-grade phosphate ore. The ore has high dolomite content and low apatite content, and is a typical refractory ore. The CYS-1 is used to carry out one-roughing one-scavenging reverse flotation process on the ore sample, as shown in Table 1. Figure 1

[0045] ​The CYS-1 is used for roughing and scavenging reverse flotation of the ore sample, and the flotation process conditions are as follows:

[0046] (1) Ore pretreatment: the raw ore is crushed, screened and ball milled, and the grinding size is 83.45% of -200 mesh.

[0047] (2) Reverse flotation roughing enrichment: 500 g of raw ore is added to a 1.5 L flotation tank, and tap water is used for slurry, and after sufficient stirring, 30 kg / t of pH adjusting agent sulfuric acid (40%) is added, stirred for 1 min, then 400 g / t of dispersant sodium hexametaphosphate is added, stirred for 2 min, then 4 kg / t of inhibitor phosphoric acid (10%) is added, stirred for 2 min, and finally 2.7 kg / t of the prepared collector is added, stirred for 3 min, and after aeration and bubbling, it is floated for 5 min.

[0048] (3) Reverse flotation scavenging enrichment: the product in the tank obtained in step (2) is taken, tap water is added to the flotation tank, and the total volume of the water in the tank is the same as in step (2), and after sufficient stirring, 0.9 kg / t of the prepared collector is added, stirred for 2 min, and after aeration and bubbling, it is floated for 3 min.

[0049] Example Three

[0050] The collector with code CYS-2 is obtained by using the compounding method of Example One, and the same de-magnesium collector is used in this example to take a roughing and scavenging reverse flotation process condition, and a high-magnesium and low-grade phosphate ore in Guizhou is floated.

[0051] The CYS-2 is used for roughing and scavenging reverse flotation of the ore sample, and the flotation process conditions are as follows:

[0052] (1) Ore pretreatment: the raw ore is crushed, screened and ball milled, and the grinding size is 86.57% of -200 mesh.

[0053] (2) Reverse flotation roughing enrichment: 500 g of raw ore is added to a 1.5 L flotation tank, and tap water is used for slurry, and after sufficient stirring, 30 kg / t of pH adjusting agent sulfuric acid (40%) is added, stirred for 1 min, then 400 g / t of dispersant sodium hexametaphosphate is added, stirred for 2 min, then 4 kg / t of inhibitor phosphoric acid (10%) is added, stirred for 2 min, and finally 2.7 kg / t of the prepared collector is added, stirred for 3 min, and after aeration and bubbling, it is floated for 5 min.

[0054] (3) Reverse flotation scavenging enrichment: taking the product in the tank obtained in step (2), tap water is supplemented to the flotation tank, the total volume of water in the tank is the same as that in step (2), after being fully stirred and made uniform, 0.9 kg / t of the collector prepared above is added, stirring for 2 min, after being aerated and bubbled, flotation is carried out for 3 min.

[0055] Example Four

[0056] The collector with code CYS-3 is obtained by using the compounding method of Example One, and then a high-magnesium low-grade phosphate ore in Guizhou is floated by using the demagnetizing collector of this example.

[0057] The ore sample is subjected to one roughing and one scavenging reverse flotation by using CYS-3, and the flotation process conditions are as follows:

[0058] (1) Ore pretreatment: the raw ore is subjected to crushing, screening and ball milling operations, and the grinding size is 89.31% of -200 mesh.

[0059] (2) Reverse flotation roughing enrichment: 500 g of raw ore is added to a 1.5 L flotation tank, tap water is used for slurry, after being fully stirred and made uniform, 30 kg / t of pH adjusting agent sulfuric acid (40%) is first added, stirring for 1 min, then 400 g / t of dispersant sodium hexametaphosphate is added, stirring for 2 min, then 4 kg / t of inhibitor phosphoric acid (10%) is added, stirring for 2 min, and finally 2.7 kg / t of the collector prepared above is added, stirring for 3 min, after being aerated and bubbled, flotation is carried out for 5 min.

[0060] (3) Reverse flotation scavenging enrichment: taking the product in the tank obtained in step (2), tap water is supplemented to the flotation tank, the total volume of water in the tank is the same as that in step (2), after being fully stirred and made uniform, 0.9 kg / t of the collector prepared above is added, stirring for 2 min, after being aerated and bubbled, flotation is carried out for 3 min.

[0061] Example Five

[0062] The collector with code CYS-4 is obtained by using the compounding method of Example One, and then a high-magnesium low-grade phosphate ore in Guizhou is floated by using the collector of this example.

[0063] The ore sample is subjected to one roughing and one scavenging reverse flotation by using CYS-4, and the flotation process conditions are as follows:

[0064] (1) Ore pretreatment: the raw ore is subjected to crushing, screening and ball milling operations, and the grinding size is 80.19% of -200 mesh.

[0065] (2) Reverse flotation roughing enrichment: 500 g of raw ore was added into a 1.5 L flotation tank, and tap water was used for slurry preparation. After sufficient stirring, 30 kg / t of pH adjusting agent, sulfuric acid (40%), was added first, and stirred for 1 min. Then 400 g / t of dispersant, sodium hexametaphosphate, was added, and stirred for 2 min. Next, 4 kg / t of depressant, phosphoric acid (10%), was added, and stirred for 2 min. Finally, 2.7 kg / t of the collector prepared above was added, and stirred for 3 min. After aeration and bubbling, the flotation was carried out for 5 min.

[0066] (3) Reverse flotation scavenging enrichment: the tank product obtained in step (2) was taken, and tap water was added to the flotation tank. The total volume of water in the tank was the same as that in step (2). After sufficient stirring, 0.9 kg / t of the collector prepared above was added, and stirred for 2 min. After aeration and bubbling, the flotation was carried out for 3 min.

[0067] Comparative Example 1

[0068] The difference between this comparative example and Example 1 is that in the demagnetizing collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:0:5.

[0069] Comparative Example 2

[0070] The difference between this comparative example and Example 1 is that in the demagnetizing collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:1:4.

[0071] Comparative Example 3

[0072] The difference between this comparative example and Example 1 is that in the demagnetizing collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:2:3.

[0073] Comparative Example 4

[0074] The difference between this comparative example and Example 1 is that in the demagnetizing collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:4:1.

[0075] Comparative Example 5

[0076] The difference between this comparative example and Example 1 is that in the demagnetizing collector, the basic material ratio is fatty acid soap: surfactant: auxiliary agent = 11:5:0.

[0077] Experimental Part

[0078] Experiment 1

[0079] The obtained concentrates and tailings of examples 2-5 are subjected to chemical detection, and the detection results are shown in Table 1. The raw ore is a high-magnesium low-grade phosphate ore, and the phosphate ore is separated by flotation using the collector of the present application. In the same collector dosage per unit of phosphate ore, the collector dosage in examples 2-5 is 2700 g / t.

[0080] Table 1 Chemical detection results

[0081]

[0082] As can be seen from Table 1, in example two, the particle size of the feed is 83.45% -200 mesh, and from the feed with a raw ore 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 by one roughing and one scavenging reverse flotation process, and the P2O5 recovery rate is 92.27%.

[0083] In example three, the particle size of the feed is 86.57% -200 mesh, and from the feed with a raw ore 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 by one roughing and one scavenging reverse flotation process, and the P2O5 recovery rate is 91.78%.

[0084] In example four, the particle size of the feed is 89.31% -200 mesh, and from the feed with a raw ore 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 by one roughing and one scavenging reverse flotation process, and the P2O5 recovery rate is 87.14%.

[0085] In example five, the particle size of the feed is 80.19% -200 mesh, and from the feed with a raw ore 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 by one roughing and one scavenging reverse flotation process, and the P2O5 recovery rate is 86.41%.

[0086] The results show that for high-magnesium low-grade phosphate ore, the collector for reverse flotation of phosphate ore of the present application has good selectivity and strong magnesium capture ability (from examples two to five, most of the magnesium in the feed is captured into the tailings, and the content of magnesium in the obtained phosphate concentrate is greatly reduced), and the flotation separation index is good. Meanwhile, in view of the difference in ore properties and grinding fineness, the de-magnesium collector provided by the present application has strong adaptability and stability, and under the condition of the same dosage, high-quality phosphate concentrate products can be stably obtained.

[0087] Experiment two

[0088] The demagnetizing collector obtained from Example 1 and Comparative Examples 1 to 5 is used to float a high-magnesium and low-grade phosphate ore in Guizhou by the technical solution of Example 2, and the concentrate obtained is subjected to chemical detection to test the P2O5 grade, and the P2O5 recovery rate is calculated through the concentrate yield and the P2O5 grade, and the results are shown in Table 1. Figure 2 As shown in Table 1, when the ratio of the surfactant to the auxiliary agent is 3:2 (Example 1), the phosphate concentrate with a P2O5 grade of 34.12% is obtained, and the P2O5 recovery rate is 90.48%; the P2O5 grade of the concentrate of Comparative Examples 1 to 5 is lower than that of Example 1; the P2O5 recovery rate of Comparative Examples 1 to 4 is also poorer 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 the concentrate is poor; in summary, when the ratio of the surfactant to the auxiliary agent is 3:2, the effect is the best.

Claims

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

2. A fluorapatite phosphate ore reverse flotation demagnification collector as claimed in claim 1, characterized in that, The preparation method of the reverse flotation magnesium removal collector is as follows: Step one: configure the fatty acid soap into a 1%-3% fatty acid soap aqueous solution, and configure the surfactant into a 1%-3% surfactant aqueous solution; Step two: add the fatty acid soap aqueous solution and the surfactant aqueous solution into a reaction container, and mix by stirring; Step three: while stirring and mixing, add the auxiliary agent into the reaction container during the stirring process; Step four: after the auxiliary agent is added dropwise, stop stirring, and after the liquid surface is calm, the collector finished product is obtained.

3. A fluorapatite phosphate ore reverse flotation demagnification collector as claimed in claim 2, characterized in that, The capacity of the reaction container is 500-1000 ml, and the stirring and mixing are performed by a magnetic stirring rod with a rotation speed of 300 r / min.

4. Use of a fluorapatite phosphate ore reverse flotation demagnification collector according to any one of claims 1 to 3, characterized in that, The specific method is as follows: S1, crush, screen, and ball mill the fluorapatite phosphate ore to obtain a fine-grained raw ore; S2, use reverse flotation roughing enrichment on the fine-grained raw ore, and add the reverse flotation magnesium removal collector in the reverse flotation roughing enrichment to obtain an intermediate product; S3, use reverse flotation scavenging enrichment on the intermediate product to obtain a magnesium-removed phosphate concentrate product.

5. Use of a fluoroapatite phosphate ore reverse flotation demagnification collector as claimed in claim 4, characterized in that, The specific method of step S2 is as follows: S51, use water to adjust the fine-grained raw ore to be slurry, and fully stir and mix it; S52, adjust the ore slurry to a pH of 4-5 using a pH adjuster, and stir for 1 min; S53, add a dispersing agent at a dosage of 400 g / t, stir for 2 min, then add an inhibitor at a dosage of 4 kg / t, stir for 2 min, and finally add the reverse flotation magnesium removal collector at a dosage of 2.7 kg / t, stir for 3 min, and scrape to obtain the intermediate product.

6. Use of a fluoroapatite phosphate ore reverse flotation demagnification collector as claimed in claim 5, characterized in that, In step S3, the specific method for obtaining the phosphate concentrate is as follows: add water to the intermediate product, fully stir and mix it, then add the reverse flotation magnesium removal collector at a dosage of 0.9 kg / t, stir for 2 min, bubble after charging, and scrape for 3 min to obtain the magnesium-removed phosphate concentrate product.

7. Use of a fluorine apatite phosphate ore reverse flotation demagnification collector as claimed in claim 4, characterized in that, In the fine-grained raw ore, the feed size is not less than 80% of -200 mesh.

8. Use of a fluorine apatite phosphate ore reverse flotation demagnification collector as claimed in claim 5, characterized in that, The pH adjuster is sulfuric acid, the concentration of the sulfuric acid is 40%, and the dispersing agent is sodium hexametaphosphate.

9. Use of a fluorine apatite phosphate ore reverse flotation demagnification collector as claimed in claim 5, characterized in that, The inhibitor is phosphoric acid, and the concentration of the phosphoric acid is 10%.

10. Use of a fluorine apatite phosphate ore reverse flotation demagnification collector as claimed in claim 5, characterized in that, It is used for separating apatite from dolomite.

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