Preparation method and application of a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate

Abstract

The invention discloses a preparation method and application of a fluorine-sulfur synchronous removal collector in a magnetite concentrate, wherein step 1 selects 50 80 parts of oleic acid, 10 20 parts of benzohydroxamic acid, and 0 10 parts of lauric acid, and the formed mixture is added to a reaction vessel to carry out saponification reaction; step 2, the saponified product obtained in step 1 is stirred and mixed with xanthate and black medicine to obtain a final collector, which is used for reverse flotation desulfurization and defluorination of magnetite concentrate. The present invention provides a method for preparing a flotation collector for synchronous desulfurization and defluorination of a magnetite concentrate having stable operation, economy, environmental protection, high efficiency and strong adaptability, and provides an application method of the flotation collector.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, in particular to a preparation method and application of a collector for simultaneously removing fluorine and sulfur from magnetite concentrate. Background Art

[0002] The selective adsorption of target minerals by collectors is the key to the quality of mineral flotation separation indicators, and collector design is the core of mineral flotation technology. Currently, as iron ore grades become lower and lower, particle sizes become finer, and the harmful elements (sulfur and fluorine) contained become more and more complex, extracting more and higher-quality iron concentrate from limited iron ore requires collectors with higher performance against these harmful impurities.

[0003] Currently, commonly used sulfur (pyrrhotite or pyrite) collectors include xanthate, nitrosulfate, thiocarbamate, and thiourea, while commonly used fluorine (fluorite, phosphate rock, or bastnaesite) collectors include oleic acid, hydroxamic acid, and organophosphonic acids. However, the desulfurization process generally requires use in weakly acidic slurry conditions, while defluorination collectors require use in weakly alkaline slurry conditions. Therefore, when magnetite concentrate requires both desulfurization and defluorination, the beneficiation plant generally requires two flotation processes, and the conversion between acidic and alkaline slurry conditions consumes more acid and alkali. Existing patents do not yet address the process of step-by-step desulfurization.

[0004] To achieve simultaneous desulfurization and defluorination in a single flotation process, the flotation slurry conditions for both desulfurization and defluorination must be standardized. Modifying the desulfurization and defluorination collectors to maximize their capture capacity and selectivity under natural pH conditions is the key to simultaneous desulfurization and defluorination technology. Summary of the Invention

[0005] In order to overcome the above-mentioned deficiencies of the prior art, the object of the present invention is to provide a preparation method and application of a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate;

[0006] The first object of the present invention is to provide a method for preparing a flotation collector for simultaneous desulfurization and defluorination of magnetite concentrate, which is stable in operation, economical, environmentally friendly, efficient and adaptable.

[0007] The second object of the present invention is to provide an application method of the flotation collector.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] A method for preparing a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate comprises the following steps:

[0010] Step 1: 50-80 parts by weight of oleic acid, 10-20 parts by weight of benzohydroxamic acid, and 0-10 parts by weight of lauric acid are mixed and added to a reaction vessel for saponification reaction to obtain a saponification product;

[0011] Step 2: By weight, 60-80 parts of the saponification product obtained in step 1 are stirred and mixed with 10-20 parts of xanthate and 5-10 parts of black powder to obtain the collector for simultaneous removal of fluorine and sulfur in the magnetite concentrate.

[0012] After the mixture is added to the reaction vessel in step 1, water is added to the reaction vessel, with the mass ratio of the mixture to water being 1:20-1:5; too much water will result in low reaction efficiency, while too little water will result in a high viscosity of the reaction product, which is difficult to stir.

[0013] After the mixture and water are evenly stirred, sodium hydroxide is added to the reaction vessel in a mass ratio of the mixture to sodium hydroxide of 10:1-10:3. The concentration of sodium hydroxide will affect the saponification reaction process. Too much sodium hydroxide will result in excessive alkalinity of the final product, while too little sodium hydroxide will result in insufficient saponification reaction.

[0014] In step 1, the saponification reaction temperature is between 20°C and 100°C, and the saponification reaction time is 10-50 minutes. A reaction temperature that is too high can lead to carbonization and numerous side reactions; a temperature that is too low can result in a slow saponification reaction rate. A reaction time that is too long can lead to side reactions, while a reaction time that is too short can result in an incomplete reaction.

[0015] In the step 2, the saponification product is cooled to room temperature, and the saponification product is mixed with xanthate and black medicine to form a mixture, which is stirred and mixed at room temperature until the color is uniform.

[0016] The xanthate in step 2 is butyl xanthate, pentyl xanthate or hexyl xanthate; these agents are used as reverse flotation desulfurization agents for magnetite concentrate;

[0017] The mass ratio of xanthate to black powder in step 2 is 5:1-2:1; black powder has a strong collecting ability but poor selectivity. A too high ratio will result in excessive loss of iron concentrate, while a too low ratio will reduce the collecting ability of the desulfurization agent and increase the dosage of the agent;

[0018] In the step 2, the mass ratio of the saponification product to the sum of the xanthate and the black medicine is 20:1-5:1.

[0019] A collector for simultaneous fluorine and sulfur removal from magnetite concentrate is used for the flotation of sulfur and fluorine minerals. Research has shown that the collector has excellent capture efficiency for sulfur and fluorine minerals, improving their grade and recovery rate, and reducing the magnetite content in the froth product.

[0020] The sulfur mineral contains at least one of pyrrhotite and pyrite; the fluorine mineral contains at least one of fluorite, phosphate rock, and fluorocarbon cerium; and both the sulfur mineral and the fluorine mineral must be included.

[0021] The collector can capture at least two minerals selected from pyrrhotite, pyrite, fluorite, phosphate rock and bastnaesite during the flotation process.

[0022] An application of a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate comprises the following specific steps:

[0023] Step (1): passing the magnetite concentrate through a vertical mill washing machine, adding water to adjust the pulp concentration to 20-50%, stirring evenly, adding an activator, the collector, and finally adding a regulator, and performing a roughing operation. During the roughing process, highly hydrophobic mineral particles will adhere to the bubbles, and as the bubbles rise to the liquid surface, a foam product will be formed. The scraper of the flotation machine will scrape out the foam product to obtain a coarse concentrate (foam product) and tailings (bottom product);

[0024] Step (2): After the coarse concentrate is stirred evenly, the collector is added, and after stirring evenly, a beneficiation operation is performed; the rough selected tailings are added with an activator and the collector, and then a scavenging operation is performed.

[0025] In the step (1), the vertical grinding scrubbing time is 1-3 minutes, the slurry mixing time of adding water is 1-5 minutes, the stirring time of adding the activator is 1-5 minutes, the stirring time of adding the collector is 1-5 minutes, the stirring time of adding the regulator is 1-5 minutes, and then the roughing time is carried out; if the stirring time is less than 1 minute, the slurry mixing is not uniform enough or the agent action time is insufficient, and the ideal effect cannot be achieved; if the time is more than 5 minutes, the surface of the sulfide ore is easily oxidized, affecting the effect of the agent, or the stirring time is too long, affecting the residence time of the agent.

[0026] In the step (1), 50-300 g / activator is added per ton of magnetically separated iron ore concentrate; in the step (1), the activator is a mixture of copper sulfate and ammonium chloride in a ratio of (1:0.5)-(1:2); the purpose of setting the parameters in this way is to achieve a synergistic activation effect of copper sulfate and ammonium chloride, and too high or too low will affect the activation effect.

[0027] In the step (1), 150-450 g / t of the flotation collector is added per ton of magnetically separated iron ore;

[0028] In the step (1), 50-200 g / t of the adjusting agent is added per ton of magnetically separated iron ore concentrate;

[0029] In the step (1), the added adjusting agent is at least one of sodium hexametaphosphate, water glass, and oxalic acid;

[0030] In the step (2), the collector, activator, and regulator added are of the same type as the reagents in the step (1), and the dosage of the reagents is 1 / 3-1 / 2 of the dosage of the reagents in the step (1).

[0031] The purpose of this setting is that in the selection or scavenging operation, if the amount of collector added is too large, the foam product will contain higher impurities, and if the amount is too small, the selection or scavenging effect will be poor; if the amount of inhibitor added is too large, the target mineral will be suppressed too strongly and not easy to float, and if the amount is too small, the inhibition effect will be too poor and the foam product will contain too many impurities; if the amount of activator added is too large, the cost will be too high, and if the amount is too small, the activation effect will not be obvious.

[0032] Beneficial effects of the present invention:

[0033] ① The collector provided by the present invention has a strong ability to capture sulfur-containing minerals and fluorine-containing minerals in magnetite concentrate, and can simultaneously perform flotation recovery on these two minerals, thereby realizing a shortened process for desulfurization and defluorination.

[0034] ② The collectors provided by the present invention are synthesized and compounded using commonly used collectors in mineral processing plants as raw materials. Compared with other special-effect collectors, they have the advantages of being environmentally friendly, widely available, low in price, effective, and having little environmental pollution.

[0035] ③ The collector provided by the present invention has a simple preparation method, mild reaction conditions, good solubility, and can be added directly. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a flow chart of the flotation principle of the present invention. DETAILED DESCRIPTION

[0037] The present invention will be described in further detail below with reference to the accompanying drawings.

[0038] like Figure 1 As shown, an application of a collector for simultaneous removal of fluorine and sulfur in magnetite concentrate comprises the following specific steps:

[0039] Step (1): passing the magnetite concentrate through a vertical mill washing machine, adding water to adjust the pulp concentration to 20-50%, stirring evenly, adding an activator, the collector, and finally adding a regulator, and performing a roughing operation. During the roughing process, highly hydrophobic mineral particles will adhere to the bubbles, and as the bubbles rise to the liquid surface, a foam product will be formed. The scraper of the flotation machine will scrape out the foam product to obtain a coarse concentrate (foam product) and tailings (bottom product);

[0040] Step (2): After the coarse concentrate is stirred evenly, the collector is added, and after stirring evenly, a beneficiation operation is performed; the rough selected tailings are added with an activator and the collector, and then a scavenging operation is performed.

[0041] In the step (1), the vertical grinding scrubbing time is 1-3 minutes, the slurry mixing time of adding water is 1-5 minutes, the stirring time of adding the activator is 1-5 minutes, the stirring time of adding the collector is 1-5 minutes, the stirring time of adding the regulator is 1-5 minutes, and then the roughing time is carried out; if the stirring time is less than 1 minute, the slurry mixing is not uniform enough or the agent action time is insufficient, and the ideal effect cannot be achieved; if the time is more than 5 minutes, the surface of the sulfide ore is easily oxidized, affecting the effect of the agent, or the stirring time is too long, affecting the residence time of the agent.

[0042] In the step (1), 50-300 g / activator is added per ton of magnetically separated iron ore concentrate; in the step (1), the activator is a mixture of copper sulfate and ammonium chloride, and the ratio is between (1:0.5) and (1:2); the purpose of setting the parameters in this way is to achieve a synergistic activation effect of copper sulfate and ammonium chloride, and too high or too low will affect the activation effect.

[0043] In the step (1), 150-450 g / t of the flotation collector is added per ton of magnetically separated iron ore;

[0044] In the step (1), 50-200 g / t of the adjusting agent is added per ton of magnetically separated iron ore concentrate;

[0045] In the step (1), the added adjusting agent is at least one of sodium hexametaphosphate, water glass, and oxalic acid;

[0046] In the step (2), the collector, activator, and regulator added are of the same type as the reagents in the step (1), and the dosage of the reagents is between 1 / 3 and 1 / 2 of the dosage of the reagents in the step (1).

[0047] The purpose of this setting is that in the selection or scavenging operation, if the amount of collector added is too large, the foam product will contain higher impurities, and if the amount is too small, the selection or scavenging effect will be poor; if the amount of inhibitor added is too large, the target mineral will be suppressed too strongly and not easy to float, and if the amount is too small, the inhibition effect will be too poor and the foam product will contain too many impurities; if the amount of activator added is too large, the cost will be too high, and if the amount is too small, the activation effect will not be obvious.

[0048] Example 1

[0049] In a reaction vessel equipped with a stirrer and a thermometer, 50 parts of oleic acid, 30 parts of benzohydroxamic acid, 20 parts of lauric acid, 15 parts of sodium hydroxide, and 1150 parts of water were added, and the mixture was heated to 50° C. in a water bath and the saponification reaction time was 30 minutes to obtain a saponified product.

[0050] After the saponification product was cooled to room temperature, 10 parts of butyl xanthate and 5 parts of black medicine were added to the reactor and stirred until the color was uniform. The obtained product was recorded as Example 1.

[0051] Comparative Example 1

[0052] Other conditions were the same as those in Example 1, except that oleic acid was 70 parts and lauric acid was not added. The obtained product was recorded as Comparative Example 1.

[0053] Comparative Example 2

[0054] Other conditions were the same as those in Example 1, except that the saponification reaction temperature was 20° C. The obtained product was recorded as Comparative Example 2.

[0055] Comparative Example 3

[0056] Other conditions were the same as those in Example 1, except that the saponification reaction temperature was 100° C. The obtained product was recorded as Comparative Example 3.

[0057] Comparative Example 4

[0058] Other conditions were the same as those in Example 1, except that 10 parts of amyl xanthate were added. The resulting product was recorded as Comparative Example 4.

[0059] Comparative Example 5

[0060] Other conditions were the same as those in Example 1, except that 10 parts of hexyl xanthate were added. The resulting product was recorded as Comparative Example 5.

[0061] Application Example 1:

[0062] raw material

[0063] The mineral raw material is magnetically separated iron ore concentrate. Phase analysis results show that the main sulfur-containing mineral in the mineral is pyrrhotite, with a small amount of pyrite. The main fluorine-containing mineral is fluorite, with a small amount of bastnaesite. The grinding fineness is -0.045, accounting for 80-85%. The collector used is the collector obtained in Example 1 and Comparative Examples 1-5.

[0064] Steps

[0065] Take 500g of magnetically separated iron concentrate, scrub it with a vertical mill for 1 minute, add water to adjust the pulp to a pulp concentration of 30-40%, add the 150g / t activator (copper sulfate and ammonium chloride mixed in a ratio of 1:1), stir for 3 minutes, add 200g / t collector, stir for 3 minutes, and finally add 50g / t of adjusting agent sodium hexametaphosphate, stir for 3 minutes, and then perform roughing operation to obtain coarse concentrate and tailings; add 100g / t and 50g / t collector to the coarse concentrate and perform two concentration operations respectively, add 20g / t and 10g / t sodium hexametaphosphate and 100g / t and 50g / t collector to the roughing tailings respectively, and perform two scavenging operations. The concentrating and scavenging ore are returned to the previous flotation operation in sequence. The test process is shown in FIG. Figure 1 , the test results are shown in Table 1.

[0066] Table 1 Flotation test results

[0067]

[0068] The experimental results obtained in Example 1 and Comparative Examples 1-5 show that the collector obtained by the present invention has a collecting effect on both sulfur-containing and fluorine-containing minerals, and has an excellent collecting ability for sulfur-containing minerals. It can be widely used in reverse flotation operations for removing impurities from various sulfur-containing and fluorine-containing iron concentrates. At the same time, the experimental results of Example 1 and Comparative Examples 2-3 show that excessively high or low temperatures during the preparation of the collector of the present invention will affect the collecting effect of the collector, especially the collecting ability of fluorine-containing minerals. The experimental results of Example 1 and Comparative Examples 4-5 show that the effect of adding xanthate is slightly better than that of butyl xanthate and amyl xanthate.

Claims

1. A method for preparing a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate, characterized in that: The following steps are included: Step 1: 50-80 parts by weight of oleic acid, 10-20 parts by weight of benzohydroxamic acid, and 0-10 parts by weight of lauric acid are mixed and added to a reaction vessel for saponification reaction to obtain a saponification product; Step 2, by weight, mixing 60-80 parts of the saponification product obtained in step 1 with 10-20 parts of xanthate and 5-10 parts of black powder to obtain a collector for simultaneous removal of fluorine and sulfur in the magnetite concentrate; After the mixture is added to the reaction vessel in step 1, water is added to the reaction vessel, with the mass ratio of the mixture to water being 1:20-1:5; After the mixture and water are stirred evenly, sodium hydroxide is added to the reaction vessel, with the mass ratio of the mixture to sodium hydroxide being 10:1-10:3; The saponification reaction temperature in step 1 is between 20-100° C. and the saponification reaction time is 10-50 minutes.

2. The method for preparing a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate according to claim 1, characterized in that: In the step 2, the saponification product is cooled to room temperature, and the saponification product is mixed with xanthate and black medicine to form a mixture, which is stirred and mixed at room temperature until the color is uniform.

3. The method for preparing a collector for simultaneous removal of fluorine and sulfur from magnetite concentrate according to claim 1, characterized in that: The xanthate in step 2 is butyl xanthate, pentyl xanthate or hexyl xanthate; The mass ratio of yellow medicine to black medicine in step 2 is 5:1-2:1; In the step 2, the mass ratio of the saponification product to the sum of the xanthate and the black medicine is 20:1-5:

1.

4. An application of a collector for simultaneous removal of fluorine and sulfur in magnetite concentrate, characterized in that: The collector is prepared by the method according to any one of claims 1 to 3, and the collector is used for flotation of sulfur minerals and fluorine minerals; The sulfur mineral contains at least one of pyrrhotite and pyrite; the fluorine mineral contains at least one of fluorite, phosphate rock, and bastnaesite; both the sulfur mineral and the fluorine mineral must be contained; The collector can capture at least two minerals selected from pyrrhotite, pyrite, fluorite, phosphate rock and bastnaesite during the flotation process.

5. The use of a collector for simultaneous removal of fluorine and sulfur in magnetite concentrate according to claim 4, characterized in that: The following specific steps are included: Step 1): The magnetite concentrate passes through the vertical mill and cymbal washing machine, and water is added to adjust the pulp concentration to 20-50%. After stirring evenly, the activator, the collector, and finally the regulator are added to perform roughing operations. During the roughing process, the hydrophobic mineral particles will adhere to the bubbles. As the bubbles rise to the liquid surface, foam products are formed. The scraper of the flotation machine will scrape out the foam products to obtain rough concentrate and tailings. Step 2): After the coarse concentrate is stirred evenly, the collector is added, and after stirring evenly, the beneficiation operation is carried out; for the rough tailings, an activator is added, the collector is added, and then a scavenging operation is carried out.

6. The use of a collector for simultaneous removal of fluorine and sulfur in magnetite concentrate according to claim 5, characterized in that: In the step 1), the vertical grinding scrubbing time is 1-3 minutes, the water slurry mixing time is 1-5 minutes, the activator is added and stirred for 1-5 minutes, the collector is added and stirred for 1-5 minutes, the regulator is added and stirred for 1-5 minutes, and then the roughing time is carried out; In the step 1), 50-300 g / activator is added per ton of magnetically separated iron ore concentrate; in the step 1), the activator is a mixture of copper sulfate and ammonium chloride in a ratio of (1:0.5) to (1:2); In the step 1), 150-450 g / t of the flotation collector is added per ton of magnetically separated iron ore; In the step 1), 50-200 g / t of the adjusting agent is added per ton of magnetically separated iron ore concentrate; In the step 1), the added adjusting agent is at least one of sodium hexametaphosphate, water glass, and oxalic acid.

7. The use of a collector for simultaneous removal of fluorine and sulfur in magnetite concentrate according to claim 6, characterized in that: In the step 2), the collector, activator, and regulator added are of the same type as those in the step 1), and the dosage of the agents is 1 / 3-1 / 2 of the dosage of the agents in the step 1).

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