A method for the pretreatment of a mineral in conjunction with a separation process of a flotation reagent

Abstract

The present application relates to a kind of mineral pretreatment method and separation process of synergistic flotation reagent, belong to flotation technical field, to solve at least one of the problems such as poor collecting effect, poor selectivity and large dosage of reagent during flotation in the rough and fine flotation method of prior art ilmenite.Most of the Fe 2+ On the surface of ilmenite is oxidized to Fe 3+ By adjusting the ratio and flow of argon and oxygen, the surface properties of ilmenite and peridot are improved.In addition, the use of oxidized tianjing glue is more conducive to the combination of calcium and magnesium active sites on the surface of gangue minerals, and the oxidized tianjing glue can be uniformly adsorbed on the surface of gangue minerals, further improving the hydrophilicity of gangue minerals and enhancing the hydrophilic and hydrophobic difference between the surface of target minerals and gangue minerals.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ilmenite, and particularly relates to a pretreatment method of mineral and a separation process of flotation reagent. BACKGROUND

[0002] China is rich in titanium resources, accounting for about 28% of the total reserves in the world. Ilmenite is the main source of titanium resources in China, mainly distributed in Panzhihua and Xichang areas of Sichuan. The ilmenite resources in China are characterized by "more lean ore, less rich ore, and fine particle size", which makes it difficult to achieve efficient separation and restricts the further utilization of titanium resources. Flotation is an important method to realize efficient separation of fine-grained mineral resources. Due to the similar surface properties of the target mineral and the gangue mineral, the traditional fatty acid collector has good collecting property, but it is difficult to achieve efficient separation of the two. Arsonic acid and phosphoric acid collectors have certain collecting agent and selectivity, but there are problems such as environmental pollution, so it is necessary to develop environmentally friendly high-selectivity flotation collectors.

[0003] In recent years, hydroxamic acid collectors have been widely concerned in ilmenite flotation process due to their excellent flotation performance, but the dosage of hydroxamic acid collectors in the existing one-roughing and one-cleaning flotation method is large, and the selective separation ability for low-grade ilmenite and gangue minerals is limited. SUMMARY

[0004] In view of the above analysis, the present application aims to provide a pretreatment method of mineral and a separation process of flotation reagent, to solve at least one of the problems of poor collecting effect, poor selectivity of ilmenite in the existing one-roughing and one-cleaning flotation method, and large dosage of reagents during flotation.

[0005] In the first aspect, the present application provides a pretreatment method of mineral and a separation process of flotation reagent, comprising the following steps:

[0006] (1) treating the raw ore slurry by plasma to obtain treated ore slurry;

[0007] (2) adding oxidized mucilage and a collector to the treated ore slurry to perform first flotation to obtain rough concentrate, and performing second flotation on the rough concentrate to obtain ilmenite concentrate;

[0008] The structure of the collector is as follows:

[0009]

[0010] Further, in step (1), the power in the plasma treatment is 100-200 W, and the treatment time is 3-6 min.

[0011] Further, in step (1), the plasma treatment uses a plasma treatment gas, and the flow rate of the treatment gas is 300-500 mL / min.

[0012] Further, in step (2), the oxidized sesbania gum is prepared by the following method:

[0013] (a) dispersing sesbania gum in anhydrous ethanol, adding water, stirring uniformly, adjusting the pH value to 8 with an alkali solution to obtain a slurry;

[0014] (b) subjecting the slurry to plasma treatment, precipitating by adding an ethanol aqueous solution with a volume fraction of 60-80% to obtain a precipitate;

[0015] (c) sequentially subjecting the precipitate to recrystallization, drying and crushing to obtain the oxidized sesbania gum.

[0016] Further, in step (a), the viscosity-average molecular weight of the sesbania gum is 1-1.1 million.

[0017] Further, in step (b), the power in the plasma treatment is 200-500 W, and the treatment time is 5-10 min.

[0018] Further, in step (2), the added amount of the oxidized sesbania gum is 200-300 g / t.

[0019] Further, the collector is prepared by the following method:

[0020] (I) mixing 2-sulfobenzene acetic acid and methanol to perform esterification, adjusting the pH value to weak acidity after the reaction is completed to obtain an ester compound;

[0021] (II) dissolving hydroxylamine salt and alkali in methanol, ultrasonic dispersion and dissolution, reacting under ice water bath conditions to obtain free hydroxylamine, then adding the ester compound and heating to perform hydroximic acidization, adjusting the pH value, filtering and drying to obtain the collector.

[0022] Further, in step (I), the temperature of the esterification is 60-80°C, and the pH value is adjusted to 5-6.

[0023] Further, in step (II), the hydroxylamine salt is one of hydroxylamine hydrochloride, hydroxylamine carbonate and hydroxylamine sulfate.

[0024] Compared with the prior art, the present application can at least achieve one of the following beneficial effects:

[0025] (1) The method of the present application first subjects the raw ore to plasma treatment to strip the impurities on the surface of ilmenite, and by adjusting the proportion and flow rate of argon and oxygen, part of Fe 2+ is oxidized to Fe3+ This invention enhances the difference in surface properties between ilmenite and forsterite. Furthermore, the use of oxidized guar gum in this invention is more conducive to binding with the calcium and magnesium active sites on the surface of gangue minerals. Simultaneously, the oxidized guar gum can be uniformly adsorbed on the surface of gangue minerals, further improving the hydrophilicity of gangue minerals and enhancing the difference in hydrophilicity and hydrophobicity between the target mineral and the gangue mineral surface. On the surface of the target mineral, compared to high molecular weight inhibitors, the unstable oxidized guar gum is more easily displaced by collector molecules, which is beneficial for the selective adsorption of subsequent collector molecules on the ilmenite surface, while reducing the consumption of oxidized guar gum reagents.

[0026] (2) In this invention, plasma treatment is used to oxidize and decompose guar gum. The molecular weight of oxidized guar gum is 100,000 to 120,000 viscosity-average molecular weight. Oxidized guar gum has carboxyl groups, which makes it easier to interact with the surface of gangue minerals and easier to displace collector molecules. This is beneficial for the selective adsorption of collector molecules on the surface of ilmenite, while reducing the consumption of reagents for oxidized guar gum.

[0027] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained through the details specifically pointed out in the description and drawings. Attached Figure Description

[0028] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0029] Figure 1 The mass spectrum of the collector prepared in Example 1 of this invention;

[0030] Figure 2 The image shows the nuclear magnetic resonance (NMR) spectrum of the collector prepared in Example 1 of this invention. Detailed Implementation

[0031] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the scope of the present invention.

[0032] A specific embodiment of the present invention discloses a mineral pretreatment method combined with a flotation reagent separation process, comprising the following steps:

[0033] (1) The raw ore slurry is subjected to plasma treatment to obtain the treated slurry;

[0034] (2) adding oxidized phyllite glue and a collector into the treated ore slurry to perform first flotation to obtain a rough concentrate, and performing second flotation on the rough concentrate to obtain ilmenite concentrate;

[0035] The structure of the collector is as follows:

[0036]

[0037] Compared with the prior art, the method of the present application first uses plasma to treat the raw ore to strip the impurities on the surface of ilmenite, and by adjusting the proportion and flow rate of argon and oxygen, part of Fe 2+ is oxidized to Fe 3+ , thereby improving the difference in surface properties between ilmenite and peridot. In addition, the use of oxidized phyllite glue in the present application is more conducive to the combination with the active sites of calcium and magnesium on the surface of gangue minerals, and the oxidized phyllite glue can be uniformly adsorbed on the surface of the gangue minerals, further improving the hydrophilicity of the gangue minerals and enhancing the difference in hydrophilicity and hydrophobicity between the target minerals and the gangue minerals. On the surface of the target minerals, the unstable oxidized phyllite glue is more easily displaced by the collector molecules than the macromolecular inhibitors, which is conducive to the selective adsorption of the collector molecules on the surface of ilmenite, and reduces the consumption of oxidized phyllite glue.

[0038] In one specific embodiment, in step (1), the mass concentration of the raw ore slurry is 30-40%. The concentration in the above range is consistent with the concentration of the flotation slurry, and a too low or too high concentration is not conducive to the floating of the minerals.

[0039] In one specific embodiment, in step (1), the power in the plasma treatment is 100-200 W, for example, 100 W, 120 W, 140 W, 160 W, 180 W, or 200 W, and the treatment time is 3-6 min, for example, 3 min, 4 min, 5 min, or 6 min.

[0040] In one specific embodiment, in step (1), the plasma treatment uses a plasma treatment gas, the plasma treatment gas is a mixture of argon and oxygen in a volume ratio of 2:3, and the flow rate of the treatment gas is 300-500 mL / min, for example, 300 mL / min, 320 mL / min, 340 mL / min, 360 mL / min, 380 mL / min, 400 mL / min, 420 mL / min, 440 mL / min, 460 mL / min, 480 mL / min, or 500 mL / min.

[0041] It should be noted that if there is only argon in the treatment gas, the plasma cleaning machine only has the effect of cleaning surface impurities, and if there is oxygen, the surface of the ilmenite can be oxidized to be more hydrophilic, and the divalent iron ions can be oxidized to trivalent iron ions, which is more conducive to the adsorption of the collector. The surface of the forsterite (gangue) is oxidized, which is more hydrophilic, and the difference in the surface properties of the two minerals after the pretreatment is greater, which is conducive to flotation. The volume ratio of the plasma treatment gas according to the present application is beneficial to prevent the ilmenite from being oxidized too much, so that the degree of surface oxidation is too large and the hydrophilicity is enhanced. If the oxidation is too much, the surfaces of the two minerals will have strong hydrophilicity, and the difference will decrease, so the proportion of oxygen introduced is controlled.

[0042] In one specific embodiment, in step (2), the oxidized sesbania gum is prepared by the following method:

[0043] (a) dispersing the sesbania gum with anhydrous ethanol, adding water, stirring uniformly, adjusting the pH value to 8 with an alkali solution, and obtaining a slurry;

[0044] (b) treating the slurry with plasma, precipitating with an ethanol aqueous solution with a volume fraction of 60-80%, and obtaining a precipitate;

[0045] (c) sequentially performing recrystallization, drying, and crushing treatment on the precipitate, and obtaining the oxidized sesbania gum.

[0046] In one specific embodiment, in step (a), the alkali solution is a sodium hydroxide solution with a concentration of 1-2 mol / L.

[0047] Specifically, in step (a), the viscosity-average molecular weight of the sesbania gum is 1-1.1 million.

[0048] In one specific embodiment, in step (b), the power in the plasma treatment is 200-500 W, for example, 200 W, 250 W, 300 W, 350 W, 400 W, 450 W, 500 W, and the treatment time is 5-10 min, for example, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min.

[0049] In one specific embodiment, in step (b), the plasma treatment uses a plasma treatment gas, and the plasma treatment gas is oxygen. The flow rate of the treatment gas is 300-500 mL / min, for example, 300 mL / min, 320 mL / min, 340 mL / min, 360 mL / min, 380 mL / min, 400 mL / min, 420 mL / min, 440 mL / min, 460 mL / min, 480 mL / min, 500 mL / min.

[0050] The oxidized sesbania gum is used in the present application to be decomposed by plasma treatment, and the molecular weight of the oxidized sesbania gum is 100-120 thousand of viscosity average molecular weight. The oxidized sesbania gum has carboxyl group, and is more easily to react with the surface of gangue mineral and to be removed by the collector molecules on the surface of target mineral, which is beneficial to the selective adsorption of the collector molecules on the surface of ilmenite, and reduces the consumption of the oxidized sesbania gum.

[0051] In a specific embodiment, in step (2), the adding amount of the oxidized sesbania gum is 200-300 g / t, for example, 200 g / t, 250 g / t, 300 g / t, 350 g / t, 400 g / t, 450 g / t, 500 g / t; and the adding amount of the collector is 300-600 g / t, for example, 300 g / t, 350 g / t, 400 g / t, 450 g / t, 500 g / t, 550 g / t, 600 g / t.

[0052] In a specific embodiment, sulfuric acid and a foaming agent are added in the first and second flotation.

[0053] Preferably, sulfuric acid is added in the first flotation to make the pH of the ore pulp 4-5, and sulfuric acid is added in the second flotation to make the pH of the ore pulp 3-4.

[0054] Specifically, the adding amount of the foaming agent is 40.1 g / t, and preferably, the foaming agent is methyl isobutyl carbinol.

[0055] Specifically, the time of the two flotation is the same.

[0056] In a specific embodiment, in step (2), the collector is prepared by the following method:

[0057] (I) 2-sulfobenzene acetic acid and methanol are mixed to carry out esterification reaction, and after the reaction is completed, the pH is adjusted to weak acidity to obtain an ester compound;

[0058] (II) hydroxylamine salt and alkali are dissolved in methanol, ultrasonic dispersion and dissolution are carried out, free hydroxylamine is prepared under the condition of ice water bath, the ester compound is added, hydroxamidation reaction is carried out by heating, the pH is adjusted, filtration is carried out, and drying is carried out to obtain the collector.

[0059] The reaction equation of the collector of the present application is as follows:

[0060]

[0061] Specifically, in step (I), the molar ratio of 2-sulfobenzene acetic acid and methanol is 1-1.2:70-80.

[0062] In step (I), the temperature of the esterification reaction is 60-80℃, and the pH value is adjusted to 5-6.

[0063] In one specific embodiment, in step (II), the hydroxylamine salt is one of hydroxylamine hydrochloride, hydroxylamine carbonate, or hydroxylamine sulfate.

[0064] In one specific embodiment, in step (II), the heating temperature is 30-60℃.

[0065] In one specific embodiment, in step (II), the base is one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, or potassium bicarbonate.

[0066] Specifically, in step (II), the molar ratio of hydroxylamine salt to base is 1-1.5:2-2.5, and the pH value is adjusted to 5-6.

[0067] The collector of the present application is prepared by esterification and hydroxamidation, and the preparation method is simple and easy to operate.

[0068] The present application combines a bifunctional collector with strong selectivity. The polar group of the collector is composed of two adjacent sulfonic acid groups and hydroxamic acid groups, wherein the sulfonic acid groups and the hydroxamic acid groups can each form a ring with the active sites on the mineral surface, or can form a stable multi-ring with the same active site on the mineral surface, which can significantly enhance the collecting performance of the collector. In addition, the benzene ring as a non-polar group can adjust the charge distribution and electron cloud density of the polar group, thereby effectively improving the reaction performance of the polar group with metal ions, enhancing the selectivity of the collector molecules, improving the concentrate grade and recovery rate, and reducing the amount of the bifunctional collector.

[0069] The crude ore treated in the present application is calcium-magnesium-titanium ilmenite, wherein the grade of TiO2 is ≤12%.

[0070] The flotation method of the present application can not only be used for ilmenite, but also for phosphate rock, rutile, fluorite, tungsten ore, etc.

[0071] The technical solutions of the present application are further explained and described in combination with specific examples, and all raw materials in the present application are commercially available.

[0072] The technical solutions of the present application are further explained and described in combination with specific examples.

[0073] Example 1

[0074] A high-efficiency separation method of ilmenite, comprising the following steps:

[0075] (1) the raw ore slurry with mass concentration of 40% is subjected to plasma treatment, the power in the plasma treatment is 150 W, the treatment time is 6 min, the plasma treatment gas is used in the plasma treatment, the plasma treatment gas is argon and oxygen mixed in a volume ratio of 2:3, the treatment gas flow is 400 mL / min, and the treated slurry is obtained;

[0076] (2) the treated slurry is transferred into a first flotation tank, 200 g / t of oxidized sesbania gum and 300 g / t of collector are added, and first flotation is carried out, the rough concentrate is obtained, and the rough concentrate is subjected to second flotation to obtain ilmenite concentrate, wherein sulfuric acid and 40.1 g / t of foaming agent are further added during the first flotation and the second flotation, sulfuric acid is added during the first flotation to make the slurry pH = 4.5, and sulfuric acid is added during the second flotation to make the slurry pH = 3.5.

[0077] The preparation method of the oxidized sesbania gum in the embodiment is as follows:

[0078] (a) sesbania gum with a molecular weight of 1 million is dispersed with anhydrous ethanol, water is added, and stirred uniformly, and an alkaline solution is used to adjust the pH value to 8 to obtain a slurry with a mass fraction of 2%;

[0079] (b) the slurry is subjected to plasma treatment, the power in the plasma treatment is 200 W, the treatment time is 10 min, the plasma treatment gas is used in the plasma treatment, the plasma treatment gas is oxygen, the treatment gas flow is 300 mL / min, and a volume fraction of 60% of ethanol aqueous solution is added for precipitation to obtain a precipitate;

[0080] (c) the precipitate is subjected to recrystallization, drying and crushing in sequence to obtain oxidized sesbania gum with a molecular weight of 100,000.

[0081] The structural formula of the collector in the embodiment is as follows:

[0082]

[0083] The preparation method of the collector in the embodiment is as follows:

[0084] (I) 2-sulfobenzene acetic acid and methanol are weighed in a molar ratio of 1:70, mixed and placed in a 100 mL round-bottom flask, and refluxed at 60℃ for 18 h, after the reaction is completed, a mass fraction of 40% of sodium hydroxide solution is used to adjust the pH to 5-6 to obtain a benzene acetic acid methyl ester-2-sodium sulfonate solution.

[0085] (II) Hydroxylamine hydrochloride and sodium hydroxide were weighed in a molar ratio of 1.5:2.5, and hydroxylamine hydrochloride and sodium hydroxide were dissolved in 30 mL of methanol respectively, and then ultrasonic dispersion was performed for dissolution, and then the mixture was stirred in an ice water bath for 1 h to allow the hydroxylamine to be fully dissociated, and then the obtained methyl phenylacetate-2-sodium sulfonate solution was added, and the reaction was performed at 50℃ for 6 h to obtain sodium phenylhydroxamic acid-2-sodium sulfonate.

[0086] (III) The solution was acidified with concentrated sulfuric acid to adjust the pH to 5-6, and then filtered to obtain white solid as crude phenylhydroxamic acid-2-sulfonic acid, which was dispersed in ethyl acetate, filtered with a sand core funnel to remove ethyl acetate, dried, and ground to obtain a relatively pure phenylhydroxamic acid-2-sulfonic acid product.

[0087] The mass spectrum (M+Na) of the collector prepared in this example is shown in Figure 1 The nuclear magnetic resonance spectrum of the collector prepared in this example is shown in Figure 2

[0088] Example 2

[0089] A high-efficiency separation method of ilmenite, comprising the following steps:

[0090] (1) The raw ore slurry with a mass concentration of 30% is subjected to plasma treatment, the power in the plasma treatment is 100 W, the treatment time is 4.5 min, the plasma treatment gas is used in the plasma treatment, the plasma treatment gas is argon and oxygen mixed in a volume ratio of 2:3, the treatment gas flow is 300 mL / min, and a treated slurry is obtained.

[0091] (2) The treated slurry is transferred to a first flotation tank, 250 g / t of oxidized sesbania gum and 450 g / t of collector are added, and first flotation is performed to obtain a rough concentrate, and the rough concentrate is subjected to second flotation to obtain ilmenite concentrate, wherein sulfuric acid and 42 g / t of a foaming agent are further added during the first flotation and the second flotation, sulfuric acid is added during the first flotation to make the slurry pH=4, and sulfuric acid is added during the second flotation to make the slurry pH=3.

[0092] The preparation method of the oxidized sesbania gum in this example is as follows:

[0093] (a) Sesbania gum with a molecular weight of 1.05 million is dispersed with anhydrous ethanol, water is added, and stirring is performed until uniform, and an alkaline solution is used to adjust the pH value to 8 to obtain a slurry with a mass fraction of 2%;

[0094] ​(b) the slurry is treated with plasma, the power of the plasma treatment being 350 W, the treatment time being 7.5 min, the plasma treatment using a plasma treatment gas, the plasma treatment gas being oxygen, the flow rate of the treatment gas being 400 mL / min, and the precipitation being carried out by adding an ethanol aqueous solution with a volume fraction of 70% to obtain a precipitate;

[0095] (c) the precipitate is sequentially subjected to recrystallization, drying and crushing treatment to obtain the esculin with a molecular weight of 110,000.

[0096] The structural formula of the collector of the embodiment is as follows:

[0097]

[0098] The preparation method of the collector of the embodiment is as follows:

[0099] (I) 2-sulfobenzene acetic acid and methanol are weighed in a molar ratio of 1:76, mixed and placed in a 100 mL round-bottom flask, and refluxed at 70°C for 18 h. After the reaction is completed, the pH is adjusted to 5-6 by using a 40% sodium hydroxide solution to obtain a benzene acetic acid methyl ester-2-sodium sulfonate solution.

[0100] (II) hydroxylamine hydrochloride and sodium hydroxide are weighed in a molar ratio of 1:2, and are respectively dissolved in 30 mL of methanol by ultrasonic dispersion and dissolution. After mixing, the mixture is stirred in an ice water bath for 1 h to allow the hydroxylamine to be fully dissociated. Then, the obtained benzene acetic acid methyl ester-2-sodium sulfonate solution is added, and the temperature is raised to 30°C for reaction for 6 h to prepare a benzene hydroxamic acid sodium-2-sodium sulfonate.

[0101] (III) the solution is acidified by using concentrated sulfuric acid to adjust the pH to 5-6, and filtration is performed to obtain a white solid as a benzene hydroxamic acid-2-sulfonic acid crude product. The benzene hydroxamic acid-2-sulfonic acid crude product is dispersed in ethyl acetate, and a sand core funnel is used to filter the ethyl acetate, and drying and grinding are performed to prepare a relatively pure benzene hydroxamic acid-2-sulfonic acid product.

[0102] The collector prepared in the embodiment is also subjected to the test of Example 1, and the results are basically consistent. Due to the limited space, they are not listed one by one.

[0103] Example 3

[0104] An efficient separation method of ilmenite includes the following steps:

[0105] (1) the raw ore slurry with mass concentration of 35% is subjected to plasma treatment, the power in the plasma treatment is 200W, the treatment time is 3min, the plasma treatment gas is used in the plasma treatment, the plasma treatment gas is argon and oxygen mixed in a volume ratio of 2:3, the treatment gas flow is 500mL / min, and the treated slurry is obtained;

[0106] (2) the treated slurry is transferred into a first flotation tank, 300g / t of oxidized sesbania gum and 600g / t of collector are added, and first flotation is carried out, and the rough concentrate is obtained, and the rough concentrate is subjected to second flotation to obtain ilmenite concentrate, wherein sulfuric acid and 45g / t of frother are further added during the first flotation and the second flotation, sulfuric acid is added during the first flotation to make the slurry pH=5, and sulfuric acid is added during the second flotation to make the slurry pH=4.

[0107] The preparation method of the oxidized sesbania gum in the embodiment is as follows:

[0108] (a) sesbania gum with a molecular weight of 1.1 million is dispersed with anhydrous ethanol, water is added, and stirred uniformly, and the pH value is adjusted to 8 with an alkali solution to obtain a slurry with a mass fraction of 2%;

[0109] (b) the slurry is subjected to plasma treatment, the power in the plasma treatment is 500W, the treatment time is 5min, the plasma treatment gas is used in the plasma treatment, the plasma treatment gas is oxygen, the treatment gas flow is 500mL / min, and an ethanol aqueous solution with a volume fraction of 80% is added for precipitation to obtain a precipitate;

[0110] (c) the precipitate is subjected to recrystallization, drying and crushing in sequence to obtain oxidized sesbania gum with a molecular weight of 120,000.

[0111] The structural formula of the collector in the embodiment is as follows:

[0112]

[0113] The preparation method of the collector in the embodiment is as follows:

[0114] (I) 2-sulfobenzenacetic acid and methanol are weighed in a molar ratio of 1.2:80, mixed and placed in a 100mL round-bottom flask, 50mL of methanol is added, and reflux reaction is carried out at 80℃ for 18h, after the reaction is completed, the pH is adjusted to 5-6 with a 40% mass fraction sodium hydroxide solution, and a methyl benzoate-2-sodium sulfonate solution is obtained.

[0115] (II) Hydroxylamine hydrochloride and sodium hydroxide were weighed in a molar ratio of 1.25:2.25, and hydroxylamine hydrochloride and sodium hydroxide were dissolved in 30 mL of methanol respectively, and then ultrasonic dispersion was performed for dissolution, and then the mixture was stirred in an ice water bath for 1 h to allow the hydroxylamine to be fully dissociated, and then the obtained methyl phenylacetate-2-sodium sulfonate solution was added, and the reaction was performed at 60°C for 6 h to obtain sodium phenylhydroxamic acid-2-sodium sulfonate.

[0116] (III) The solution was acidified with concentrated sulfuric acid to adjust the pH to 5-6, and then filtered to obtain white solid as crude phenylhydroxamic acid-2-sulfonic acid, which was dispersed in ethyl acetate, filtered with a sand core funnel to remove ethyl acetate, dried, and ground to obtain a relatively pure phenylhydroxamic acid-2-sulfonic acid product.

[0117] The collector prepared in this example was also subjected to the test of Example 1, and the results were basically consistent. Due to the limited space, they are not listed one by one.

[0118] Comparative Example 1

[0119] The efficient separation method of ilmenite in this comparative example was the same as that in Example 1, except that in step (1), the slurry was not subjected to plasma treatment.

[0120] Comparative Example 2

[0121] The efficient separation method of ilmenite in this comparative example was the same as that in Example 1, except that in step (2), the oxidized tamarind gum was replaced by tamarind gum with a molecular weight of 500,000.

[0122] Comparative Example 3

[0123] The efficient separation method of ilmenite in this comparative example was the same as that in Example 1, except that in step (b), the power in the plasma treatment was 150 W, and the treatment time was 15 min.

[0124] Comparative Example 4

[0125] The efficient separation method of ilmenite in this comparative example was the same as that in Example 1, except that in step (b), the flow rate of the treatment gas was 250 mL / min.

[0126] Comparative Example 5

[0127] The efficient separation method of ilmenite in this comparative example was the same as that in Example 1, except that the collector was 2-sulfobenzoic acid.

[0128] Test Example 1

[0129] The ilmenite ore with grade of 11.86% was separated by the method of example 1-3 and comparative example 1-5 respectively, the ore pulp of 1.5L was treated, the first and second flotation time was same, both were 3min, the results were shown in table 1.

[0130] Table 1

[0131]

[0132] The data results of example 1 and example 2 and 3 showed that the lower the power and the shorter the time of the plasma on the ilmenite, the smaller the surface oxidation degree and the content of Fe 3+ of the mineral, the smaller the difference between the surface of the target mineral and the gangue mineral; the greater the power and the longer the time, the greater the surface oxidation degree of the mineral, the enhanced hydrophilicity of the surface of the target mineral, and the grade and yield of the flotation concentrate were reduced.

[0133] The comparison of example 1 and comparative example 1 showed that the plasma pretreatment could effectively change the properties of the mineral surface, and improve the recovery rate and grade of the target mineral.

[0134] The results of example 1 and comparative example 2 showed that the small molecule oxidized tianjiaojian glue had more significant selective inhibition effect on the gangue mineral.

[0135] The results of example 1 and comparative example 3 and 4 showed that the plasma treatment tianjiaojian glue for too long time and the large gas flow were not conducive to control the process of tianjiaojian glue oxidation and decomposition, so that the inhibition performance was reduced.

[0136] The results of example 1 and comparative example 5 showed that the collector of the application had better flotation performance.

[0137] Test example 2

[0138] The ilmenite ore with grade of 11.86% was separated by the method of example 1-3 and comparative example 1-5 respectively, the ore pulp of 1.5L was treated, the first and second flotation time was same, both were 3min, only the amount of the collector was changed, the TiO2 grade and recovery rate in the concentrate under different amount of the collector were investigated, the results were shown in table 2.

[0139] Table 2

[0140]

[0141]

[0142] The TiO2 grade and recovery rate in the concentrate obtained by flotation under different collector dosages are investigated, and results show that the optimal dosage of the collector in the application is 500 g / t, and with the increase of the collector dosage, the yield of the ilmenite concentrate increases, but the grade and recovery rate decrease, which shows that the dosage of the collector in the application is low.

[0143] The above merely describes a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered in the protection scope of the present application.

Claims

1. A method for the pretreatment of minerals in conjunction with a separation process of flotation reagents, characterized by, The method comprises the following steps: (1) subjecting the raw ore slurry to plasma treatment to obtain treated ore slurry; (2) adding oxidized sesbania gum and a collector to the treated ore slurry, performing first-time flotation to obtain rough concentrate, and performing second-time flotation on the rough concentrate to obtain ilmenite concentrate; The structure of the collector is as follows:

2. A process for the pre-treatment of minerals in conjunction with a separation process of a flotation reagent according to claim 1, characterized in that, In step (1), the power in the plasma treatment is 100-200 W, and the treatment time is 3-6 min.

3. A process for the pre-treatment of minerals in conjunction with a separation process of a flotation reagent according to claim 1, characterized in that, In step (1), the plasma treatment uses plasma treatment gas, and the treatment gas flow rate is 300-500 mL / min.

4. A process for the pre-treatment of a mineral according to any one of claims 1 to 3, characterized in that, In step (2), the oxidized sesbania gum is prepared by the following method: (a) dispersing sesbania gum with anhydrous ethanol, adding water, stirring uniformly, adjusting the pH value to 8 with an alkali solution to obtain slurry; (b) subjecting the slurry to plasma treatment, precipitating with 60-80% (volume fraction) ethanol aqueous solution to obtain precipitate; (c) sequentially performing recrystallization, drying and crushing treatment on the precipitate to obtain oxidized sesbania gum.

5. A process for the pre-treatment of minerals in conjunction with a separation process of a flotation reagent according to claim 4, characterized by, In step (a), the viscosity-average molecular weight of the sesbania gum is 1-1.1 million.

6. A process for the pre-treatment of minerals in conjunction with a separation process of a flotation reagent as claimed in claim 4, characterized in that, In step (b), the power in the plasma treatment is 200-500 W, and the treatment time is 5-10 min.

7. A process for the pre-treatment of a mineral according to any one of claims 1 to 3, characterized in that, In step (2), the addition amount of the oxidized sesbania gum is 200-300 g / t.

8. A process for the pre-treatment of a mineral according to any one of claims 1 to 3, characterized in that, The collector is prepared by the following method: (I) mixing 2-sulfobenzene acetic acid and methanol to perform esterification reaction, adjusting the pH value to weak acidity after the reaction is completed to obtain ester compound; (II) dissolving hydroxylamine salt and alkali in methanol, ultrasonically dispersing and dissolving, reacting under ice water bath condition to obtain free hydroxylamine, then adding the ester compound and heating to perform hydroximic reaction, adjusting the pH value, filtering and drying to obtain the collector.

9. A process for the pre-treatment of minerals in conjunction with a separation process of a flotation reagent according to claim 8, characterized by, In step (I), the esterification reaction temperature is 60-80℃, and the pH value is adjusted to 5-6.

10. A process for the pre-treatment of minerals in conjunction with a separation process of a flotation reagent according to claim 8, characterized by, In step (II), the hydroxylamine salt is one of hydroxylamine hydrochloride, hydroxylamine carbonate and hydroxylamine sulfate.

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