Separation process of mineral pretreatment method cooperating with flotation reagent

Abstract

The invention relates to a mineral pretreatment method cooperating with a separation process of a flotation reagent, belongs to the technical field of flotation, and is used for solving at least one of the problems of poor ilmenite collecting effect, poor selectivity, large reagent dosage during flotation and the like in a one-rough one-fine flotation method in the prior art. According to the method, firstly, raw ore is subjected to plasma treatment, impurities on the surface of the ilmenite are stripped, part of Fe < 2 + > on the surface of the ilmenite is oxidized into Fe < 3 + > by adjusting the proportion and flow of argon and oxygen, and the surface property difference of the ilmenite and forsterite is improved. In addition, the oxidized sesbania gum is more favorable for being combined with calcium and magnesium active sites on the surface of the gangue mineral, and meanwhile, the oxidized sesbania gum can be uniformly adsorbed on the surface of the gangue mineral, so that the hydrophilicity of the gangue mineral is further improved, and the hydrophilic-hydrophobic difference between the target mineral and the surface of the gangue mineral is enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of ilmenite, and in particular to a separation process of a mineral pretreatment method and a flotation agent. Background Art

[0002] my country has rich reserves of titanium resources, accounting for about 28% of the world's total reserves. Ilmenite is the main source of titanium resources in my country, mainly distributed in Panzhihua and Xichang areas of Sichuan. my country's ilmenite resources have the characteristics of "more poor ores, fewer rich ores, and fine particle size", making it difficult to achieve efficient sorting, restricting the further utilization of titanium resources. Flotation is an important method for achieving efficient sorting of fine-grained mineral resources. Due to the similar surface properties of the target minerals and gangue minerals, traditional fatty acid collectors have good collection properties, but it is difficult to achieve efficient separation of the two. Arsonic acid and phosphoric acid collectors have certain collectors and selectivities, but there are problems such as environmental pollution. Therefore, it is necessary to develop environmentally friendly and highly selective flotation collectors.

[0003] In recent years, hydroxamic acid collectors have attracted extensive attention in ilmenite flotation processes due to their excellent flotation performance. However, the dosage of hydroxamic acid collectors in the existing coarse-fine flotation method is relatively large, and the selective separation ability for low-grade ilmenite and gangue minerals is limited. Summary of the invention

[0004] In view of the above analysis, the present invention aims to provide a mineral pretreatment method and a separation process of a flotation agent to solve at least one of the problems of the prior art one-rough-one-fine flotation method, such as poor ilmenite capture effect, poor selectivity, and large amount of agent used during flotation.

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

[0006] (1) subjecting raw ore pulp to plasma treatment to obtain treated ore pulp;

[0007] (2) adding sesbania gum and a collector to the treated slurry, performing a first flotation to obtain a coarse concentrate, and performing a second flotation on the coarse concentrate to obtain an ilmenite concentrate;

[0008] Wherein, the structural formula of the collector is as follows:

[0009]

[0010] Furthermore, in step (1), the power of the plasma treatment is 100 to 200 W, and the treatment time is 3 to 6 minutes.

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

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

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

[0014] (b) treating the slurry with plasma, adding 60-80% by volume ethanol aqueous solution to precipitate, thereby obtaining a precipitate;

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

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

[0017] Furthermore, in step (b), the power of the plasma treatment is 200 to 500 W, and the treatment time is 5 to 10 minutes.

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

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

[0020] (I) mixing 2-sulfophenylacetic acid and methanol for esterification reaction, and adjusting the pH to a weak acidic state after the reaction to obtain an ester compound;

[0021] (II) dissolving hydroxylamine salt and alkali in methanol, dispersing and dissolving by ultrasonication, reacting in an ice-water bath to obtain free hydroxylamine, adding the ester compound, heating to carry out hydroxylamine reaction, adjusting pH, filtering, and drying to obtain the collector.

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

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

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

[0025] (1) The method of the present invention first uses plasma treatment on the raw ore to remove impurities on the surface of the ilmenite, and then adjusts the ratio and flow rate of argon and oxygen to remove part of the Fe 2+ Oxidized to Fe3+ , improve the difference in surface properties between ilmenite and forsterite. In addition, the use of sesbania gum in the present invention is more conducive to combining with the calcium and magnesium active sites on the surface of the gangue mineral, and the sesbania gum can be uniformly adsorbed on the surface of the gangue mineral, further improving the hydrophilicity of the gangue mineral, and enhancing the difference in hydrophilicity and hydrophobicity between the target mineral and the gangue mineral surface; and on the surface of the target mineral, compared with the inhibitor with a large molecular weight, the sesbania gum with unstable adsorption is easier to be expelled by the collector molecules, which is conducive to the selective adsorption of the subsequent collector molecules on the surface of the ilmenite, while reducing the agent consumption of sesbania gum;

[0026] (2) In the present invention, plasma treatment is used to oxidize and decompose sesbania gum, and the molecular weight of oxidized sesbania gum is a viscosity average molecular weight of 100,000 to 120,000. Oxidized sesbania gum has carboxyl groups, which are easier to react with the surface of gangue minerals and easier to be displaced by collector molecules, which is conducive to the subsequent selective adsorption of collector molecules on the surface of ilmenite, while reducing the reagent consumption of oxidized sesbania gum.

[0027] In the present invention, the above-mentioned technical solutions can also be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description, and some advantages can become obvious from the description, or can be understood by practicing the present invention. The purpose and other advantages of the present invention can be achieved and obtained through the contents particularly pointed out in the description and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The drawings are only for the purpose of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference symbols denote like components throughout the drawings.

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

[0030] Figure 2 This is the nuclear magnetic resonance image of the collector prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0031] The preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, wherein the accompanying drawings 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 used to limit the scope of the present invention.

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

[0033] (1) subjecting raw ore pulp to plasma treatment to obtain treated ore pulp;

[0034] (2) adding sesbania gum and a collector to the treated slurry, performing a first flotation to obtain a coarse concentrate, and performing a second flotation on the coarse concentrate to obtain an ilmenite concentrate;

[0035] Wherein, the structural formula of the collector is as follows:

[0036]

[0037] Compared with the prior art, the method of the present invention firstly treats the raw ore with plasma to remove impurities on the surface of ilmenite, and then removes part of the Fe 2+ Oxidized to Fe 3+ , improve the difference in surface properties between ilmenite and forsterite. In addition, the use of sesbania gum in the present invention is more conducive to combining with calcium and magnesium active sites on the surface of gangue minerals, and sesbania 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 surface of gangue minerals; and on the surface of the target mineral, compared with inhibitors with large molecular weight, sesbania gum with unstable adsorption is easier to be expelled by collector molecules, which is conducive to the selective adsorption of subsequent collector molecules on the surface of ilmenite, while reducing the agent consumption of sesbania gum.

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

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

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

[0041] It should be noted that if there is only argon gas in the treatment gas and no oxygen, the plasma cleaning machine only has the effect of cleaning surface impurities. When there is oxygen, the surface oxidation of ilmenite can be made more hydrophilic, while the divalent iron ions are oxidized to trivalent iron ions, which is more conducive to the adsorption of collectors, and the surface oxidation of forsterite (gangue) is more hydrophilic, and the surface properties of the two minerals obtained after the final pretreatment are more different, which is conducive to flotation. The volume ratio of plasma treatment gas selection of the present invention is conducive to ensuring that ilmenite is not over-oxidized, so that its surface oxidation degree is too large, and hydrophilicity is enhanced. If over-oxidation can make both mineral surfaces have strong hydrophilicity, the difference is reduced, and therefore the ratio of oxygen introduced is controlled.

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

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

[0044] (b) treating the slurry with plasma, adding 60-80% by volume ethanol aqueous solution to precipitate, thereby obtaining a precipitate;

[0045] (c) sequentially subjecting the precipitate to recrystallization, drying and pulverization to obtain oxidized sesbania gum.

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

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

[0048] In a specific embodiment, in step (b), the power of the plasma treatment is 200-500 W, for example, 200 W, 250 W, 300 W, 350 W, 400, 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 a specific embodiment, in step (b), the plasma treatment adopts a plasma treatment gas, the plasma treatment gas is oxygen, 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, 500 mL / min.

[0050] In the present invention, plasma treatment is used to oxidize and decompose sesbania gum, and the molecular weight of the oxidized sesbania gum is a viscosity-average molecular weight of 100,000 to 120,000. The oxidized sesbania gum has a carboxyl group, which is easier to react with the surface of gangue minerals, and is easier to be displaced by collector molecules on the surface of the target mineral, which is conducive to the subsequent selective adsorption of collector molecules on the surface of ilmenite, and at the same time reduces the reagent consumption of the oxidized sesbania gum.

[0051] In a specific embodiment, in step (2), the amount of oxidized sesbania gum added 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; the amount of collector added 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 frother are added during the first flotation and the second flotation.

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

[0054] Specifically, the amount of the foaming agent added is 40.1 g / t. Preferably, the foaming agent is methyl isobutyl carbinol.

[0055] Specifically, the two flotation times are the same.

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

[0057] (I) mixing 2-sulfophenylacetic acid and methanol for esterification reaction, and adjusting the pH to a weak acidic state after the reaction to obtain an ester compound;

[0058] (II) dissolving hydroxylamine salt and alkali in methanol, dispersing and dissolving by ultrasonication, reacting in an ice-water bath to obtain free hydroxylamine, adding the ester compound, heating to carry out hydroxylamine reaction, adjusting pH, filtering, and drying to obtain the collector.

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

[0060]

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

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

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

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

[0065] In a 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 invention is prepared by esterification reaction and hydroxyoximation reaction, and the preparation method is simple and easy to operate.

[0068] The present invention combines a highly selective bifunctional collector. The polar group of the collector is composed of two adjacent sulfonic acid groups and hydroxyoxime groups, wherein the sulfonic acid group and the hydroxyoxime group can each form a ring with the active site on the mineral surface, or can form a stable polycyclic ring with the same active site on the mineral surface, which can significantly enhance the capture 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 molecule, improving the concentrate grade and recovery rate, and the bifunctional collector can also reduce the amount of the collector.

[0069] The raw ore treated in the present invention is calcium-magnesium-rich ilmenite, wherein the grade of TiO2 is ≤12%.

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

[0071] The technical solution of the present invention is further explained below in conjunction with specific embodiments. All raw materials in the present invention are commercially available raw materials.

[0072] The technical solution of the present invention is further explained below in conjunction with specific embodiments.

[0073] Example 1

[0074] An efficient separation method for ilmenite comprises the following steps:

[0075] (1) treating the raw ore pulp with a mass concentration of 40% by plasma, wherein the power of the plasma treatment is 150 W, the treatment time is 6 min, the plasma treatment uses a plasma treatment gas, and the plasma treatment gas is a mixture of argon and oxygen in a volume ratio of 2:3, and the treatment gas flow rate is 400 mL / min, to obtain a treated ore pulp;

[0076] (2) The treated pulp is transferred to the first flotation tank, 200 g / t of sesbania gum and 300 g / t of collector are added, and the first flotation is performed to obtain a coarse concentrate. The coarse concentrate is subjected to a second flotation to obtain an ilmenite concentrate, wherein sulfuric acid and 40.1 g / t of frother are also added during the first and second flotations. Sulfuric acid is added during the first flotation to make the pulp pH = 4.5, and sulfuric acid is added during the second flotation to make the pulp pH = 3.5.

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

[0078] (a) dispersing sesbania gum with a molecular weight of 1 million with anhydrous ethanol, adding water, stirring evenly, and adjusting the pH value to 8 with an alkaline solution to obtain a slurry with a mass fraction of 2%;

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

[0080] (c) sequentially subjecting the precipitate to recrystallization, drying and pulverization to obtain oxidized sesbania gum with a molecular weight of 100,000.

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

[0082]

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

[0084] (I) 2-sulfophenylacetic acid and methanol were weighed at a molar ratio of 1:70 and mixed in a 100 mL round-bottom flask, and refluxed at 60° C. for 18 h. After the reaction, the pH was adjusted to 5-6 with a 40% sodium hydroxide solution to obtain a sodium methyl phenylacetate-2-sulfonate solution.

[0085] (II) Hydroxylamine hydrochloride and sodium hydroxide were weighed at a molar ratio of 1.5:2.5, and the hydroxylamine hydrochloride and sodium hydroxide were respectively dissolved in 30 mL of methanol, and ultrasonically dispersed and dissolved. After mixing, the mixture was stirred in an ice-water bath for 1 h to fully free the hydroxylamine, and then the obtained sodium methyl phenylacetate-2-sulfonate solution was added, and the temperature was raised to 50° C. to react for 6 h to obtain sodium phenylethylhydroxamate-2-sulfonate.

[0086] (III) Acidifying the solution with concentrated sulfuric acid to adjust the pH to 5-6, filtering, and obtaining a white solid as a crude product of phenylethylhydroxamic acid-2-sulfonic acid. Dispersing the crude product of phenylethylhydroxamic acid-2-sulfonic acid in ethyl acetate, filtering with a sand core funnel to remove the ethyl acetate, drying, and grinding to obtain a relatively pure phenylethylhydroxamic acid-2-sulfonic acid product.

[0087] The mass spectrum (M+Na) of the collector prepared in this example is as follows: Figure 1 As shown, the nuclear magnetic resonance image of the collector prepared in this embodiment is as follows Figure 2 shown.

[0088] Example 2

[0089] An efficient separation method for ilmenite comprises the following steps:

[0090] (1) treating the raw ore pulp with a mass concentration of 30% by plasma, wherein the power of the plasma treatment is 100 W, the treatment time is 4.5 min, the plasma treatment uses a plasma treatment gas, and the plasma treatment gas is a mixture of argon and oxygen in a volume ratio of 2:3, and the treatment gas flow rate is 300 mL / min, to obtain a treated ore pulp;

[0091] (2) The treated pulp is transferred to the first flotation tank, 250 g / t of sesbania gum and 450 g / t of collector are added, and the first flotation is performed to obtain a coarse concentrate. The coarse concentrate is subjected to a second flotation to obtain an ilmenite concentrate, wherein sulfuric acid and 42 g / t of frother are also added during the first and second flotations. Sulfuric acid is added during the first flotation to make the pulp pH = 4, and sulfuric acid is added during the second flotation to make the pulp pH = 3.

[0092] The preparation method of oxidized sesbania gum of the present embodiment is as follows:

[0093] (a) dispersing sesbania gum with a molecular weight of 1.05 million with anhydrous ethanol, adding water, stirring evenly, and adjusting the pH value to 8 with an alkaline solution to obtain a slurry with a mass fraction of 2%;

[0094] (b) treating the slurry with plasma, wherein the power of the plasma treatment is 350 W, the treatment time is 7.5 min, the plasma treatment uses a plasma treatment gas, the plasma treatment gas is oxygen, the treatment gas flow rate is 400 mL / min, and a 70% volume fraction of ethanol aqueous solution is added for precipitation to obtain a precipitate;

[0095] (c) sequentially subjecting the precipitate to recrystallization, drying and pulverization to obtain oxidized sesbania gum with a molecular weight of 110,000.

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

[0097]

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

[0099] (I) 2-sulfophenylacetic acid and methanol were weighed at a molar ratio of 1:76 and mixed in a 100 mL round-bottom flask, and refluxed at 70° C. for 18 h. After the reaction, the pH was adjusted to 5-6 with a 40% sodium hydroxide solution to obtain a sodium methyl phenylacetate-2-sulfonate solution.

[0100] (II) Hydroxylamine hydrochloride and sodium hydroxide were weighed in a molar ratio of 1:2, and the hydroxylamine hydrochloride and sodium hydroxide were respectively dissolved in 30 mL of methanol, and ultrasonically dispersed and dissolved. After mixing, the mixture was stirred in an ice-water bath for 1 h to fully free the hydroxylamine, and then the obtained sodium methyl phenylacetate-2-sulfonate solution was added, and the temperature was raised to 30° C. to react for 6 h to obtain sodium phenylethylhydroxamate-2-sulfonate.

[0101] (III) Acidifying the solution with concentrated sulfuric acid to adjust the pH to 5-6, filtering, and obtaining a white solid as a crude product of phenylethylhydroxamic acid-2-sulfonic acid. Dispersing the crude product of phenylethylhydroxamic acid-2-sulfonic acid in ethyl acetate, filtering with a sand core funnel to remove the ethyl acetate, drying, and grinding to obtain a relatively pure phenylethylhydroxamic acid-2-sulfonic acid product.

[0102] The collector prepared in this example was also tested in Example 1, and the results were basically the same. Due to limited space, they are not listed one by one.

[0103] Example 3

[0104] An efficient separation method for ilmenite comprises the following steps:

[0105] (1) treating the raw ore pulp with a mass concentration of 35% by plasma, wherein the power of the plasma treatment is 200 W, the treatment time is 3 min, the plasma treatment uses a plasma treatment gas, and the plasma treatment gas is a mixture of argon and oxygen in a volume ratio of 2:3, and the treatment gas flow rate is 500 mL / min, to obtain a treated ore pulp;

[0106] (2) The treated slurry is transferred to the first flotation tank, 300 g / t of sesbania gum and 600 g / t of collector are added, and the first flotation is performed to obtain a coarse concentrate. The coarse concentrate is subjected to a second flotation to obtain an ilmenite concentrate, wherein sulfuric acid and 45 g / t of frother are also added during the first and second flotations. 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 oxidized sesbania gum of the present embodiment is as follows:

[0108] (a) dispersing sesbania gum with a molecular weight of 1.1 million with anhydrous ethanol, adding water, stirring evenly, and adjusting the pH value to 8 with an alkaline solution to obtain a slurry with a mass fraction of 2%;

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

[0110] (c) sequentially subjecting the precipitate to recrystallization, drying and pulverization to obtain oxidized sesbania gum with a molecular weight of 120,000.

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

[0112]

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

[0114] (I) 2-sulfophenylacetic acid and methanol were weighed at a molar ratio of 1.2:80 and mixed in a 100 mL round-bottom flask, 50 mL of methanol was added, and the mixture was refluxed at 80° C. for 18 h. After the reaction was completed, the pH was adjusted to 5-6 with a 40% sodium hydroxide solution to obtain a sodium methyl phenylacetate-2-sulfonate solution.

[0115] (II) Hydroxylamine hydrochloride and sodium hydroxide were weighed at a molar ratio of 1.25:2.25, and the hydroxylamine hydrochloride and sodium hydroxide were respectively dissolved in 30 mL of methanol, and ultrasonically dispersed and dissolved. After mixing, the mixture was stirred in an ice-water bath for 1 h to fully free the hydroxylamine, and then the obtained sodium methyl phenylacetate-2-sulfonate solution was added, and the temperature was raised to 60° C. to react for 6 h to obtain sodium phenylethylhydroxamate-2-sulfonate.

[0116] (III) Acidifying the solution with concentrated sulfuric acid to adjust the pH to 5-6, filtering, and obtaining a white solid as a crude product of phenylethylhydroxamic acid-2-sulfonic acid. Dispersing the crude product of phenylethylhydroxamic acid-2-sulfonic acid in ethyl acetate, filtering with a sand core funnel to remove the ethyl acetate, drying, and grinding to obtain a relatively pure phenylethylhydroxamic acid-2-sulfonic acid product.

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

[0118] Comparative Example 1

[0119] The high-efficiency separation method of ilmenite in this comparative example is the same as that in Example 1, except that in step (1), the ore pulp is not subjected to plasma treatment.

[0120] Comparative Example 2

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

[0122] Comparative Example 3

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

[0124] Comparative Example 4

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

[0126] Comparative Example 5

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

[0128] Test Example 1

[0129] The methods of Examples 1-3 and Comparative Examples 1-5 were used to separate the actual ilmenite ore with a grade of 11.86%. The processed ore pulp was 1.5 L. The first flotation and the second flotation time were the same, both 3 minutes. The results are shown in Table 1.

[0130] Table 1

[0131]

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

[0133] Comparison of Example 1 with Comparative Example 1 shows that plasma pretreatment can 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 show that the small molecule sesbania gum oxide has a more significant selective inhibition effect on gangue minerals.

[0135] The results of Example 1 and Comparative Examples 3 and 4 show that the plasma treatment time of sesbania gum is too long and the large gas flow rate is not conducive to controlling the oxidation and decomposition process of sesbania gum, resulting in a decrease in its inhibition performance.

[0136] The results of Example 1 and Comparative Example 5 show that the collector of the present invention has better flotation performance.

[0137] Test Example 2

[0138] The methods of Examples 1-3 and Comparative Examples 1-5 were respectively used to separate the actual ilmenite ore with a grade of 11.86%. The processed ore pulp was 1.5L. The first flotation and second flotation times were the same, both 3 minutes. Only the amount of collector was changed. The flotation under different collector amounts was investigated to obtain the TiO2 grade and recovery rate in the concentrate. The results are shown in Table 2.

[0139] Table 2

[0140]

[0141]

[0142] The TiO2 grade and recovery rate in the flotation concentrate obtained under different collector dosages were investigated. The results showed that the optimal dosage of the collector in the present invention was 500 g / t. With the increase of the collector dosage, the yield of the ilmenite concentrate increased, but the grade and recovery rate decreased, which indicates that the dosage of the agent in the present invention is relatively low.

[0143] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A mineral pretreatment method and a separation process using a flotation agent, characterized in that: The steps include: (1) subjecting raw ore pulp to plasma treatment to obtain treated ore pulp; (2) adding sesbania gum and a collector to the treated slurry, performing a first flotation to obtain a coarse concentrate, and performing a second flotation on the coarse concentrate to obtain an ilmenite concentrate; Wherein, the structural formula of the collector is as follows:

2. The separation process of a mineral pretreatment method and a flotation agent according to claim 1 is characterized in that: In step (1), the power of the plasma treatment is 100 to 200 W, and the treatment time is 3 to 6 minutes.

3. The separation process of a mineral pretreatment method and a flotation agent according to claim 1, characterized in that: In step (1), the plasma treatment uses a plasma treatment gas, and the treatment gas flow rate is 300 to 500 mL / min.

4. A separation process of a mineral pretreatment method in combination with a flotation agent 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 evenly, and adjusting the pH value to 8 with an alkaline solution to obtain a slurry; (b) treating the slurry with plasma, adding 60-80% by volume ethanol aqueous solution to precipitate, thereby obtaining a precipitate; (c) sequentially subjecting the precipitate to recrystallization, drying and pulverization to obtain oxidized sesbania gum.

5. The separation process of a mineral pretreatment method and a flotation agent according to claim 4 is characterized in that: In step (a), the viscosity average molecular weight of sesbania gum is 1 to 1.1 million.

6. The separation process of a mineral pretreatment method and flotation reagent according to claim 4 is characterized in that: In step (b), the power of the plasma treatment is 200-500W, and the treatment time is 5-10 minutes.

7. A separation process of a mineral pretreatment method in conjunction with a flotation agent according to any one of claims 1 to 3, characterized in that: In step (2), the amount of oxidized sesbania gum added is 200-300 g / t.

8. A separation process of a mineral pretreatment method in conjunction with a flotation agent according to any one of claims 1 to 3, characterized in that: The collector is prepared by the following method: (I) mixing 2-sulfophenylacetic acid and methanol for esterification reaction, and adjusting the pH to a weak acidic state after the reaction to obtain an ester compound; (II) dissolving hydroxylamine salt and alkali in methanol, dispersing and dissolving by ultrasonication, reacting in an ice-water bath to obtain free hydroxylamine, adding the ester compound, heating to carry out hydroxylamine reaction, adjusting pH, filtering, and drying to obtain the collector.

9. The separation process of a mineral pretreatment method and flotation reagent according to claim 8, characterized in that: In step (I), the temperature of the esterification reaction is 60-80° C., and the pH value is adjusted to 5-6.

10. The separation process of a mineral pretreatment method and a flotation agent according to claim 8, characterized in that: In step (II), the hydroxylamine salt is one of hydroxylamine hydrochloride, hydroxylamine carbonate or hydroxylamine sulfate.

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