Fluorite flotation sodium petroleum sulfonate collector and preparation method and application method thereof

Abstract

The application discloses a fluorite flotation petroleum sulfonate sodium collector, which comprises petroleum sulfonate sodium and non-polar oil, and the molar ratio of the non-polar oil to the petroleum sulfonate sodium is 3.33-5.67; the petroleum sulfonate sodium comprises raw oil and active substance; the molecular weight of the petroleum sulfonate sodium is 500-750; the molecular weight of the raw oil is 350-450; the content of the active substance is 35%-60%; the raw oil comprises aromatic hydrocarbon; the content of the aromatic hydrocarbon is 10%-31%; the molar ratio of the aromatic hydrocarbon to sulfur trioxide is 2.4-5; the aromatic hydrocarbon comprises benzene ring hydrocarbon and naphthalene ring hydrocarbon; the content of the benzene ring hydrocarbon is 5%-11%; and the content of the naphthalene ring hydrocarbon is 5%-5.2%; and the non-polar oil is kerosene, dodecane or monomethylnaphthalene; in the preparation and application, the dissolved petroleum sulfonate sodium solution is first placed into a volumetric flask, then the non-polar oil is placed into the volumetric flask, the volume is fixed, and the solution is poured into a beaker, and then ultrasonic emulsification is carried out to obtain the petroleum sulfonate sodium collector. The petroleum sulfonate sodium collector prepared by the design is high in efficiency and resistant to low temperature.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation technology, and in particular to a sodium petroleum sulfonate collector for fluorite flotation, its preparation method, and its application method. Background Technology

[0002] Fluorite's main chemical component is calcium fluoride, and it often occurs in association with quartz, calcite, barite, and metal sulfide minerals. Due to its unique chemical properties, fluorine atoms are widely used in emerging and traditional industries such as metallurgy, new energy, chemicals, nuclear energy, building materials, and pesticides.

[0003] In the beneficiation process of fluorite, flotation is currently the main beneficiation method for separating fluorite from gangue minerals. Fluorite collectors can be classified into fatty acid collectors, modified fatty acid collectors, combined collectors, and novel collectors. Among these collectors, commonly used ones include anionic oxyacids, cationic amines, and ionic variable amphoteric collectors. However, these collectors have certain shortcomings in terms of low-temperature resistance. A survey conducted by Feng Ansheng et al. on the "three rates" of fluorite resource development and utilization across the country found that the beneficiation recovery rate in North China is generally lower than that in South China. Annual economic losses exceeding 100 million yuan are caused by low recovery rates. Besides differences in beneficiation processes and ore properties, the main reason is the poor low-temperature resistance of the oleic acid series collectors commonly used in beneficiation plants, resulting in low separation recovery rates (approximately 8% lower in winter than in summer). Heating the slurry for flotation not only causes inconvenience in production management but also increases energy consumption. Therefore, how to improve the flotation effect of collectors at room temperature or even low temperature has become an important issue in fluorite flotation. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects and problems of inefficiency and poor low-temperature resistance in the existing technology, and to provide a highly efficient and low-temperature resistant sodium petroleum sulfonate collector for fluorite flotation, as well as its preparation method and application method.

[0005] To achieve the above objectives, the technical solution of the present invention is: a sodium petroleum sulfonate collector for fluorite flotation, comprising sodium petroleum sulfonate and non-polar oil, wherein the molar ratio of the non-polar oil to the sodium petroleum sulfonate is 3.33–5.67, the sodium petroleum sulfonate comprises feedstock oil and active ingredient, the molecular weight of the sodium petroleum sulfonate is 500–750, the molecular weight of the feedstock oil is 350–450, the content of the active ingredient is 35%–60%, the feedstock oil comprises aromatics, the content of the aromatics is 10%–31%, the feedstock oil is sulfonated with sulfur trioxide, the molar ratio of the aromatics to sulfur trioxide in the feedstock oil is 2.4–5, the aromatics comprise benzene ring hydrocarbons and naphthalene ring hydrocarbons, the content of the benzene ring hydrocarbons is 5%–11%, and the content of the naphthalene ring hydrocarbons is 5%–5.2%.

[0006] The non-polar oil is kerosene, dodecane, or monomethylnaphthalene.

[0007] The sodium petroleum sulfonate is sodium alkylbenzene sulfonate, which is the sodium salt of a straight-chain alkylbenzene sulfonic acid consisting of 14 to 18 carbon atoms, with the structural formula CH3(CH2)nSO3Na (n=13 to 17).

[0008] A method for preparing a sodium petroleum sulfonate collector for fluorite flotation, the method comprising the following steps:

[0009] S1. Dissolve sodium petroleum sulfonate in water;

[0010] S2. First, put the sodium petroleum sulfonate solution into a volumetric flask, then put the non-polar oil into the volumetric flask, then make up to volume and pour into a beaker;

[0011] S3. The sodium petroleum sulfonate collector is obtained by oscillating in an ultrasonic oscillator for more than 9 minutes.

[0012] In step S1, the sodium petroleum sulfonate is obtained by first sulfonating C14-C18 straight-chain alkanes in petroleum products to obtain oil-soluble sulfonic acid, then neutralizing the acidity of the oil-soluble sulfonic acid with sodium hydroxide to obtain crude sodium petroleum sulfonate, then extracting the crude sodium petroleum sulfonate from the neutral oil with low-carbon alcohol water, and then obtaining refined sodium petroleum sulfonate through a series of treatments such as dehydration, decolorization, deoiling, water washing, and concentration.

[0013] In step S2, the non-polar oil is kerosene, dodecane, or monomethylnaphthalene.

[0014] A method for applying sodium petroleum sulfonate collector in fluorite flotation, the method comprising the following steps:

[0015] S1. Fluorite is mixed with water to form a slurry and then kept warm;

[0016] S2. First, dissolve sodium petroleum sulfonate in water, then put the sodium petroleum sulfonate solution into a volumetric flask, then put the non-polar oil into the volumetric flask, then make up to volume and pour into a beaker, and then perform ultrasonic emulsification to obtain sodium petroleum sulfonate collector.

[0017] S3. First, add the slurry to the flotation machine and adjust the slurry. Then, add sodium hydroxide to adjust the pH value. Next, add sodium petroleum sulfonate collector, stir, aerate, and then scrape the foam to obtain the frothy product, which is fluorite concentrate.

[0018] In step S2, the non-polar oil is kerosene, dodecane, or monomethylnaphthalene.

[0019] In step S2, sodium petroleum sulfonate collector is obtained by oscillating in an ultrasonic oscillator for more than 9 minutes.

[0020] In step S2, the sodium petroleum sulfonate is obtained by first sulfonating C14-C18 straight-chain alkanes in petroleum products to obtain oil-soluble sulfonic acid, then neutralizing the acidity of the oil-soluble sulfonic acid with sodium hydroxide to obtain crude sodium petroleum sulfonate, then extracting the crude sodium petroleum sulfonate from the neutral oil with low-carbon alcohol water, and then obtaining refined sodium petroleum sulfonate through a series of treatments such as dehydration, decolorization, deoiling, water washing, and concentration.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] 1. In the present invention, a sodium petroleum sulfonate collector for fluorite flotation, its preparation method and application method, the prepared sodium petroleum sulfonate collector can have a good collection effect at room temperature or even low temperature; at the same time, the active substances in the sodium petroleum sulfonate collector have a good synergistic flotation effect with non-polar oil, have strong chemical interaction with fluorite, and are less affected by changes in the pulp.

[0023] 2. In the present invention, a sodium petroleum sulfonate collector for fluorite flotation, its preparation method, and its application method, the molecular weight of the sodium petroleum sulfonate is 500-750, and the molecular weight of the feed oil is 350-450, resulting in the optimal number of sulfonate groups and the highest degree of sulfonation of the sodium petroleum sulfonate; the active ingredient content is 35%-60%, resulting in the best flotation effect of the collector on fluorite mineral particles; the aromatic hydrocarbon content is 10%-31%, the benzene ring hydrocarbon content is 5%-11%, and the naphthalene ring hydrocarbon content is 5%-5.2%, resulting in good collection effect of the collector during the flotation process; the molar ratio of aromatic hydrocarbons to sulfur trioxide is 2.4-5, resulting in good hydrophobicity of the collector; the molar ratio of non-polar oil to sodium petroleum sulfonate is 3.33-5.67, which not only results in good flotation effect of the collector but also good hydrophobicity of the collector.

[0024] 3. In the present invention, a sodium petroleum sulfonate collector for fluorite flotation, its preparation method and application method, the non-polar oil is kerosene, dodecane or methylnaphthalene, which not only has a good synergistic effect, but also makes the collector have good hydrophobic properties; the sodium petroleum sulfonate is sodium alkylbenzene sulfonate, which makes the synergistic effect between sodium petroleum sulfonate and non-polar oil good. Detailed Implementation

[0025] The present invention will be further described in detail below with reference to specific embodiments.

[0026] A sodium petroleum sulfonate collector for fluorite flotation comprises sodium petroleum sulfonate and non-polar oil, wherein the molar ratio of the non-polar oil to the sodium petroleum sulfonate is 3.33–5.67, the sodium petroleum sulfonate comprises feedstock oil and active ingredient, the molecular weight of the sodium petroleum sulfonate is 500–750, the molecular weight of the feedstock oil is 350–450, the content of the active ingredient is 35%–60%, the feedstock oil comprises aromatics, the content of the aromatics is 10%–31%, the feedstock oil is sulfonated with sulfur trioxide, the molar ratio of the aromatics to sulfur trioxide in the feedstock oil is 2.4–5, the aromatics comprise benzene ring hydrocarbons and naphthalene ring hydrocarbons, the content of the benzene ring hydrocarbons is 5%–11%, and the content of the naphthalene ring hydrocarbons is 5%–5.2%.

[0027] The non-polar oil is kerosene, dodecane, or monomethylnaphthalene.

[0028] The sodium petroleum sulfonate is sodium alkylbenzene sulfonate, which is the sodium salt of a straight-chain alkylbenzene sulfonic acid consisting of 14 to 18 carbon atoms, with the structural formula CH3(CH2)nSO3Na (n=13 to 17).

[0029] A method for preparing a sodium petroleum sulfonate collector for fluorite flotation, the method comprising the following steps:

[0030] S1. Dissolve sodium petroleum sulfonate in water;

[0031] S2. First, put the sodium petroleum sulfonate solution into a volumetric flask, then put the non-polar oil into the volumetric flask, then make up to volume and pour into a beaker;

[0032] S3. The sodium petroleum sulfonate collector is obtained by oscillating in an ultrasonic oscillator for more than 9 minutes.

[0033] In step S1, the sodium petroleum sulfonate is obtained by first sulfonating C14-C18 straight-chain alkanes in petroleum products to obtain oil-soluble sulfonic acid, then neutralizing the acidity of the oil-soluble sulfonic acid with sodium hydroxide to obtain crude sodium petroleum sulfonate, then extracting the crude sodium petroleum sulfonate from the neutral oil with low-carbon alcohol water, and then obtaining refined sodium petroleum sulfonate through a series of treatments such as dehydration, decolorization, deoiling, water washing, and concentration.

[0034] In step S2, the non-polar oil is kerosene, dodecane, or monomethylnaphthalene.

[0035] A method for applying sodium petroleum sulfonate collector in fluorite flotation, the method comprising the following steps:

[0036] S1. Fluorite is mixed with water to form a slurry and then kept warm;

[0037] S2. First, dissolve sodium petroleum sulfonate in water, then put the sodium petroleum sulfonate solution into a volumetric flask, then put the non-polar oil into the volumetric flask, then make up to volume and pour into a beaker, and then perform ultrasonic emulsification to obtain sodium petroleum sulfonate collector.

[0038] S3. First, add the slurry to the flotation machine and adjust the slurry. Then, add sodium hydroxide to adjust the pH value. Next, add sodium petroleum sulfonate collector, stir, aerate, and then scrape the foam to obtain the frothy product, which is fluorite concentrate.

[0039] In step S2, the non-polar oil is kerosene, dodecane, or monomethylnaphthalene.

[0040] In step S2, sodium petroleum sulfonate collector is obtained by oscillating in an ultrasonic oscillator for more than 9 minutes.

[0041] In step S2, the sodium petroleum sulfonate is obtained by first sulfonating C14-C18 straight-chain alkanes in petroleum products to obtain oil-soluble sulfonic acid, then neutralizing the acidity of the oil-soluble sulfonic acid with sodium hydroxide to obtain crude sodium petroleum sulfonate, then extracting the crude sodium petroleum sulfonate from the neutral oil with low-carbon alcohol water, and then obtaining refined sodium petroleum sulfonate through a series of treatments such as dehydration, decolorization, deoiling, water washing, and concentration.

[0042] The principle of this invention is explained as follows:

[0043] Sodium petroleum sulfonate has a long history of use as a collector in flotation, and has been widely applied in the froth flotation of andalusite group minerals, mica-quartz silicate minerals, and iron-manganese minerals, exhibiting excellent low-temperature resistance. The superior performance of sodium petroleum sulfonate as a flotation collector is inextricably linked to its composition and structure. However, due to the complexity of the composition and structure of synthetic feedstock oils and differences in sulfonation processes, the flotation behavior of different types of sodium petroleum sulfonate varies significantly. Therefore, a sodium petroleum sulfonate collector that is both highly efficient and resistant to low temperatures for fluorite was developed, taking into account the hydrocarbon content in the feedstock oil, different degrees of sulfonation, and the synergistic effect between different types of hydrocarbon sulfonates and non-polar oils.

[0044] The change in the molecular weight of sodium petroleum sulfonate reflects the change in the content of sulfonic acid groups in the collector. The more sulfonic acid groups, the larger the molecular weight of sodium petroleum sulfonate, and the higher the degree of sulfonation of the flotation collector; conversely, the fewer sulfonic acid groups, the smaller the molecular weight of sodium petroleum sulfonate, and the lower the degree of sulfonation of the flotation collector. For sodium petroleum sulfonate, when used as a collector in the flotation process, the main reactive group is the sulfonate group. Therefore, the number of sulfonate groups in the structure of sodium petroleum sulfonate, i.e., the degree of sulfonation, is inextricably linked to the flotation collecting performance of the collector. By comparing sodium petroleum sulfonate with different molecular weights, it was determined that sodium petroleum sulfonate with a molecular weight between 500 and 750 has the optimal number of sulfonate groups and the highest degree of sulfonation.

[0045] The active ingredient content of sodium petroleum sulfonate reflects the content of effective anionic surfactants in the collector. Experimental results show that when the active ingredient content in the collector exceeds 35%, the higher the content, the greater the flotation recovery rate of fluorite. However, after the content exceeds 60%, the flotation recovery rate no longer increases and may even slightly decrease. Furthermore, the same trend is observed in both comparisons between different groups of collectors and between different batches of experiments. This indicates that the active ingredient content of sodium petroleum sulfonate is optimal for the flotation of fluorite mineral particles. This is because when the active ingredient content is below 35%, the adsorption density on the fluorite surface is too low, affecting the flotation effect; while when the content exceeds 60%, the content of alcohols and non-polar hydrocarbon oils, which are beneficial for flotation, relatively decreases. Alcohols and non-polar hydrocarbon oils can enhance the collector's solubility and improve its hydrophobicity.

[0046] For collectors, the degree of sulfonation significantly affects their colloidal chemical properties, particularly their dispersing and stabilizing abilities. In sodium petroleum sulfonate, the sulfonated components are the aromatic compounds in the feedstock. The chemical composition of aromatic hydrocarbons determines their collecting performance, and the electron density around the chain and ring structures of the hydrocarbon group in the collector determines the adsorption capacity of aromatic hydrocarbons. Therefore, it is necessary to study the influence of the aromatic hydrocarbon composition and structure on the collecting performance of sodium petroleum sulfonate. Experiments show that the higher the aromatic hydrocarbon content in the feedstock oil used to prepare sodium petroleum sulfonate, the higher the flotation recovery rate of fluorite, and the better the collecting effect of the collector during the flotation process. However, when the aromatic hydrocarbon content exceeds 31%, the stable bond length adsorbed on the fluorite surface will become shorter; when the benzene ring hydrocarbon content exceeds 11%, the adsorption energy will decrease; and when the naphthalene ring hydrocarbon content exceeds 5.2%, the collecting effect will deteriorate. Aromatic hydrocarbons also include polycyclic aromatic hydrocarbons (biphenyl) and other fused-ring aromatic hydrocarbons (anthracene). When the molar ratio of aromatics to sulfur trioxide is less than 2.4, the sulfonation degree of sodium petroleum sulfonate is insufficient, causing the collector to form a monolayer adsorption on the fluorite surface, i.e., insufficient hydrophobicity. When the molar ratio is too large, greater than 5, the sulfonation degree of sodium sulfonate is too heavy, and a large amount of sodium sulfonate forms disulfonyl or even trisulfonyl groups. After adsorption on the fluorite surface, the unadsorbed sulfonyl groups have a repulsive effect, affecting the adsorption of other sodium sulfonates. Furthermore, the nonpolar ends become weaker, resulting in insufficient hydrophobicity for adsorbing fluorite particles.

[0047] The components of sodium petroleum sulfonate can be classified into hydrocarbon sulfonates (active components), unsulfonated hydrocarbon oils, inorganic salts, n-butanol, and volatile components (water). The complexity of petroleum determines the diversity of the structure of sodium petroleum sulfonate. The nonpolar groups of hydrocarbon sulfonates can be aliphatic, aromatic, alicyclic, and fatty hydrocarbon groups, and the number of aryl and cycloalkyl groups in the nonpolar end varies. The side chain alkyl part often contains multiple branches. The complexity of the structure is not only reflected in hydrocarbon sulfonates but also in the structure of nonpolar oils.

[0048] As the second largest component after hydrocarbon sulfonates, the content and composition of non-polar oils significantly influence the effects of hydrocarbon sulfonates. Therefore, it is necessary to conduct a detailed study on the synergistic effect between non-polar oils and hydrocarbon sulfonates. The type of hydrocarbon sulfonates and non-polar oils, the dosing method, and the optimal molar content of hydrocarbon sulfonates in the mixed collector all have a significant impact on the synergistic effect.

[0049] The structure of sodium petroleum sulfonate determines its flotation performance on fluorite. Besides affecting the association force between collectors and thus their solubility, it also determines the aggregation state on the target mineral surface during adsorption. This aggregation state of the collector on the target mineral surface inevitably affects the secondary adsorption of non-polar oil on that surface. From the flotation test results of sodium dodecylbenzene sulfonate and its combination with non-polar oil, regardless of the structure of the non-polar oil used as the auxiliary collector, the synergistic effect between sodium dodecylbenzene sulfonate and non-polar oil is significantly stronger than that between sodium dodecylbenzene sulfonate and non-polar oil. Structural differences significantly affect the synergistic effect between hydrocarbon sulfonates and non-polar oil. The main structural difference between sodium dodecylbenzene sulfonate and sodium dodecylbenzene sulfonate lies in whether or not a benzene ring is present at the non-polar end. The presence of the benzene ring gives sodium dodecylbenzene sulfonate a larger cross-sectional area, making it difficult for its non-polar ends to aggregate. This phenomenon allows non-polar oil molecules to intersect between the unaggregated non-polar end chains, increasing the hydrophobicity of the fluorite surface.

[0050] The influence of the structure of nonpolar oils on synergistic effects: Kerosene exhibits the best synergistic effect, followed by dodecane and methylnaphthalene. Kerosene and dodecane have similar structures, differing only in carbon chain length. Their adsorption mechanisms between collectors are also largely the same. The stronger synergistic effect of kerosene is due to its longer carbon chain, resulting in stronger association with the nonpolar hydrocarbon chains of the collector. Furthermore, the longer carbon chain length also contributes to better hydrophobic properties.

[0051] The dosing method for the mixed collector is as follows: sodium dodecylbenzenesulfonate is added first, followed by emulsified kerosene, and the amount of collector added is controlled to maintain the ratio between the two. Overall, the mixed collector shows better flotation performance than the single collector. When the sodium dodecylbenzenesulfonate content in the mixed collector is 77.66%, the flotation performance of the mixed collector is almost identical to that of the single collector, and even slightly higher in some concentration ranges, indicating a strong synergistic effect between sodium dodecylbenzenesulfonate and kerosene. When the sodium dodecylbenzenesulfonate content in the collector is below 77.66%, the flotation performance of the mixed collector is weaker than that of the single collector across the entire concentration range. Proportional condition experiments show that the synergistic effect is significantly influenced by the sodium dodecylbenzenesulfonate content, with the optimal molar content between 77.66% and 85%. Surfactant-based collectors work by adsorbing their polar ends onto the mineral surface, altering the surface hydrophobicity through adsorption onto the non-polar ends. Non-polar oil-based collectors, however, do not spontaneously adsorb onto the surface of polar minerals. In mixed collectors, the adsorption of non-polar oil-based collectors is contingent upon the adsorption of surfactants onto the mineral surface. Non-polar oils adsorb onto the mineral surface through association between hydrocarbon chains, thus altering the surface hydrophobicity. This illustrates that the synergistic effect is predicated on the prior adsorption of sodium dodecylbenzenesulfonate. Only when the concentration of sodium dodecylbenzenesulfonate adsorbed on the mineral surface reaches a certain level will kerosene achieve the purpose of increasing the surface hydrophobicity through co-adsorption via hydrocarbon chain association or secondary adsorption.

[0052] Example 1:

[0053] A fluorite flotation collector containing sodium petroleum sulfonate comprises sodium petroleum sulfonate and kerosene, wherein the molar ratio of kerosene to sodium petroleum sulfonate is 3.33. The sodium petroleum sulfonate comprises feedstock oil and active ingredient (hydrocarbon sulfonate). The molecular weight of the sodium petroleum sulfonate is 538, the molecular weight of the feedstock oil is 367, and the content of the active ingredient is 41.55%. The feedstock oil comprises aromatics, and the content of the aromatics is 19.51%. The feedstock oil is sulfonated with sulfur trioxide, and the molar ratio of aromatics to sulfur trioxide in the feedstock oil is 2.4. The aromatics comprise benzene ring hydrocarbons and naphthalene ring hydrocarbons, the content of the benzene ring hydrocarbons is 10.8%, and the content of the naphthalene ring hydrocarbons is 5.2%.

[0054] The sodium petroleum sulfonate is sodium alkylbenzene sulfonate, which is the sodium salt of a straight-chain alkylbenzene sulfonic acid consisting of 14-18 carbon atoms, with the structural formula CH3(CH2)nSO3Na (n=13-17). The sodium petroleum sulfonate is produced by first sulfonating C14-C18 straight-chain alkanes in petroleum products, separating the insoluble acid residue, and then obtaining oil-soluble sulfonic acid. The acidity of the oil-soluble sulfonic acid is then neutralized with sodium hydroxide to obtain crude sodium petroleum sulfonate. The crude sodium petroleum sulfonate is then extracted from neutral oil using low-carbon alcohol water. Finally, it undergoes a series of treatments including dehydration, decolorization, deoiling, washing, and concentration to obtain refined sodium petroleum sulfonate. The chemical reaction formulas involved are shown below:

[0055] ;

[0056] .

[0057] A method for preparing a sodium petroleum sulfonate collector for fluorite flotation, the method comprising the following steps:

[0058] S1. Dissolve sodium petroleum sulfonate in water;

[0059] S2. First, put the sodium petroleum sulfonate solution into a volumetric flask, then put the kerosene into the volumetric flask, then make up to volume and pour into a beaker;

[0060] S3. Vibrate in an ultrasonic oscillator for more than 9 minutes (to ensure full emulsification) to obtain sodium petroleum sulfonate collector.

[0061] A method for applying sodium petroleum sulfonate collector in fluorite flotation, the method comprising the following steps:

[0062] S1. Fluorite is mixed with water to prepare a slurry with a mass concentration of 35%, and the temperature is maintained at around 5℃; the calcium fluoride grade in the raw fluorite ore is 47.68%, and the fluorite ore is provided by a fluorite mine in Jiangxi Province;

[0063] S2. First, dissolve sodium petroleum sulfonate in water, then put the sodium petroleum sulfonate solution into a volumetric flask, then put kerosene into the volumetric flask, then make up to volume and pour into a beaker, and then perform ultrasonic emulsification to obtain sodium petroleum sulfonate collector.

[0064] S3. First, add the slurry to the flotation machine and adjust the slurry at 1600 r / min for 2 minutes. Then, add sodium hydroxide to adjust the pH value to 8.5. Continue stirring for 2 minutes and then add sodium petroleum sulfonate collector at a dosage of 1000 g / t. Stir for 3 minutes, aerate for 30 seconds, and then skim the foam for 5 minutes to obtain the frothy product, which is the fluorite concentrate.

[0065] Example 2:

[0066] The basic content is the same as in Example 1, except that:

[0067] The sodium petroleum sulfonate has a molecular weight of 563 and an active ingredient content of 53.16%.

[0068] Example 3:

[0069] The basic content is the same as in Example 1, except that:

[0070] The sodium petroleum sulfonate has a molecular weight of 563, the active ingredient content is 47.82%, and the benzene ring hydrocarbon content is 11%.

[0071] Example 4:

[0072] The basic content is the same as in Example 1, except that:

[0073] The sodium petroleum sulfonate has a molecular weight of 538, the active ingredient content is 61.56%, and the molar ratio of aromatic hydrocarbon to sulfur trioxide is 2.66.

[0074] Example 5:

[0075] The basic content is the same as in Example 1, except that:

[0076] The sodium petroleum sulfonate has a molecular weight of 606, the active ingredient content is 48.42%, and the molar ratio of aromatic hydrocarbon to sulfur trioxide is 2.66.

[0077] Example 6:

[0078] The basic content is the same as in Example 1, except that:

[0079] The raw material oil has a molecular weight of 448, the active ingredient content is 45.44%, and the aromatic hydrocarbon content is 30.81%.

[0080] Example 7:

[0081] The basic content is the same as in Example 1, except that:

[0082] The active ingredient content is 61.56%, the aromatic hydrocarbon content is 30.81%, the naphthalene ring hydrocarbon content is 5.6%, and the molar ratio of the aromatic hydrocarbon to sulfur trioxide is 2.8.

[0083] Example 8:

[0084] The basic content is the same as in Example 1, except that:

[0085] The sodium petroleum sulfonate has a molecular weight of 621, the feedstock oil has a molecular weight of 415, the active ingredient content is 42.04%, and the aromatic hydrocarbon content is 30.81%.

[0086] Example 9:

[0087] The basic content is the same as in Example 1, except that:

[0088] The sodium petroleum sulfonate has a molecular weight of 621, the feedstock oil has a molecular weight of 415, the active ingredient content is 44.26%, and the aromatic hydrocarbon content is 30.81%.

[0089] Example 10:

[0090] The basic content is the same as in Example 1, except that:

[0091] The sodium petroleum sulfonate has a molecular weight of 621, the feedstock oil has a molecular weight of 415, the active ingredient content is 42.13%, and the aromatic hydrocarbon content is 30.81%.

[0092] The flotation results tested according to the methods described in Examples 1 to 10 above are shown in Table 1 below.

[0093] Table 1 - Flotation results of different embodiments of the flotation method

[0094]

[0095] Comparative studies of Examples 1-10 show that, within the parameter range proposed in this design, sodium petroleum sulfonate exhibits excellent flotation recovery performance for fluorite at low temperatures. At 5°C, the fluorite concentrate grade reaches over 98%, and the recovery rate is over 95%. Therefore, this design is highly effective for fluorite flotation at low temperatures.

Claims

1. A method for applying sodium petroleum sulfonate collector in fluorite flotation, characterized in that: The application method includes the following steps: S1. Fluorite is mixed with water to prepare a slurry with a mass concentration of 35%, and the temperature is maintained at 5℃; S2. First, dissolve sodium petroleum sulfonate in water, then put the sodium petroleum sulfonate solution into a volumetric flask, then put the non-polar oil into the volumetric flask, then make up to volume and pour into a beaker, and then shake in an ultrasonic oscillator for more than 9 minutes to obtain sodium petroleum sulfonate collector. The sodium petroleum sulfonate is sodium alkylbenzene sulfonate, which is the sodium salt of a straight-chain alkylbenzene sulfonic acid composed of 14 to 18 carbon atoms, with the structural formula CH3(CH2)nSO3Na (n=13 to 17). The sodium petroleum sulfonate is obtained by first sulfonating C14-C18 straight-chain alkanes in petroleum products to obtain oil-soluble sulfonic acid, then neutralizing the acidity of the oil-soluble sulfonic acid with sodium hydroxide to obtain crude sodium petroleum sulfonate, then extracting the crude sodium petroleum sulfonate from the neutral oil with low-carbon alcohol water, and then obtaining refined sodium petroleum sulfonate through dehydration, decolorization, deoiling, water washing and concentration. The sodium petroleum sulfonate collector comprises sodium petroleum sulfonate and a non-polar oil, wherein the molar ratio of the non-polar oil to sodium petroleum sulfonate is 3.33–5.

67. The sodium petroleum sulfonate comprises a feedstock oil and an active ingredient. The molecular weight of the sodium petroleum sulfonate is 500–750, the molecular weight of the feedstock oil is 350–450, and the content of the active ingredient is 35%–60%. The feedstock oil comprises aromatics, wherein the aromatic content is 10%–31%. The feedstock oil is sulfonated with sulfur trioxide, wherein the molar ratio of aromatics to sulfur trioxide in the feedstock oil is 2.4–5. The aromatics include benzene ring hydrocarbons and naphthalene ring hydrocarbons, wherein the content of benzene ring hydrocarbons is 5%–11%, and the content of naphthalene ring hydrocarbons is 5%–5.2%. The non-polar oil is kerosene. S3. First, add the slurry to the flotation machine and adjust the slurry at 1600 r / min for 2 minutes. Then, add sodium hydroxide to adjust the pH value to 8.

5. Continue stirring for 2 minutes and then add sodium petroleum sulfonate collector at a dosage of 1000 g / t. Stir for 3 minutes, aerate for 30 seconds, and then skim the foam for 5 minutes to obtain the frothy product, which is the fluorite concentrate.

2. The application method of sodium petroleum sulfonate collector for fluorite flotation according to claim 1, characterized in that: In step S2, the non-polar oil is dodecane or monomethylnaphthalene.

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