Gypsum flotation collector and gypsum flotation method

Abstract

The invention provides a gypsum flotation collecting agent and a gypsum flotation method, and relates to the technical field of lithium slag flotation. The gypsum flotation collecting agent comprises the following components in parts by mass: 4-8 parts of fatty amine, 4-24 parts of acid, 1-2 parts of an activating agent and 5-10 parts of ethyl alcohol. According to the gypsum flotation collecting agent, the fatty amine, the acid, the activating agent and the ethyl alcohol cooperate with one another, and the selectivity and collecting capacity of the collecting agent to gypsum are remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of lithium slag flotation, and in particular to a gypsum flotation collector and a gypsum flotation method. Background Art

[0002] Lithium is the lightest metal in nature, with high electrical conductivity and strong chemical activity. With the rapid development of my country's new energy industry, the demand for lithium has risen sharply. my country has large reserves of lithium mica, which is the main source of lithium minerals in my country. However, a large amount of by-products - lithium slag - will be produced during the smelting process of lithium mica.

[0003] Lithium slag is the waste residue produced when lithium mica is used to produce lithium salt. It is the waste residue produced after lithium mica concentrate is roasted by 950℃ high-temperature sulfate method, leached in water at normal pressure, and separated into solid and liquid. At present, lithium slag is basically treated by stacking. Lithium slag contains sulfate residues, which may cause serious pollution to soil and water bodies during stacking. Therefore, if lithium slag is not utilized, it will inevitably become a heavy burden for enterprises and the environment, which will seriously restrict the development of lithium battery new energy industry in Yichun area.

[0004] At present, lithium slag is mainly used in cement building materials industry, with low value and limited consumption capacity. Therefore, developing a collector for flotation of gypsum from lithium slag and its flotation method can not only effectively save auxiliary material costs, but also the desulfurized lithium slag after flotation can meet the requirements of high value-added applications in ceramics, glass fiber, molecular sieves, etc., and can reduce the impact of lithium slag on the environment, which has important application significance for the comprehensive utilization of lithium slag in Yichun area. Summary of the invention

[0005] 1. Technical issues to be solved

[0006] In view of the deficiencies of the prior art, the present invention provides a gypsum flotation collector and a method for flotation of gypsum, which solves the technical problem of how to reuse lithium slag.

[0007] (II) Technical solution

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0009] In a first aspect, the present invention provides a gypsum flotation collector, comprising the following components in parts by weight:

[0010] 4-8 parts of fatty amine, 4-24 parts of acid, 1-2 parts of activator, 5-10 parts of ethanol.

[0011] The gypsum flotation collector of the present invention comprises 4-8 parts of fatty amine, 4-24 parts of acid, 1-2 parts of activator and 5-10 parts of ethanol. The fatty amine, acid, activator and ethanol work together to significantly improve the selectivity and collection capacity of the collector for gypsum.

[0012] The gypsum flotation collector of the invention can improve the annexation capacity of flotation foam, thereby significantly improving the flotation efficiency of gypsum in lithium slag.

[0013] Preferably, the fatty amine is selected from at least one of dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine and octadecylamine.

[0014] And / or, the acid is selected from any one of hydrochloric acid and acetic acid, the hydrochloric acid accounts for 4-8 parts of the gypsum flotation collector, and the acetic acid accounts for 12-24 parts of the gypsum flotation collector. Acetic acid or hydrochloric acid reacts with fatty amine to generate fatty acid salts, and the collector has stronger action ability.

[0015] The above-mentioned fatty amine has an obvious effect on the flotation of fine-grained gypsum, so the gypsum flotation collector of the present invention can be used for the flotation of fine-grained gypsum in lithium slag.

[0016] Preferably, the activator is selected from at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium hexadecyl sulfate and sodium octadecyl sulfate.

[0017] The above activator can make the gypsum flotation collector of the present invention have good water solubility and uniformity even under low temperature conditions. Therefore, the gypsum flotation collector of the present invention has good low temperature water solubility and the flotation effect is not affected at low temperatures.

[0018] In a second aspect, the present invention provides a method for flotation of gypsum using the gypsum flotation collector described in the first aspect, comprising the following steps:

[0019] S1, providing lithium slag, grinding the lithium slag and adding water to obtain slurry, adjusting the pH of the slurry, adding an inhibitor and the gypsum flotation collector and stirring sufficiently, performing gypsum flotation operation, and obtaining gypsum rough concentrate and rougher tailings;

[0020] S2. The gypsum coarse concentrate is subjected to secondary concentration to obtain concentrated middlings and gypsum concentrate.

[0021] The gypsum concentrate floated by the above-mentioned gypsum flotation method can be returned to the lepidolite roasting ingredients as an auxiliary material, thereby reducing production costs. At the same time, after flotation, the impact of lithium slag on the environment can be reduced.

[0022] Preferably, the inhibitor is selected from any one of sodium hexametaphosphate, water glass and sodium fluorosilicate, and the dosage is 1000-1500 g / t.

[0023] Preferably, the pH of the slurry is adjusted to 8-10.

[0024] Under the alkaline condition, the collector's ability to absorb flotation foam is improved, thereby significantly improving the collector's flotation efficiency for gypsum in lithium slag.

[0025] Preferably, the method further comprises S3, adding the gypsum flotation collector to the roughing tailings for secondary scavenging to obtain scavenged roughing tailings and scavenged tailings.

[0026] The roughing tailings are subjected to secondary scavenging to obtain scavenged ore, and the scavenged ore is returned to the previous level in sequence, which can improve the utilization rate of lithium slag. After the secondary scavenging, the scavenged tailings have a low sulfur content and can be used in high value-added products, thereby improving the comprehensive utilization value of lithium slag.

[0027] Preferably, in S1, the SO3 grade of the gypsum contained in the lithium slag is 10%-18%,

[0028] and / or, the slurry concentration is 25-35%,

[0029] And / or, any one of sodium carbonate, sodium hydroxide and potassium hydroxide is used to adjust the pH of the slurry.

[0030] Preferably, the SO3 grade of the gypsum concentrate is 40%-45%, the recovery rate is 85-90%, and the particle size is -300 mesh, accounting for 60%-69%. The above gypsum concentrate can be returned to the calcination ingredients of lepidolite as an auxiliary material, thereby reducing production costs.

[0031] Preferably, the method satisfies at least one of the following conditions:

[0032] In S1, the dosage of gypsum flotation collector is 150-300 g / t,

[0033] In said S2, an inhibitor is added in both the secondary cleaning, and the amount of the inhibitor is 0.6 to 1 times of the inhibitor in step S1.

[0034] In said S3, the gypsum flotation collector is added in both the second scavenging and the amount of the gypsum flotation collector is 0.3-0.6 times the amount of the gypsum flotation collector in step S1. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0036] Figure 1 Example 1 is a process flow chart for flotation of lithium slag. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0039] Example 1

[0040] This embodiment provides a method for preparing a gypsum flotation collector, comprising the following steps:

[0041] Take 4 g of dodecylamine, 4 g of hydrochloric acid, 1 g of sodium dodecyl sulfate, and 5 g of anhydrous ethanol, and add water to prepare a 2 wt% concentration of gypsum flotation collector aqueous solution.

[0042] The above gypsum flotation collector aqueous solution was used to flotate lithium slag from a lithium mica smelting plant in Yichun. The SO3 content in the lithium slag was 12.52%. Figure 1 The specific flotation method is as follows:

[0043] S1. Grind the lithium slag to a fineness of less than 200 meshes accounting for 70% to fully dissociate the gypsum, add water to adjust the pulp concentration to 30%, the pulp temperature to 25°C, first add sodium carbonate to the pulp to adjust the pulp pH to 9, then add 1000g / t of water glass and stir for 3min, then add 150g / t of the above-mentioned gypsum flotation collector and stir for 4min, perform gypsum flotation operation, and obtain gypsum coarse concentrate and rougher tailings;

[0044] S2. The gypsum coarse concentrate obtained in step S1 is subjected to secondary concentration. In the first concentration (hereinafter referred to as concentration one), 800 g / t of water glass is added and stirred for 3 min. In the second concentration (hereinafter referred to as concentration two), 1000 g / t of water glass is added and stirred for 4 min to obtain concentrated medium ore and gypsum concentrate. The concentrated medium ore is returned to the previous level in sequence.

[0045] S3, the roughing tailings obtained in step S1 are subjected to secondary scavenging, and the first scavenging (referred to as scavenging 1) is added with 100g / t of the above-mentioned gypsum flotation collector and stirred for 4 minutes, and the second scavenging (referred to as scavenging 2) is added with 50g / t of the above-mentioned gypsum flotation collector and stirred for 4 minutes to obtain scavenged ores and scavenged tailings. The scavenged ores are returned to the previous level in sequence, and the scavenged tailings are tailings.

[0046] After testing, the lithium slag from the lithium mica smelting in Yichun was finally obtained after flotation, with a SO3 grade of 41.76%, a recovery rate of 88.46%, a gypsum concentrate with a particle size of -300 mesh accounting for 60%, and a tailings with a SO3 grade of 0.5%, with good sorting indicators.

[0047] Example 2

[0048] This embodiment provides a method for preparing a gypsum flotation collector, and the specific steps are as follows:

[0049] Take 4 g of octadecylamine, 4 g of hydrochloric acid, 1 g of sodium dodecyl sulfate, and 6 g of anhydrous ethanol, and add water to prepare a 2 wt % concentration of gypsum flotation collector aqueous solution.

[0050] The above gypsum flotation collector aqueous solution was used to flotate a lithium slag from a lithium mica smelting plant in Yichun. The SO3 content in the lithium slag was 13.47%. The specific flotation method was as follows:

[0051] S1. Grind the lithium slag to a fineness of less than 200 meshes accounting for 70% to fully dissociate the gypsum, add water to adjust the slurry concentration to 30%, the slurry temperature to 24°C, first add sodium carbonate to the slurry to adjust the slurry pH to 9, then add 1000g / t of water glass and stir for 3min, then add 200g / t of the above-mentioned gypsum flotation collector and stir for 4min, perform gypsum flotation operation, and obtain gypsum coarse concentrate and rougher tailings;

[0052] S2, the gypsum coarse concentrate obtained in step S1 is subjected to secondary concentration, wherein 800 g / t of water glass is added to the concentrate in the first concentration and stirred for 3 min, and 1000 g / t of water glass is added to the concentrate in the second concentration and stirred for 4 min to obtain concentrated medium ore and gypsum concentrate. The concentrated medium ore is returned to the previous level in sequence.

[0053] S3, the roughing tailings obtained in step S1 are subjected to secondary scavenging, wherein the scavenging first step is to add 100g / t of the above-mentioned gypsum flotation collector and fully stir for 4min, and the scavenging second step is to add 50g / t of the above-mentioned gypsum flotation collector and fully stir for 4min to obtain scavenged ores and scavenged tailings. The scavenged ores are returned to the previous level in sequence, and the scavenged tailings are tailings.

[0054] After flotation of lithium slag from a lithium mica smelter in Yichun, the final products were gypsum concentrate with a SO3 grade of 42.85%, a recovery rate of 89.06%, a particle size of -300 mesh accounting for 62%, and tailings with a SO3 grade of 0.48%, with good sorting indicators.

[0055] Example 3

[0056] This embodiment provides a method for preparing a gypsum flotation collector, comprising the following steps:

[0057] Take 8 g of dodecylamine, 8 g of hydrochloric acid, 2 g of sodium dodecyl sulfate, and 5 g of anhydrous ethanol, and add water to prepare a 2 wt% concentration of gypsum flotation collector aqueous solution.

[0058] The above gypsum flotation collector aqueous solution was used to flotate a lithium slag from a lithium mica smelting plant in Yichun. The SO3 content in the lithium slag was 11.56%. The specific flotation method steps are as follows:

[0059] S1. Grind the lithium slag to a fineness of less than 200 meshes, accounting for 80%, to fully dissociate the gypsum, add water to adjust the slurry concentration to 30%, the slurry temperature to 25°C, first add sodium hydroxide to the slurry to adjust the slurry pH to 9.5, then add 1500g / t of water glass and stir for 4min, then add 200g / t of gypsum flotation collector and stir for 4min, perform gypsum flotation operation, and obtain gypsum coarse concentrate and rougher tailings;

[0060] S2, the gypsum coarse concentrate obtained in step S1 is subjected to secondary concentration, wherein 800 g / t of water glass is added to the concentrate for 3 min, and 800 g / t of water glass is added to the concentrate for 4 min to obtain concentrated medium ore and gypsum concentrate. The concentrated medium ore is returned to the previous level in sequence.

[0061] S3, the roughing tailings obtained in step S1 are subjected to secondary scavenging, scavenging the first ore with a dosage of 100 g / t gypsum flotation collector and fully stirred for 4 min, scavenging the second ore with a dosage of 50 g / t gypsum flotation collector and fully stirred for 4 min, to obtain scavenged ore and scavenged tailings. The scavenged ore is returned to the previous level in sequence, and the scavenged tailings are tailings.

[0062] After flotation, the lithium slag from the lithium mica smelting project in Yichun finally obtained a gypsum concentrate with a SO3 grade of 40.95%, a recovery rate of 87.48%, a particle size of -300 mesh accounting for 68%, and a tailings with a SO3 grade of 0.51%, with good sorting indicators.

[0063] Example 4

[0064] This embodiment provides a method for preparing a gypsum flotation collector, comprising the following steps:

[0065] Take 4 g of dodecylamine, 12 g of acetic acid, 1 g of sodium dodecyl sulfate, and 5 g of anhydrous ethanol, and add water to prepare a 2 wt% concentration of gypsum flotation collector aqueous solution.

[0066] The gypsum flotation collector aqueous solution was used to flotate the lithium slag from a lithium mica smelting plant in Yifeng County. The SO3 content in the lithium slag was 14.12%. The flotation method steps are as follows:

[0067] S1. Grind the lithium slag to a fineness of less than 200 meshes, accounting for 80%, to fully dissociate the gypsum, add water to adjust the slurry concentration to 28%, the slurry temperature to 20°C, first add sodium carbonate to the slurry to adjust the slurry pH to 8.5, then add 1500g / t of water glass and stir for 3min, then add 200g / t of gypsum flotation collector and stir for 4min, perform gypsum flotation operation, and obtain gypsum coarse concentrate and rougher tailings;

[0068] S2, the gypsum coarse concentrate obtained in step S1 is subjected to secondary concentration, wherein 800 g / t of water glass is added to the concentrate in the first concentration and stirred for 3 min, and 1000 g / t of water glass is added to the concentrate in the second concentration and stirred for 4 min to obtain concentrated medium ore and gypsum concentrate. The concentrated medium ore is returned to the previous level in sequence.

[0069] S3, the roughing tailings obtained in step S1 are subjected to secondary scavenging, scavenging the first ore with a dosage of 100 g / t gypsum flotation collector and fully stirred for 4 min, scavenging the second ore with a dosage of 50 g / t gypsum flotation collector and fully stirred for 4 min, to obtain scavenged ore and scavenged tailings. The scavenged ore is returned to the previous level in sequence, and the scavenged tailings are tailings.

[0070] After flotation of lithium slag from a lithium mica smelter in Yichun, the final products were gypsum concentrate with a SO3 grade of 43.67%, a recovery rate of 88.52%, a particle size of -300 mesh accounting for 69%, and tailings with a SO3 grade of 0.52%, with good sorting indicators.

[0071] Example 5

[0072] The difference between this embodiment and embodiment 1 is that the slurry temperature is 9° C., and the rest is the same as embodiment 1.

[0073] After testing, the lithium slag from the lithium mica smelting in Yichun was finally flotated to obtain a gypsum concentrate with a SO3 grade of 40.16%, a recovery rate of 87.16%, a particle size of -300 mesh accounting for 60%, and a tailings with a SO3 grade of 0.6%, with good sorting indicators.

[0074] Comparative Example 1

[0075] The difference between this comparative example and Example 1 is that in the preparation method of the gypsum flotation collector, sodium dodecyl sulfate is not contained, dodecylamine is 4.3 g, hydrochloric acid is 4.3 g, and anhydrous ethanol is 5.4 g. Others are the same as Example 1.

[0076] After flotation of lithium slag from a lithium mica smelting plant in Yichun, the final products were gypsum concentrate with a SO3 grade of 30.86%, a recovery rate of 66.53%, a particle size of -300 mesh accounting for 60%, and tailings with a SO3 grade of 0.85%.

[0077] Comparative Example 2

[0078] The difference between this comparative example and Example 1 is that in the preparation method of the gypsum flotation collector, dodecylamine is not contained, 5.6 g of hydrochloric acid, 1.4 g of sodium dodecyl sulfate, and 7 g of anhydrous ethanol are used. The rest is the same as Example 1.

[0079] After flotation of lithium slag from a lithium mica smelting plant in Yichun, the final products were gypsum concentrate with a SO3 grade of 19.12%, a recovery rate of 35.65%, a particle size of -300 mesh accounting for 60%, and tailings with a SO3 grade of 6.53%.

[0080] Comparative Example 3

[0081] The difference between this comparative example and Example 1 is that in the preparation method of the gypsum flotation collector, hydrochloric acid is not contained, 5.6 g of dodecylamine, 1.4 g of sodium dodecyl sulfate, and 7 g of anhydrous ethanol are used. The rest is the same as Example 1.

[0082] After flotation of lithium slag from a lithium mica smelting plant in Yichun, the final products were gypsum concentrate with a SO3 grade of 32.64%, a recovery rate of 73.63%, a particle size of -300 mesh accounting for 60%, and tailings with a SO3 grade of 0.79%.

[0083] Comparative Example 4

[0084] The difference between this comparative example and Example 1 is that in the preparation method of the gypsum flotation collector, anhydrous ethanol is not contained, 6.3 g of dodecylamine, 6.3 g of hydrochloric acid, and 1.4 g of sodium dodecyl sulfate are contained. The rest is the same as Example 1.

[0085] After flotation of lithium slag from a lithium mica smelting plant in Yichun, the final products were gypsum concentrate with a SO3 grade of 30.47%, a recovery rate of 71.53%, a particle size of -300 mesh accounting for 60%, and tailings with a SO3 grade of 0.81%.

[0086] From the comparison of comparative examples 1-4 with embodiment 1, it can be seen that the collector of the present invention includes dodecylamine, hydrochloric acid, sodium dodecyl sulfate and anhydrous ethanol. Dodecylamine, hydrochloric acid, sodium dodecyl sulfate and anhydrous ethanol work together to significantly improve the selectivity and collection capacity of the collector for gypsum.

[0087] Comparative Example 5

[0088] The difference between this comparative example and Example 1 is that in the preparation method of the gypsum flotation collector, no pH adjuster is added to S1, and the pH of the slurry is measured to be 7. The rest is the same as Example 1.

[0089] After flotation of lithium slag from a lithium mica smelter in Yichun, the final results were gypsum concentrate with a SO3 grade of 35.13%, a recovery rate of 75.76%, a particle size of -300 mesh accounting for 60%, and tailings with a SO3 grade of 0.77%, indicating that the gypsum flotation collector has better flotation efficiency under alkaline conditions. This is because the alkaline conditions improve the collector's ability to absorb flotation foam, thereby significantly improving its flotation efficiency for gypsum in lithium slag.

[0090] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0091] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A gypsum flotation collector, characterized in that: The composition comprises the following components in parts by weight:

2. The gypsum flotation collector according to claim 1, characterized in that: The fatty amine is selected from at least one of dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine and octadecylamine. And / or, the acid is selected from any one of hydrochloric acid and acetic acid, the hydrochloric acid accounts for 4-8 parts in the gypsum flotation collector, and the acetic acid accounts for 12-24 parts in the gypsum flotation collector.

3. The gypsum flotation collector according to claim 1, characterized in that: The activator is selected from at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium hexadecyl sulfate and sodium octadecyl sulfate.

4. A method for flotation of gypsum using the gypsum flotation collector according to any one of claims 1 to 3, characterized in that: The steps include: S1, providing lithium slag, grinding the lithium slag and adding water to obtain slurry, adjusting the pH of the slurry, adding an inhibitor and the gypsum flotation collector and stirring sufficiently, performing gypsum flotation operation, and obtaining gypsum rough concentrate and rougher tailings; S2. The gypsum coarse concentrate is subjected to secondary concentration to obtain concentrated middlings and gypsum concentrate.

5. The method for flotation of gypsum as claimed in claim 4, characterized in that: The inhibitor is selected from any one of sodium hexametaphosphate, water glass and sodium fluorosilicate, and the dosage is 1000-1500g / t.

6. The method for flotation of gypsum according to claim 4, characterized in that: The pH of the slurry is adjusted to 8-10.

7. The method for flotation of gypsum according to claim 4, characterized in that: The method further comprises S3, adding the gypsum flotation collector to the roughing tailings for secondary scavenging to obtain scavenged roughing tailings and scavenged tailings.

8. The method for flotation of gypsum according to claim 4, characterized in that: In the S1, the SO3 grade of the gypsum contained in the lithium slag is 10%-18%, and / or, the slurry concentration is 25-35%, And / or, any one of sodium carbonate, sodium hydroxide and potassium hydroxide is used to adjust the pH of the slurry.

9. The method for flotation of gypsum according to claim 4, characterized in that: The SO3 grade of the gypsum concentrate is 40%-45%, the recovery rate is 85-90%, and the particle size of -300 mesh accounts for 60%-69%.

10. The method for flotation of gypsum according to claim 7, characterized in that: The method satisfies at least one of the following conditions: In S1, the dosage of gypsum flotation collector is 150-300 g / t, In said S2, an inhibitor is added in both the secondary cleaning, and the amount of the inhibitor is 0.6 to 1 times the amount of the inhibitor in step S1. In S3, the gypsum flotation collector is added in both the second scavenging and the amount of the gypsum flotation collector is 0.3-0.6 times the amount of the gypsum flotation collector in step S1.

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