Collecting agent compound, preparation method and mixed collecting agent

Abstract

The invention discloses a collecting agent compound, a preparation method and a mixed collecting agent, and the preparation method comprises the following steps: measuring 50 mL of 0.6 mol of 1, 3-propane sultone A by using a measuring cylinder, and dissolving the 1, 3-propane sultone A in 0.1-1.0 L of ethyl acetate; slowly adding 155mL and 0.6 mL of N, N-dimethyl octylamine B into the reaction solution obtained in the previous step; stirring the mixture for 1-10 hours at the temperature of 20-100 DEG C to carry out alkylation reaction of amine; after the reaction is finished, filtering a reaction mixture to obtain a white precipitate; washing the precipitate twice with 10ml of ethyl acetate and 10ml of petroleum ether respectively, and finally drying a white solid C in a vacuum oven at the temperature of 100 DEG C; compared with a single-group collecting agent, the prepared collecting agent compound can be selectively adsorbed on the surface of spodumene due to the unique structure and charge distribution after the sulfonic acid and the amino are combined, and the flotation recovery rate of the spodumene can be effectively increased.

Description

Technical Field

[0001] The invention relates to a collector compound, a preparation method and a mixed collector. Background Art

[0002] At present, there are many types of collectors used for lithium mica flotation, including anionic collectors, amine collectors and new collectors. Anionic collectors such as fatty acids can only have the ability to collect lithium mica after it is activated by lithium salts or hydrofluoric acid; while amine collectors have strong collecting ability but lack selectivity, and are sensitive to ore slimes, and are easily adsorbed on the surface of ore slimes in large quantities, which not only increases the amount of collectors used, reduces flotation efficiency, but also makes the selectivity worse. The research and development and testing of new lithium mica collectors are in the initial stage, and the cost is high, so there are few practical applications. Therefore, it is of great application significance to develop a lithium mica flotation collector with good selectivity, strong collecting ability, short defoaming time, which can reduce the amount of desludging while improving the sorting effect of lithium mica, and is low in cost and simple to prepare. Summary of the invention

[0003] The main purpose of the present invention is to provide a collector compound, a preparation method and a mixed collector, aiming to solve the above technical problems.

[0004] To achieve the above object, the present invention provides a method for preparing a collector compound, comprising:

[0005] Use a measuring cylinder to measure 50 mL, 0.6 mol of 1,3-propane sultone A and dissolve it in 0.1-1.0 L of ethyl acetate;

[0006] Slowly add 155 mL and 0.6 mL of N, N-dimethyloctylamine B to the previous reaction solution;

[0007] stirring the mixture at 20-100° C. for 1-10 h to carry out alkylation reaction of the amine;

[0008] After the reaction was completed, the reaction mixture was filtered to obtain a white precipitate;

[0009] The precipitate was washed twice with 10 ml of ethyl acetate and petroleum ether respectively, and finally the white solid C was dried in a vacuum oven at 100 °C;

[0010] The chemical formula of C is:

[0011]

[0012] In addition, the present invention also provides a collector compound, wherein the collector compound C is prepared by the collector compound preparation method as described above, and the chemical formula of the collector compound C is:

[0013]

[0014] In addition, the present invention also provides a mixed flotation agent, characterized in that the mixed flotation agent comprises 35-65% of the collector compound as described above, 5-32% of a foaming agent, 5-25% of a depressant, 10-30% of a regulator and 10-50% of a solvent.

[0015] In one embodiment, the foaming agent includes one or more of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride, pine oil, methyl isobutyl carbinol and polypropylene glycol.

[0016] In one embodiment, the inhibitor includes one or more of dextrin, starch, water glass, and sodium hexametaphosphate.

[0017] In one embodiment, the adjusting agent includes one or more of lime, hydrochloric acid, sulfuric acid, sodium sulfide, copper sulfate and sodium hexametaphosphate.

[0018] In one embodiment, the solvent includes water or alcohol.

[0019] In the technical solution of the present invention, compared with a single group collector, after sulfonic acid and amino are combined, due to their unique structure and charge distribution, they can be more selectively adsorbed on the surface of spodumene, while the adsorption of some gangue minerals is relatively weak. Gangue minerals such as quartz have different surface properties from spodumene. The collector combined with sulfonic acid and amino can be preferentially adsorbed on the surface of spodumene based on the difference in charge complementarity and chemical bonding, reducing the collection of gangue minerals such as quartz. This helps to better separate spodumene and gangue minerals during the flotation process and improve the grade of the concentrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] 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 the structures shown in these drawings without paying creative work.

[0021] Figure 1 This is a schematic diagram of an experiment on the effect of pH on the flotation of spodumene ore samples according to an embodiment of the present invention.

[0022] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only 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.

[0024] In addition, in the present invention, descriptions such as "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0025] Furthermore, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in the field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0026] The invention provides a method for preparing a collector compound.

[0027] The collector compound preparation method comprises:

[0028] Use a measuring cylinder to measure 50 mL, 0.6 mol of 1,3-propane sultone A and dissolve it in 0.1-1.0 L of ethyl acetate;

[0029] Slowly add 155 mL and 0.6 mL of N, N-dimethyloctylamine B to the previous reaction solution;

[0030] stirring the mixture at 20-100° C. for 1-10 h to carry out alkylation reaction of the amine;

[0031] After the reaction was completed, the reaction mixture was filtered to obtain a white precipitate;

[0032] The precipitate was washed twice with 10 ml of ethyl acetate and petroleum ether respectively, and finally the white solid C was dried in a vacuum oven at 100 °C;

[0033] The chemical formula of C is:

[0034]

[0035] In this embodiment, the sulfonic acid group (-SO 3 H) is a strong acidic group, which is easily ionized into hydrogen ions (H + ), forming a negatively charged sulfonate ion (-SO3 - ). Amino group (-NH 2 ) can be protonated under certain conditions to form a positively charged -NH 3 + The presence of metal ions (such as Li + The negatively charged sulfonate ions can interact with the metal ions on the spodumene surface through electrostatic attraction, while the positively charged -NH 3 + It can also produce electrostatic adsorption with certain negatively charged areas on the surface of spodumene. In addition, sulfonic acid groups and amino groups can also form chemical bonds with metal ions on the surface of spodumene, such as coordination bonds, and this chemical bonding can make the collector firmly adsorbed on the surface of spodumene. This strong adsorption performance helps to improve the collector's ability to collect spodumene, making spodumene more easily attached to bubbles, thereby improving the flotation recovery rate.

[0036] Compared with single-group collectors, the combination of sulfonic acid and amino groups can be more selectively adsorbed on the surface of spodumene due to its unique structure and charge distribution, while the adsorption of some gangue minerals is relatively weak. For example, gangue minerals such as quartz have different surface properties from spodumene. The collectors combined with sulfonic acid and amino groups can preferentially adsorb on the surface of spodumene based on the differences in charge complementarity and chemical bonding, reducing the collection of gangue minerals such as quartz. This helps to better separate spodumene and gangue minerals during the flotation process and improve the grade of the concentrate.

[0037] In addition, the present application also provides a collector compound C prepared by the above preparation method, and the chemical formula of the collector compound C is:

[0038]

[0039] In addition, the present invention also provides a mixed flotation agent, which comprises 35-65% of the collector compound as described above, 5-32% of a foaming agent, 5-25% of a depressant, 10-30% of a regulator and 10-50% of a solvent.

[0040] The foaming agent includes one or more of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride, pine oil, methyl isobutyl carbinol and polypropylene glycol.

[0041] The inhibitor includes one or more of dextrin, starch, water glass, and sodium hexametaphosphate.

[0042] The adjusting agent includes one or more of lime, hydrochloric acid, sulfuric acid, sodium sulfide, copper sulfate and sodium hexametaphosphate

[0043] The solvent includes water or alcohol.

[0044] The present application is described below through specific embodiments.

[0045] Example 1

[0046] The pH of the solution was adjusted by acid and alkali to observe the adaptability of DASA (compound C), DA and SDS to pH.

[0047] Step 1: Place the spodumene ore in a ball mill and grind it to 65%-75% below 200 mesh, and collect the slurry;

[0048] Step 2: The collected slurry is passed through a magnetic separator to remove magnetic minerals to obtain magnetic concentrate;

[0049] Step 3: Pour the concentrate after magnetic separation into a 1.5L flotation cell, adjust the speed of the flotation machine to 1250r / min, and stir the pulp in the flotation machine for 5 minutes; adjust the pH of the pulp by acid and alkali, and test it with pH test paper, and finally obtain 6 flotation cells with pH 2-12;

[0050] Step 4: slowly add 100-500 g / t of a flotation agent selected from the group consisting of DASA, DA and SDS, stir for 10 minutes, open the flotation machine for roughing, obtain roughing concentrate and roughing tailings, add 10-50 g / t of the flotation agent to the roughing tailings for scavenging, obtain scavenged ore and scavenged tailings, and return the scavenged ore to the roughing for refloatation;

[0051] Step 5: adding the flotation agent 50-150 g / t to the rougher concentrate and the scavenged ore obtained from the roughing again, performing the first concentration, obtaining the first concentrated middlings and the first concentrated concentrate, returning the first concentrated middlings to the roughing, performing the second concentration on the first concentrated concentrate, adding the flotation agent and stirring, then the concentrate participates in the next flotation, and the middlings return to the previous flotation operation to obtain spodumene concentrate.

[0052] The experimental results are as follows Figure 1 As shown, the L of DASA, DA, and SDS i2 The grade of O is the highest when pH is 4, and the maximum values ​​are 4.71, 3.32, and 3.06 respectively. As the pH increases, the L i2 The O grade has been decreasing, but the corresponding Li2O recovery rate has been increasing.

[0053] Example 2

[0054] The spodumene ore sample of this embodiment passed the test, and the original ore Li 2O grade is 1.52%, and flotation is carried out according to the flotation steps of spodumene. When configuring the flotation reagent of spodumene, the DASA of the present invention is replaced with DA / SDS, and flotation is carried out according to the same flotation steps. Finally, we obtain three spodumene concentrates.

[0055] The obtained spodumene concentrate was dried in an oven overnight, collected and mixed, and sent for testing. The test results showed that the spodumene concentrate grade of DASA agent was 4.76%, and the recovery rate could reach 87.3%, the spodumene concentrate grade of DA agent was 3.32%, and the recovery rate was 72.5%, and the spodumene concentrate grade of SDS agent was 3.03%, and the recovery rate could reach 66.9%.

[0056] For easy viewing, the following table is made:

[0057]

[0058] Table 1 Spodumene ore sample flotation concentrate

[0059] In summary, the amino- and sulfonic-acid-containing N-dodecyl-N-alkyl-sulfonic acid (compound C) provided by the present invention is compared with monosulfonic acid sodium dodecylsulfonate and monoaminododecylamine. The N-dodecyl-N-alkyl-sulfonic acid of the present invention has better selectivity for spodumene and stronger capture ability.

[0060] However, since the existence form and activity of sulfonic acid and amino groups change under different pulp conditions (such as pH value, temperature, mineral composition, etc.), their interaction mechanism with the spodumene surface is also relatively complex. This makes it difficult to accurately control the amount of collector used in the flotation process of specific production.

[0061] In general, the compound C provided by the present invention can be used under different pulp pH conditions, and the aminosulfonic acid reagent of the present invention is superior to the spodumene flotation reagent containing a sulfonic group / amino group. The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification and drawings, or directly / indirectly applied in other related technical fields under the concept of the present invention are included in the patent protection scope of the present invention.

Claims

1. A method for preparing a collector compound, characterized in that: The collector compound preparation method comprises: Use a measuring cylinder to measure 50 mL, 0.6 mol of 1,3-propane sultone A and dissolve it in 0.1-1.0 L of ethyl acetate; Slowly add 155 mL and 0.6 mL of N, N-dimethyloctylamine B to the previous reaction solution; stirring the mixture at 20-100° C. for 1-10 h to carry out alkylation reaction of the amine; After the reaction was completed, the reaction mixture was filtered to obtain a white precipitate; The precipitate was washed twice with 10 ml of ethyl acetate and petroleum ether respectively, and finally the white solid C was dried in a vacuum oven at 100 °C; The chemical formula of C is:

2. A collector compound, characterized in that The collector compound C is prepared by the collector compound preparation method according to claim 1, and the chemical formula of the collector compound C is:

3. A mixed flotation agent, characterized in that: The mixed flotation agent comprises 35-65% of the collector compound as claimed in claim 2, 5-32% of a foaming agent, 5-25% of a depressant, 10-30% of a regulator and 10-50% of a solvent.

4. The mixed flotation agent according to claim 3, characterized in that: The foaming agent includes one or more of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride, pine oil, methyl isobutyl carbinol and polypropylene glycol.

5. The mixed flotation agent according to claim 3, characterized in that: The inhibitor includes one or more of dextrin, starch, water glass, and sodium hexametaphosphate.

6. The mixed flotation agent according to claim 3, characterized in that: The adjusting agent includes one or more of lime, hydrochloric acid, sulfuric acid, sodium sulfide, copper sulfate and sodium hexametaphosphate.

7. The mixed flotation agent according to claim 3, characterized in that: The solvent includes water or alcohol.

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