Gemini type surfactant compound, preparation method and spodumene collecting agent

Abstract

The invention discloses a Gemini type surfactant compound, a preparation method and a spodumene collecting agent. The Gemini type surfactant compound provided by the invention is a compound with the following chemical structural general formula or a chemical isomer or salt thereof: # imgabs0 #. Compared with a traditional monoamine cation collecting agent, the Gemini type surfactant provided by the invention has the advantages that the selectivity is better, the collecting capacity is stronger, the dosage of the agent is lower, and the Gemini type surfactant compound is more resistant to low temperature.

Description

Technical Field

[0001] The invention relates to a Gemini type surfactant compound, a preparation method and a spodumene collector. Background Art

[0002] Gemini surfactants have shown many unique advantages in spodumene flotation. First, they have a special molecular structure. Compared with traditional surfactants, they have two hydrophilic groups and two hydrophobic groups, which makes them more adsorbed on the surface of spodumene. They can be arranged more tightly and orderly on the surface of spodumene particles, greatly changing the wettability of the spodumene surface, enhancing its adhesion to bubbles, and significantly improving the flotation recovery rate.

[0003] Secondly, the critical micelle concentration of Gemini surfactants is lower, which means that they can exert good surface activity at lower concentrations, reducing the amount of reagents used, which not only reduces flotation costs, but also reduces environmental pollution.

[0004] Furthermore, it has high selectivity. The flotation environment of spodumene is complex and there are many associated minerals. Gemini surfactants can accurately identify spodumene and preferentially adsorb on the surface of spodumene, while having a weaker effect on other impurity minerals, effectively improving the grade of spodumene concentrate, making the final lithium product of higher quality and more in line with industrial production needs. Summary of the invention

[0005] The main purpose of the present invention is to provide a Gemini surfactant compound, a preparation method and a spodumene collector, aiming to solve the above technical problems.

[0006] To achieve the above object, the present invention provides a Gemini surfactant compound having the following general chemical structure or its chemical isomer or salt:

[0007]

[0008] in:

[0009] n is 1, 2 or 3;

[0010] R is methyl or ethyl.

[0011] In one embodiment, the compound is one of the following compounds:

[0012]

[0013] In addition, the present invention also provides a method for preparing a Gemini-type surfactant compound, the method for preparing a Gemini-type surfactant compound comprising:

[0014] After mixing compound A, aluminum hydroxide and hydrochloric acid, slowly adding compound B into the mixture to obtain compound C;

[0015] Pour compound C into a mixture of phosphoric acid and chlorobenzene, heat until dissolved, drop phosphorus trichloride into the mixture, heat and stir the mixture, and then stir at room temperature;

[0016] The solvent chlorobenzene was decanted, the residue was removed under reduced pressure, water was added to the resulting yellow residue, and the mixture was heated to reflux;

[0017] Add activated carbon to the mixture, stir, filter and concentrate the solution to obtain a viscous crude product, which is then recrystallized with an appropriate amount of water and washed with acetone to obtain a white compound D;

[0018] Wherein, the chemical formula of compound A is:

[0019]

[0020] The chemical formula of the compound B is:

[0021] CI(CH 2 )nCOOH;

[0022] The chemical formula of the compound C is:

[0023]

[0024] The chemical formula of the compound D is:

[0025]

[0026] in:

[0027] n is 1, 2, or 3;

[0028] R is methyl or ethyl;

[0029] In addition, the present invention also provides a spodumene collector, which comprises 35-65% of the compound D as claimed in claim 13, 5-20% of an anion collector and 10-40% of a solvent.

[0030] In one embodiment, the anionic collector includes one or a mixture of N-dodecyl-N-alkyl-sulfonic acid, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid, sodium olefin sulfonate, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid, oleic acid, sodium oleate, cyclohexane acid soap, tall oil, peroxy fatty acid soap, salicylic hydroxamic acid, and benzohydroxamic acid.

[0031] In one embodiment, the solvent includes water or alcohol.

[0032] In the technical solution of the present invention, the Gemini surfactant compound provided in the present application has better selectivity, stronger capturing ability, lower dosage and better resistance to low temperature than the traditional monoamine cationic collector. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] 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.

[0034] Figure 1 Schematic diagram of the process of spodumene flotation method according to an embodiment of the present invention;

[0035] Figure 2 This is a schematic diagram of an experiment on the effect of pH on flotation of ore samples with different collectors in Example 1 of the present invention;

[0036] Figure 3 This is a schematic diagram of an experiment showing the effect of collector dosage on ore sample flotation in Example 2 of the present invention;

[0037] Figure 4 This is a schematic diagram of an experiment on the effect of temperature on the flotation of ore samples with different collectors in Example 3 of the present invention.

[0038] 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

[0039] 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.

[0040] 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.

[0041] 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.

[0042] The present invention provides a Gemini-type surfactant compound.

[0043] like Figure 1 As shown, the Gemini surfactant compound (Compound D) provided in the embodiment of the present invention is a compound having the following chemical structural formula or its chemical isomer or salt thereof:

[0044]

[0045] The specific steps of the synthesis are as follows: 10.0 mmol, 1.022 g of compound A (N, N'-dimethyl-1, 3-propylenediamine), aluminum hydroxide and hydrochloric acid are mixed, and then 12.0 mmol, 1.134 g of compound B (chloroformic acid) is slowly added to the mixture to obtain compound C;

[0046] Pour 10.0 mmol, 2.18 g of compound C into a mixture of phosphoric acid and 5 L of chlorobenzene, heat until dissolved, dropwise add phosphorus trichloride to the mixture, heat and stir the mixture, and then stir at room temperature;

[0047] The solvent chlorobenzene was decanted, the residue was removed under reduced pressure, water was added to the resulting yellow residue, and the mixture was heated to reflux;

[0048] Add activated carbon to the mixture, stir, filter and concentrate the solution to obtain a viscous crude product, which is then recrystallized with an appropriate amount of water and washed with acetone to obtain a white compound D;

[0049] Wherein, the chemical formula of compound A is:

[0050]

[0051] The chemical formula of the compound B is:

[0052] CI(CH 2 )nCOOH;

[0053] The chemical formula of the compound C is:

[0054]

[0055] The chemical formula of the compound D is:

[0056]

[0057] in:

[0058] n is 1, 2, or 3

[0059] R is methyl or ethyl.

[0060] Specifically, the synthesis route of Gemini surfactant compound B is as follows: Figure 1 Further, when compound A is as follows:

[0061]

[0062] When compound B is as follows:

[0063]

[0064] pass Figure 1 The Gemini surfactants produced by the synthetic route are as follows:

[0065] Further, when compound A is as follows:

[0066]

[0067] When compound B is as follows:

[0068]

[0069] pass Figure 1 The Gemini surfactants produced by the synthetic route are as follows:

[0070] Further, when compound A is as follows:

[0071]

[0072] When compound B is as follows:

[0073]

[0074] pass Figure 1 The Gemini surfactants produced by the synthetic route are as follows:

[0075] Further, when compound A is as follows:

[0076]

[0077] When compound B is as follows:

[0078]

[0079] pass Figure 1 The Gemini surfactants produced by the synthetic route are as follows:

[0080]

[0081] Further, when compound A is as follows:

[0082]

[0083] When compound B is as follows:

[0084]

[0085] pass Figure 1 The Gemini surfactants produced by the synthetic route are as follows:

[0086]

[0087] Further, when compound A is as follows:

[0088]

[0089] When compound B is as follows:

[0090]

[0091] pass Figure 1 The Gemini surfactants produced by the synthetic route are as follows:

[0092]

[0093] Further, the present invention provides a spodumene collector, which comprises 35-65% of the Gemini surfactant compound (compound D) as described above, 5-20% of anionic collector and 10-40% of solvent. Compound D is selected from at least one compound in the above embodiments.

[0094] Furthermore, the anionic collector includes one or a mixture of N-dodecyl-N-alkyl-sulfonic acid, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid, sodium olefin sulfonate, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid, oleic acid, sodium oleate, cyclohexane acid soap, tall oil, peroxy fatty acid soap, salicylic hydroxamic acid, and benzohydroxamic acid.

[0095] Furthermore, the solvent includes water or alcohol.

[0096] The dihydroxy structure gives the agent good hydrophilicity and the ability to hydrogen bond with the surface of spodumene. By forming hydrogen bonds with specific sites on the surface of spodumene, it can effectively improve the surface properties of spodumene, enhance its dispersibility in the flotation system, and make spodumene particles more easily interact with flotation agents and bubbles.

[0097] The four phosphite groups increase the chemical adsorption capacity of the reagent on spodumene. The phosphite groups can react chemically with the metal ions on the surface of spodumene to form stable chemical bonds, which are firmly adsorbed on the surface of spodumene, greatly improving the adsorption stability of the reagent on the surface of spodumene, thereby improving the flotation effect.

[0098] The two tertiary amine groups further enhance the selectivity of the agent. Due to its unique electronic structure and spatial configuration, the tertiary amine group can accurately identify spodumene, preferentially react with spodumene, and has weak adsorption on other associated minerals. In a complex flotation environment, this high selectivity can effectively reduce the floating of impurity minerals, improve the grade of spodumene concentrate, and provide high-quality raw materials for the subsequent processing and utilization of lithium products. In general, this type of Gemini surfactant can theoretically provide a strong guarantee for the efficient and accurate flotation of spodumene.

[0099] The present application is experimentally described below through specific examples.

[0100] Example 1

[0101] Flotation tests were conducted in the laboratory to adjust the pH of the solution to see the adaptability of Gemini surfactants and monoamine collectors to pH.

[0102] Step 1: Place the spodumene ore in a ball mill and grind it to 70%-85% below 200 mesh, and collect the slurry;

[0103] Step 2: The collected slurry is passed through a magnetic separator to remove magnetic minerals to obtain magnetic concentrate;

[0104] Step 3: Pour the concentrate after magnetic separation into a 1.5L flotation cell, adjust the speed of the flotation machine to 1400r / min, and stir the slurry in the flotation machine for 8 minutes; adjust the pH of the slurry and test it with pH test paper, and finally obtain 6 flotation cells with pH 2-12;

[0105] Step 4: slowly adding 50-1000 g / t of a flotation agent selected from the Gemini surfactant and the monoamine collector, stirring for 10 minutes, opening the flotation machine for roughing to obtain a roughing concentrate and a roughing tailing, adding 10-100 g / t of the flotation agent to the roughing tailing for scavenging to obtain scavenged ore and scavenged tailings, and returning the scavenged ore to the roughing for refloatation;

[0106] Step 5: adding the flotation agent 25-250 g / t to the rougher concentrate and the scavenged ore again, performing the first concentration, obtaining the first concentrated middlings and the first concentrated concentrate, returning the first concentrated middlings to the rougher, 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 the spodumene concentrate.

[0107] The experimental results are as follows Figure 2 As shown in the figure, the grade of monoamine collector is the largest at pH 2, while the grade of Gemini surfactant is the largest at pH 6. The maximum values ​​are 3.74 and 4.77 respectively. As the pH increases, the Li2O grade of DA concentrate has been decreasing, but the corresponding Li2O recovery rate is increasing. The Li2O grade of Gemini concentrate increases when the pH is 2-6, and then decreases as the pH increases. Phosphorous acid is a medium-strong acid. In a strong acidic environment (pH 2-6), phosphorous acid exists in molecular form or partially ionized and dissolved. In this case, it may react with certain components on the surface of lithium concentrate, thereby enhancing the floatability of lithium concentrate. As the pH increases to 8-12, the concentration in the solution increases, the existence form of tertiary amines may change, and some tertiary amines may exist in a free form, reducing their effective adsorption on the surface of lithium concentrate, thereby reducing the recovery rate of lithium concentrate. At the same time, too high a pH value will also cause changes in the surface properties of lithium concentrate, such as changes in surface potential, which will weaken the electrostatic adsorption between tertiary amines and lithium concentrate.

[0108] Example 2

[0109] Using the spodumene particles in the above example, the flotation test of the new Gemini collector and the DA collector at different dosages was compared at pH = 6, and the flotation was carried out according to the same flotation steps. The test results are shown in Figure 2. Figure 3 As shown in the figure, with the increase of the dosage of reagents, the grade of spodumene concentrate flotated by Gemini surfactant drops from 4.77% to 2.12%. This is because phosphorous acid may compete with the collector molecules for the metal ion active centers adsorbed on the surface of spodumene, resulting in the collector not being able to play a good role in selectively collecting spodumene. When the agglomerates are floated up, the concentrate will contain more gangue components, causing the concentrate grade to drop. Excessive hydroxyl groups will also increase the viscosity of the slurry. High-viscosity slurry will affect the dispersion of mineral particles and the bubble-particle attachment during flotation. In high-viscosity slurry, when bubbles carry mineral particles to float, they may also carry some gangue mineral particles that should not float, thereby reducing the grade of the concentrate.

[0110] Example 3

[0111] Using the above spodumene particles, the flotation test of the new Gemini collector (135g / t) and the monoamine collector (400g / t) at different temperatures was compared at pH = 6. The test results are as follows: Figure 4 As shown in the figure, as the temperature rises, the grade of Gemini increases from 2.63% to 4.78% at 25℃. As the temperature rises, the activity of phosphorous acid gradually increases. The ionization equilibrium and chemical reaction rate of phosphorous acid groups in the solution are affected by temperature. In this temperature range, the reaction of phosphorous acid with the surface of spodumene may be more sufficient, better adjust the properties of the surface of spodumene, remove some harmful impurities on the surface of spodumene, or activate the active sites on the surface of spodumene. This is conducive to the adsorption of subsequent collectors, thereby increasing the grade and recovery rate of the concentrate. When the temperature exceeds 25 degrees Celsius, phosphorous acid will undergo some side reactions or decomposition reactions. For example, phosphorous acid may undergo oxidation reactions with dissolved oxygen in water at higher temperatures, resulting in a reduction in its effective components. At the same time, excessively high temperatures will destroy the adsorption equilibrium on the surface of spodumene. Phosphorous acid molecules or ions originally adsorbed on the surface of spodumene may desorb due to excessive thermal motion, making the properties of the surface of spodumene worse, which is not conducive to the adsorption of collectors, and thus leads to a decrease in the grade and recovery rate of the concentrate.

[0112] In summary, compared with the monoamino collector, the new Gemini surfactant provided by the present invention has better selectivity, stronger collecting ability, lower dosage and better resistance to low temperature than the monoamino collector.

[0113] 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 under the concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A Gemini surfactant compound, characterized in that: The Gemini surfactant compound is a compound having the following general chemical structure or a chemical isomer or a salt thereof: in: n is 1, 2 or 3; R is methyl or ethyl.

2. The Gemini surfactant compound according to claim 1, characterized in that The compound is one of the following compounds:

3. A method for preparing a Gemini surfactant compound, characterized in that: The method for preparing the Gemini surfactant compound comprises: After mixing compound A, aluminum hydroxide and hydrochloric acid, slowly adding compound B into the mixture to obtain compound C; Pour compound C into a mixture of phosphoric acid and chlorobenzene, heat until dissolved, drop phosphorus trichloride into the mixture, heat and stir the mixture, and then stir at room temperature; The solvent chlorobenzene was decanted, the residue was removed under reduced pressure, water was added to the resulting yellow residue, and the mixture was heated to reflux; Add activated carbon to the mixture, stir, filter and concentrate the solution to obtain a viscous crude product, which is then recrystallized with an appropriate amount of water and washed with acetone to obtain a white compound D; Wherein, the chemical formula of compound A is: The chemical formula of the compound B is: C|(CH2)nCOOH; The chemical formula of the compound C is: The chemical formula of the compound D is: in: n is 1, 2, or 3 R is methyl or ethyl.

4. A spodumene collector, characterized in that, The spodumene collector comprises 35-65% of the compound D as claimed in claim 3, 5-20% of an anion collector and 10-40% of a solvent.

5. The spodumene collector according to claim 4, wherein The anionic collector includes one or a mixture of N-dodecyl-N-alkyl-sulfonic acid, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid, sodium olefin sulfonate, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid, oleic acid, sodium oleate, cyclohexane acid soap, tall oil, peroxy fatty acid soap, salicylic hydroxamic acid, and benzohydroxamic acid.

6. The spodumene collector according to claim 4, wherein The solvent includes water or alcohol.

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