Gemini type surfactant, preparation method and spodumene mixed collecting agent

Abstract

The invention discloses a Gemini type surfactant, a preparation method and a spodumene mixed collecting agent. The Gemini type surfactant provided by the invention is a compound with the following chemical structural general formula or a chemical isomer or salt thereof: # imgabs0 #. Compared with DA, the novel Gemini type surfactant provided by the invention has the advantages that the selectivity is better, the collecting capacity is higher, the dosage of the agent is lower, the low temperature resistance is higher, the influence of ore pulp environment change is relatively small, and the application range is wide. And good collecting performance can be kept within a wide pH value range and under different temperature conditions, the flotation agent adapts to the complex and changeable ore pulp environment, and the stability of the flotation effect is guaranteed.

Description

Technical Field

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

[0002] As a new type of surfactant, Gemini surfactants shine in many fields with their unique structure and excellent performance.

[0003] Structurally, it breaks the pattern of traditional single-chain surfactants and is composed of two or more identical or similar monomers connected by a special linking group, like a pair of closely cooperating "twin stars". Each monomer has a hydrophilic group and a hydrophobic chain. This unique structure gives it many advantages.

[0004] In terms of surface activity, Gemini surfactants are extraordinary. They can effectively reduce the surface tension of aqueous solutions, and the required concentration is extremely low, and the critical micelle concentration is much lower than that of traditional surfactants. This means that in practical applications, only a small amount of agents is needed to achieve the desired effect, which saves costs and improves efficiency. For example, in the field of industrial cleaning, a stronger decontamination ability can be achieved with less dosage.

[0005] Its selectivity is even more remarkable. By flexibly adjusting the hydrophilic and hydrophobic groups and connecting parts in the molecular structure, it can precisely "strike force" on minerals. During flotation, it can capture specific minerals in a targeted manner and help to efficiently separate ores. Summary of the invention

[0006] The main purpose of the present invention is to provide a Gemini surfactant, a preparation method and a spodumene mixed collector, aiming to provide a Gemini surfactant to improve the flotation effect of spodumene.

[0007] To achieve the above object, the present invention provides a method for preparing a Gemini surfactant, comprising:

[0008] 70 mL, 550 mmol, of glutaryl dichloride C5H6O2C diluted in 20 mL of DCM l2 111 mL, 1.1 mol, 2-dimethylaminoethanol (C4H) diluted in 20 mL DCM was added dropwise 11 NO, stirring for 5-30h;

[0009] The mixture was concentrated under vacuum and purified by recrystallization from THF to obtain intermediate C in the form of a dark brown solid. The precipitate was washed with hexane to remove excess glutaryl chloride, 2-dimethylaminoethanol and THF.

[0010] Product C was added to 500 mL of chloroform, and then washed and neutralized with 1N aqueous ammonium hydroxide solution at 0°C to a pH of 6-12 to obtain an intermediate product D. The liquid intermediate product D was obtained by vacuum concentrating the DCM phase;

[0011] The intermediate product D is subjected to a quaternization reaction with a halogenated hydrocarbon in anhydrous THF at 80°C for 8-20 hours, and then precipitated in ether to finally obtain a viscous liquid Gemini surfactant F;

[0012] The chemical formula of the compound A is:

[0013]

[0014] The chemical formula of the compound B is:

[0015]

[0016] The chemical formula of the compound C is:

[0017]

[0018] The chemical formula of the compound D is:

[0019]

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

[0021]

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

[0023]

[0024] in:

[0025] n and m are any integers from 1 to 10.

[0026] In one embodiment, the compound F is one of the following compounds:

[0027]

[0028] In addition, the present invention also provides a Gemini-type surfactant, wherein the Gemini-type surfactant F is prepared by the Gemini-type surfactant preparation method according to claim 1.

[0029] In addition, the present invention also provides a spodumene mixed collector, which comprises 35-65% of the Gemini surfactant as claimed in claim 3, 10-50% of anionic collector and 20-40% of solvent.

[0030] In one embodiment, the anionic collector includes 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 acid, benzoic acid, or a mixture of several thereof.

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

[0032] In the technical solution of the present invention, the Gemini surfactant provided in this application has better selectivity, stronger capture ability, lower dosage of reagents and better resistance to low temperatures than DA. 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 synthesis route of the Gemini surfactant 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 on the effect of pH on flotation of ore samples with different collectors 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 novel Gemini surfactant.

[0043] The Gemini surfactant 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] Where n and m are any integers between 1 and 10;

[0046] Please refer to Figure 1 The specific steps of synthesis are:

[0047] 70 mL, 550 mmol, of glutaryl dichloride C5H6O2C diluted in 20 mL of DCM l2 111 mL, 1.1 mol, 2-dimethylaminoethanol (C4H) diluted in 20 mL DCM was added dropwise 11 NO, stirring for 5-30h;

[0048] The mixture was concentrated under vacuum and purified by recrystallization from THF to obtain intermediate C in the form of a dark brown solid. The precipitate was washed with hexane to remove excess glutaryl chloride, 2-dimethylaminoethanol and THF.

[0049] Product C was added to 500 mL of chloroform, and then washed and neutralized with 1N aqueous ammonium hydroxide solution at 0°C to a pH of 6-12 to obtain an intermediate product D. The liquid intermediate product D was obtained by vacuum concentrating the DCM phase;

[0050] The intermediate product D is reacted with a halogenated hydrocarbon in anhydrous THF at 80°C for 8-20 hours to undergo quaternization reaction, and then precipitated in ether to finally obtain a viscous liquid Gemini surfactant F.

[0051] Where: n and m are any integers between 1 and 10;

[0052] Further, when compound A is as follows:

[0053]

[0054] When compound E is as follows:

[0055]

[0056] The Gemini surfactants produced by the above synthesis route are as follows:

[0057]

[0058] Further, when compound A is as follows:

[0059]

[0060] When compound E is as follows:

[0061]

[0062] The Gemini surfactants produced by the above synthesis route are as follows:

[0063]

[0064] Further, when compound A is as follows:

[0065]

[0066] When compound E is as follows:

[0067]

[0068] The Gemini surfactants produced by the above synthesis route are as follows:

[0069]

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

[0071]

[0072] When compound E is as follows:

[0073]

[0074] The Gemini surfactants produced by the above synthesis route are as follows:

[0075]

[0076] In addition, according to the properties of spodumene of Jiuling Lithium, the Gemini surfactant of the present invention and the anionic collector are used to form a mixed flotation agent, which includes 35-65% of Gemini surfactant, 10-50% of anionic collector and 20-40% of solvent.

[0077] Furthermore, the anionic collector includes one or a mixture of 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.

[0078] Furthermore, the solvent includes water or alcohol.

[0079] The structural characteristics of diester and diquaternary amine increase the number of interaction sites on the surface of spodumene, allowing them to adsorb more firmly on the surface of spodumene, thereby enhancing their ability to capture spodumene. At the same time, this special structure increases the difference in adsorption between spodumene and other gangue minerals, improves the selectivity of flotation, and can more accurately separate spodumene from the ore, which is beneficial to improving the grade of lithium concentrate. Due to its efficient capture performance and good selectivity, compared with traditional single collectors, when using diester and diquaternary amine collectors, the amount of reagents can be reduced while achieving the same flotation effect, thereby reducing production costs and improving economic benefits, and it is also beneficial to reduce the pollution of the reagents to the environment.

[0080] Diester and diquaternary amine may produce a synergistic effect during the flotation process, further optimizing the flotation effect. The combination of the two will change the surface properties of the pulp and the properties of the flotation interface, promote the attachment of spodumene particles and bubbles, and improve the flotation recovery rate and concentrate grade. In addition, diester and diquaternary amine collectors have good chemical stability and are relatively less affected by changes in the pulp environment. They can maintain good collection performance in a wide pH range and under different temperature conditions, adapt to complex and changeable pulp environments, and ensure the stability of the flotation effect.

[0081] The present application is described below through specific embodiments.

[0082] Example 1

[0083] Flotation tests were conducted in a laboratory environment, and the pH of the solution was adjusted with acid and alkali to see the adaptability of Gemini surfactants and DA to pH.

[0084] Step 1: Place the spodumene ore in a ball mill and grind it to 65%-75% below 200 mesh, and collect the slurry;

[0085] Step 2: The collected slurry is passed through a magnetic separator to remove magnetic minerals to obtain magnetic concentrate;

[0086] Step 3: Pour the concentrate after magnetic separation into a 1.5L flotation cell, adjust the speed of the flotation machine to 1300r / 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;

[0087] Step 4: slowly add the Gemini surfactant and a flotation agent in DA at 50-500 g / t, stir for 10 minutes, open the flotation machine for roughing, obtain roughing concentrate and roughing tailings, add the flotation agent at 10-50 g / t to the roughing tailings for scavenging, obtain scavenged ore and scavenged tailings, and return the scavenged ore to the roughing for refloatation;

[0088] 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.

[0089] The experimental results are as follows Figure 2 As shown, the grade of DA is the largest at pH 4, while the grade of Gemini surfactant is the largest at pH 6. The maximum values ​​are 3.71 and 5.19 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. This is because in a high pH environment, more functional groups such as hydroxyl (-OH) will form on the surface, resulting in an increase in its surface negative charge. For mineral particles that have already adsorbed Gemini collectors, this charge change will weaken the adsorption effect between the collector and the mineral surface. Because Gemini collectors are combined with the mineral surface through electrostatic attraction, chemical adsorption, etc., changes in the charge on the mineral surface will destroy the original electrostatic effect.

[0090] Example 2

[0091] 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 3As shown in the figure, with the increase of reagent usage, the grade of Gemini and DA decreases from 5.27% and 4.31%. This is because when the amount of collector increases, the collector will be adsorbed on the surface of some gangue minerals in addition to the target mineral surface. Because the collector molecules have certain activity, more collectors will interact with gangue minerals at high concentrations. The presence of a large amount of collectors may cause agglomeration between mineral particles in the slurry. This agglomeration may wrap some gangue minerals and target minerals. When the agglomerates are floated up, the concentrate will contain more gangue components, causing the concentrate grade to decrease.

[0092] As the grade decreases, the recovery rates of Gemini and DA both increase. This is because as the amount of collector increases, the surface of the target mineral can be more fully covered. More collectors are adsorbed on the surface of the target mineral, making the hydrophobicity of the mineral surface further enhanced. During the flotation process, the probability of bubbles attaching to the mineral surface increases, and more target minerals can attach to the bubbles and be brought to the foam layer, thereby improving the recovery rate.

[0093] Example 3

[0094] Using the above spodumene particles, the flotation test of the new Gemini collector (125g / t) and DA collector (300g / 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 3.25% to 5.21% at 25℃. The increase in temperature helps the collector molecules to better identify the target minerals, the activity of the collector molecules increases, and the chemical adsorption and physical adsorption between them and the active sites on the surface of the target minerals are more precise. The increase in temperature will change the viscosity of the slurry. As the temperature rises, the viscosity of the slurry decreases. Lower viscosity is conducive to the dispersion of mineral particles in the slurry, making it easier to separate the target minerals from the gangue minerals.

[0095] In summary, compared with monoaminododecylamine, the new Gemini surfactant provided by the present invention has better selectivity, stronger capture ability, lower dosage and better resistance to low temperature than DA.

[0096] 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 method for preparing a Gemini surfactant, characterized in that: The method for preparing the Gemini surfactant comprises: 70 mL, 550 mmol, of glutaryl dichloride C5H6O2C diluted in 20 mL of DCM l2 111 mL, 1.1 mol, 2-dimethylaminoethanol (C4H) diluted in 20 mL DCM was added dropwise 11 NO, stirring for 5-30h; The mixture was concentrated under vacuum and purified by recrystallization from THF to obtain intermediate C in the form of a dark brown solid. The precipitate was washed with hexane to remove excess glutaryl chloride, 2-dimethylaminoethanol and THF. Product C was added to 500 mL of chloroform, and then washed and neutralized with 1N aqueous ammonium hydroxide solution at 0°C to a pH of 6-12 to obtain an intermediate product D. The liquid intermediate product D was obtained by vacuum concentrating the DCM phase; The intermediate product D is subjected to a quaternization reaction with a halogenated hydrocarbon in anhydrous THF at 80°C for 8-20 hours, and then precipitated in ether to finally obtain a viscous liquid Gemini surfactant F; The chemical formula of the compound A is: The chemical formula of the compound B is: The chemical formula of the compound C is: The chemical formula of the compound D is: The chemical formula of the compound E is: The chemical formula of the compound F is: in: n and m are any integers from 1 to 10.

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

3. A Gemini surfactant, characterized in that: The Gemini surfactant F is prepared by the Gemini surfactant preparation method according to claim 1.

4. A spodumene mixed collector, characterized in that: The spodumene mixed collector comprises 35-65% of the Gemini surfactant as claimed in claim 3, 10-50% of anionic collector and 20-40% of solvent.

5. The spodumene mixed collector according to claim 5, wherein The anionic collector includes 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, cyclopentane acid soap, tall oil, peroxy fatty acid soap, salicylic hydroxamic acid, benzoic hydroxamic acid or a mixture of several thereof.

6. The spodumene mixed collector according to claim 5, characterized in that, The solvent includes water or alcohol.

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