Sulfocarboxylic acid anion collector compound, preparation method and mixed flotation agent

Abstract

The invention discloses a sulfocarboxylic acid anion collector compound, a preparation method and a mixed flotation agent. The sulfocarboxylic acid anion collector compound provided by the invention is a compound with the following chemical structural general formula or a chemical isomer or salt thereof: # imgabs0 #. A disulfonic acid group in the sulfocarboxylic acid anion collector compound disclosed by the invention has higher adsorption capacity; therefore, higher selectivity is brought. The hydrophilic and hydrophobic characteristics of the collecting agent can be adjusted in the presence of the sulfonic acid group and the carboxylic acid group, so that the collecting agent can achieve a better flotation effect under different flotation conditions.

Description

Technical Field

[0001] The invention relates to a sulfocarboxylic acid anion collector compound, a preparation method and a mixed flotation agent. Background Art

[0002] Sulfonic acid groups are strong acidic groups with strong water solubility. Collectors containing sulfonic acid groups and other flotation reagents can be better dissolved in the ore pulp aqueous solution, ensuring the uniform dispersion of the reagents in the flotation system, so as to effectively play their flotation role. For example, some anionic collectors containing sulfonic acid groups can be fully ionized in water to form negatively charged ions, increasing the chance of interaction with the positively charged or neutral lithium ore surface.

[0003] Sulfonic acid groups can interact with metal ions or other active sites on the surface of lepidolite through chemical bonding or physical adsorption. On the one hand, the oxygen atoms in the sulfonate ions can form coordination bonds with the metal ions on the surface of lepidolite, allowing the collector to be firmly adsorbed on the mineral surface; on the other hand, the polarity and charge characteristics of the sulfonic acid group also enable it to produce physical adsorption such as electrostatic attraction and van der Waals force with the mineral surface, enhancing the adsorption strength of the collector on the surface of lepidolite and improving the collection effect.

[0004] At present, in the process of lithium ore flotation, most of the anionic collectors used contain carboxylic acid groups, so how to improve the sulfonyl carboxylic acid collectors is an urgent problem to be solved. Summary of the invention

[0005] The main purpose of the present invention is to provide a sulfonylcarboxylic acid anion collector compound, aiming to solve the above technical problems.

[0006] To achieve the above object, the present invention provides a sulfocarboxylic acid anion collector compound, wherein the sulfocarboxylic acid anion collector compound is a compound having the following chemical structural formula or its chemical isomer or salt thereof:

[0007]

[0008] in:

[0009] n is any number between 1 and 10;

[0010] M is H, Na, or K.

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

[0012]

[0013]

[0014] In addition, the present invention also provides a method for preparing a sulfocarboxylic acid anion collector compound, the method for preparing a sulfocarboxylic acid anion collector compound comprising:

[0015] Take a clean and dry high temperature and high pressure reactor, weigh 0.2-0.8 of powdered or block cerium hydroxide catalyst;

[0016] Add lipoic acid dropwise into the reactor and stir for 10-30 min;

[0017] 1-10 parts of hydrogen peroxide solution are added into the stirred reactor at a rate of 1 drop / s;

[0018] Pressurizing the reactor charged with reactants;

[0019] After the pressurization is completed, the reactor is placed on a heating device for heating, the required heating temperature is, and stirring is performed;

[0020] After the reaction is completed, the mixture is naturally cooled to room temperature, and supersaturated saline is added to quench the reaction to obtain compound B;

[0021] Wherein, the chemical structure formula of the compound B is:

[0022]

[0023] in:

[0024] n is any number between 1 and 10;

[0025] M is H, Na, or K.

[0026] In one embodiment, the pressure during pressurization is 5-40 MPa, the temperature during heating is 50-700° C., and the stirring time is 0.1-2 h.

[0027] In addition, the present invention also provides a mixed flotation agent, which comprises 40-70% of the sulfonylcarboxylic acid compound B according to any one of claims 1 to 2, 15-40% of amines, 5-20% of fatty acids / salts and 10-30% of alcohols.

[0028] In one embodiment, the amines include one or more of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, and dodecyltrimethylammonium chloride.

[0029] In one embodiment, the fatty acid / salt comprises one or more of linoleic acid, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid.

[0030] In one embodiment, the alcohol includes one or more of methanol, ethanol, propanol, n-butanol, etc.

[0031] In the technical scheme of the present invention, both the sulfonic acid group and the carboxylic acid group belong to anionic collecting groups, which can react chemically with the cations on the surface of spodumene to form chemical bonds or electrostatic adsorption, so that the collector is firmly adsorbed on the surface of spodumene. This adsorption mode of double active sites greatly increases the adsorption capacity of the collector and the mineral surface compared to the collector of a single group, and improves the selectivity and recovery rate of flotation. The disulfonic acid group has a stronger adsorption capacity, thereby bringing higher selectivity. The presence of the sulfonic acid group and the carboxylic acid group can adjust the hydrophilic and hydrophobic characteristics of the collector, so that it can achieve a good flotation effect under different flotation conditions. DETAILED DESCRIPTION

[0032] 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.

[0033] 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.

[0034] 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.

[0035] The invention provides a sulfonylcarboxylic acid anion collector compound.

[0036] The sulfonylcarboxylic acid anion collector compound provided in the embodiment of the present invention is a compound having the following chemical structural formula or its chemical isomer or salt thereof:

[0037]

[0038] The specific operation steps of the synthesis are: take a clean and dry high-temperature and high-pressure reactor, and weigh 0.2-0.8 parts, preferably 0.63 parts, of a powdered or block cerium hydroxide catalyst.

[0039] Add 1 portion of lipoic acid A dropwise into the reactor and stir for 10-30 min;

[0040] After adding the raw materials to the reactor after stirring, add hydrogen peroxide solution again, the hydrogen peroxide fraction is 1-10 parts, pay attention to the dripping speed of hydrogen peroxide, it should not be too fast, the optimal speed is 1 drop / s;

[0041] Pressurize the reactor charged with reactants to a pressure of 5-40 MPa, more preferably 20-35 MPa;

[0042] After the pressurization is completed, the reactor is placed on a heating device for heating at a required heating temperature of 50-700° C., preferably 200-600° C., more preferably 350-500° C., and stirred.

[0043] The stirring time is 0.1-2h, preferably 0.1-1h, more preferably 0.1-0.3h;

[0044] After the reaction was completed, the mixture was cooled to room temperature and supersaturated saline was added to quench the reaction.

[0045] Finally, product B is obtained by column chromatography, and product C is obtained by adding the corresponding carbonate and stirring.

[0046] Wherein, the chemical structure formula of the compound A is:

[0047]

[0048] Specifically, the synthesis route of the sulfocarboxylic acid anion collector compound B is as follows:

[0049]

[0050] Further, when compound A is as follows:

[0051]

[0052] The sulfocarboxylic acid compound B / C generated by the above synthesis route is as follows:

[0053]

[0054] Further, when compound A is as follows:

[0055]

[0056] The sulfocarboxylic acid compound B / C generated by the above synthesis route is as follows:

[0057]

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

[0059]

[0060] The sulfocarboxylic acid compound B / C generated by the above synthesis route is as follows:

[0061]

[0062] Further, when compound A is as follows:

[0063]

[0064] The sulfocarboxylic acid compound B / C generated by the above synthesis route is as follows:

[0065]

[0066] In the above example:

[0067] n is any number between 1 and 10;

[0068] M is H, Na, or K.

[0069] Further, the present invention provides a flotation agent, which comprises 40-70% of the above-mentioned sulfocarboxylic acid anion collector compound C, 15-40% of amines, 2-20% of fatty acids / salts and 10-30% of alcohols. The sulfocarboxylic acid anion collector compound C is selected from at least one compound in the above-mentioned embodiments.

[0070] Both sulfonic acid groups and carboxylic acid groups are anionic collector groups, which can react chemically with cations on the surface of spodumene to form chemical bonds or electrostatic adsorption, so that the collector can be firmly adsorbed on the surface of spodumene. Compared with collectors with a single group, this dual-active site adsorption method greatly increases the adsorption capacity of the collector to the mineral surface, improves the selectivity and recovery rate of flotation. The disulfonic acid group has a stronger adsorption capacity, thus bringing higher selectivity.

[0071] After being adsorbed on the surface of spodumene, the hydrophobic chain structure in the collector will stretch outward to form a hydrophobic film, which reduces the hydrophilicity of the mineral surface and makes it easier to attach to the bubbles, thereby achieving separation from the gangue minerals. The presence of sulfonic acid groups and carboxylic acid groups can adjust the hydrophilic and hydrophobic properties of the collector, so that it can achieve better flotation effects under different flotation conditions.

[0072] Spodumene ore is usually associated with other gangue minerals, such as quartz, feldspar, mica, etc. The collector with sulfonic acid group plus carboxylic acid group can selectively adsorb spodumene, while the adsorption of gangue minerals is weak or almost non-existent. This is due to the difference in the properties of different mineral surfaces, resulting in different interactions between the collector and them. Through this selective adsorption, spodumene can be effectively separated from gangue minerals, and the grade of spodumene concentrate can be improved.

[0073] Optionally, the amines include one or more of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, and dodecyltrimethylammonium chloride.

[0074] Optionally, the fatty acid / salt includes one or more of linoleic acid, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid.

[0075] Optionally, the alcohol includes one or more of methanol, ethanol, propanol, n-butanol, etc.

[0076] In the above embodiments, the different components of sulfocarboxylic acids, amines, fatty acids / salts and alcohols mentioned can be freely combined without limitation.

[0077] Based on the above embodiments, the present application also provides a spodumene flotation method, which specifically includes:

[0078] Step 1: Place the spodumene ore in a ball mill and grind it to 55%-85% below 200 mesh, and collect the slurry;

[0079] Step 2: The collected slurry is passed through a magnetic separator to remove magnetic minerals to obtain magnetic concentrate;

[0080] Step 3: Add a concentration agent to the magnetic concentrate, dry and concentrate it, transfer the concentrated pulp to the flotation machine, adjust the flotation agent speed to 1650r / min, and stir the pulp in the flotation machine for 2-10min;

[0081] Weigh sodium carbonate and dissolve it in water, add the sodium carbonate solution to the slurry in small amounts and multiple times, continue stirring, and adjust the slurry pH to 7-14;

[0082] Add the dissolved sodium hydroxide solution, and after a period of time, add 200-1500g / t of calcium chloride, and continue stirring for 5-25min;

[0083] Step 4: slowly adding 200-1200 g / t of the flotation agent as described in any one of the claims, stirring for 10 minutes, opening the flotation machine for roughing, obtaining roughing concentrate and roughing tailings, adding 20-120 g / t of the flotation agent to the roughing tailings for scavenging, obtaining scavenged ore and scavenged tailings, and returning the scavenged ore to the roughing for refloatation;

[0084] Step 5: 200-500 g / t of the flotation agent is added again to the rougher concentrate and the scavenged ore obtained by the roughing, and the first concentration is performed to obtain the first concentrated middlings and the first concentrated concentrates. The first concentrated middlings are returned to the roughing, and the first concentrated concentrates are subjected to the second concentration, and the flotation agent is added and stirred. Then, the concentrate participates in the next flotation, and the middlings are returned to the previous flotation operation to obtain the spodumene concentrate.

[0085] The present application is described below through specific embodiments.

[0086] The spodumene ore sample of this embodiment is tested, and the raw ore Li2O grade is 1.44% (that is, the content of Li2O in the raw ore is 1.44%). A flotation method for spodumene is provided, comprising the following steps:

[0087] Step 1: Place the spodumene ore in a ball mill and grind it to 75% below 200 mesh, and collect the resulting slurry.

[0088] Step 2: The collected slurry is passed through a magnetic separator to remove magnetic minerals. After removing the magnetic minerals, we obtain magnetic concentrate.

[0089] Step 3: Add the concentration agent to the magnetic concentrate from the previous step, dry and concentrate it, transfer the concentrated pulp to the flotation machine, adjust the speed of the flotation agent to 1650r / min, and adjust the temperature to room temperature. Stir the pulp in the flotation machine for 8 minutes, during which sodium carbonate is dissolved in water and stirred continuously.

[0090] Ten minutes later, add the dissolved sodium hydroxide solution. During the process of adding the sodium hydroxide solution, the amount of sodium hydroxide solution added is determined according to the actual pH. Ten minutes after the sodium hydroxide is added, add 600g / t of activator calcium chloride and continue stirring for 10 minutes.

[0091] Step 4: slowly add 400 g / t of the spodumene flotation agent of the present invention, stir for 10 minutes, and then open the flotation machine for roughing to obtain roughing concentrate and roughing tailings. Add 40 g / t of hydroxamic acid flotation agent to the roughing tailings for scavenging, and obtain scavenging ore and scavenging tailings. The scavenging ore is returned to the roughing for refloatation.

[0092] Step 5: 100 g / t of spodumene flotation reagent is added to the rougher concentrate and the scavenged ore obtained by the rougher selection again, and the first selection is performed to obtain the first selected ore and the first selected concentrate. The first selected ore is returned to the rougher selection, and the first selected concentrate is subjected to the second selection. Similarly, the spodumene flotation reagent is added and stirred, and then the concentrate participates in the next flotation, and the ore returns to the previous flotation operation. Finally, we obtain spodumene concentrate G1.

[0093] According to the same ratio, the sulfocarboxylic acid of the present invention is replaced with dodecylsulfonic acid when preparing the spodumene flotation reagent, and the prepared spodumene collector is subjected to flotation according to the above flotation steps. Finally, we obtain the spodumene concentrate G2.

[0094] The obtained spodumene concentrate G1 was dried in an oven overnight, collected and mixed, and sent for testing. The test results showed that the Li2O grade of the spodumene concentrate G1 was 5.94%, and the recovery rate reached 88.4%.

[0095] The obtained spodumene concentrate G2 was dried in an oven overnight, collected and mixed, and sent for testing. The test results showed that the Li2O grade of the spodumene concentrate G2 was 5.33%, and the recovery rate reached 70.1%.

[0096] The grade of the concentrate floated by the developed spodumene flotation agent containing a carboxylic acid group and two sulfonic acid groups is 4.50 percentage points higher than that of the original ore.

[0097] The spodumene flotation reagent containing a carboxylic acid group and two sulfonic acid groups can obtain a higher concentrate grade and recovery rate than the spodumene flotation reagent containing dodecyl sulfonic acid.

[0098] For easy viewing, the following table is made:

[0099]

[0100] Table 1 Statistics of spodumene ore flotation under different collectors

[0101] Example 2

[0102] The spodumene flotation reagent containing a carboxylic acid group and two sulfonic acid groups in Example 1 only needs 400 g / t, while the dosage of the concentrate obtained by the spodumene flotation reagent containing dodecyl sulfonic acid is 1000 g / t:

[0103] Step 1: Place the spodumene ore in a ball mill and grind it to 75% below 200 mesh, and collect the resulting slurry.

[0104] Step 2: The collected slurry is passed through a magnetic separator to remove magnetic minerals. After removing the magnetic minerals, we obtain magnetic concentrate.

[0105] Step 3: Add the concentration agent to the magnetic concentrate from the previous step, dry and concentrate it, transfer the concentrated pulp to the flotation machine, adjust the speed of the flotation agent to 1650r / min, and adjust the temperature to room temperature. Stir the pulp in the flotation machine for 8 minutes, during which sodium carbonate is dissolved in water and stirred continuously.

[0106] Ten minutes later, add the dissolved sodium hydroxide solution. During the process of adding the sodium hydroxide solution, the amount of sodium hydroxide solution added is determined according to the actual pH. Ten minutes after the sodium hydroxide is added, add 600g / t of activator calcium chloride and continue stirring for 10 minutes.

[0107] Step 4: Slowly add 400g / t of spodumene flotation reagent containing carboxylic acid group and two sulfonic acid groups, stir for 10 minutes, and then open the flotation machine for roughing to obtain roughing concentrate and roughing tailings. Add 40g / t of hydroxamic acid flotation reagent to the roughing tailings for scavenging, and obtain scavenging ore and scavenging tailings. The scavenging ore is returned to the roughing for refloatation.

[0108] Step 5: 100 g / t of spodumene flotation reagent is added to the rougher concentrate and scavenged ore obtained by the rougher selection again, and the first selection is performed to obtain the first selection ore and the first selection concentrate. The first selection ore is returned to the rougher selection, and the first selection concentrate is subjected to the second selection. Similarly, the spodumene flotation reagent is added and stirred, and then the concentrate participates in the next flotation, and the ore returns to the previous flotation operation. Finally, we obtain spodumene concentrate H1.

[0109] According to the same operation, the sulfocarboxylic acid of the present invention is replaced with dodecyl sulfonic acid when preparing the spodumene flotation reagent, and the concentrate of the same grade is obtained and the dosage of the dodecyl sulfonic acid collector is calculated. Finally, we obtain the spodumene concentrate H2.

[0110] The obtained spodumene concentrate H1 was dried in an oven overnight, collected and mixed, and sent for testing. The test results showed that the Li2O grade of the spodumene concentrate H1 was 5.79%, and the recovery rate reached 84.9%.

[0111] The obtained spodumene concentrate H2 was dried in an oven overnight, collected and mixed, and sent for testing. The test results showed that the Li2O grade of the spodumene concentrate H2 was 5.71%, and the recovery rate reached 73.0%.

[0112] The concentrate grade floated by the sulfocarboxylic acid flotation reagent of the present invention is the same as that of the dodecylsulfonic acid, but the lithium recovery rate in the concentrate is different by more than 10%.

[0113]

[0114] Table 2 Statistics of spodumene ore flotation under different collectors

[0115] In summary, compared with the dodecyl sulfonic acid collector, the sulfocarboxylic acid flotation reagent provided by the present invention has better selectivity for spodumene and stronger collecting ability than the dodecyl sulfonic acid collector.

[0116] The introduction of sulfonic acid groups and carboxylic acid groups can improve the dispersibility and solubility of the collector in the pulp, so that it can better contact and react with spodumene particles. At the same time, this amphiphilic mineral structure collector can also reduce the surface tension of the pulp, promote the formation and dispersion of bubbles, and increase the collision probability and attachment efficiency of bubbles and mineral particles, thereby further improving the flotation efficiency.

[0117] In the slurry environment, there may be interference from a variety of ions and impurities. Due to its multiple adsorption sites and strong adsorption capacity, the disulfonic acid group collector can resist the influence of these interference factors to a certain extent and maintain good collection performance. However, the monosulfonic acid group collector may reduce the collection effect of spodumene due to interference.

[0118] In summary, the sulfonate carboxylate spodumene flotation reagent of the present invention is superior to most spodumene flotation reagents containing one sulfonate group, and requires a lower dosage.

[0119] 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 sulfocarboxylic acid anion collector compound, characterized in that: The sulfonylcarboxylic acid anion collector compound is a compound having the following general chemical structure formula or its chemical isomer or salt: in: n is any number between 1 and 10; M is H, Na, or K.

2. The sulfonylcarboxylic acid anion collector compound according to claim 1, characterized in that: The compound is one of the following compounds:

3. A method for preparing a sulfocarboxylic acid anion collector compound, characterized in that: The preparation method of the sulfonylcarboxylic acid anion collector compound comprises: Take a clean and dry high temperature and high pressure reactor, weigh 0.2-0.8 of powdered or block cerium hydroxide catalyst; Add lipoic acid dropwise into the reactor and stir for 10-30 min; 1-10 parts of hydrogen peroxide solution are added into the stirred reactor at a rate of 1 drop / s; Pressurizing the reactor charged with reactants; After the pressurization is completed, the reactor is placed on a heating device for heating, the required heating temperature is, and stirring is performed; After the reaction is completed, the mixture is naturally cooled to room temperature, and supersaturated saline is added to quench the reaction to obtain compound B; Finally, product B is obtained by column chromatography, and the corresponding carbonate is added and stirred to obtain product C; Wherein, the chemical structure formula of the compound C is: in: n is any number between 1 and 10; M is H, Na, or K.

4. The method for preparing a sulfocarboxylic acid anion collector compound according to claim 3, characterized in that: The pressure during pressurization is 5-40Mpa, the temperature during heating is 50-700°C, and the stirring time is 0.1-2h.

5. A mixed flotation agent, characterized in that: The mixed flotation agent comprises 40-70% of the sulfonylcarboxylic acid compound B as claimed in any one of claims 1 to 2, 15-40% of amines, 5-20% of fatty acids / salts and 10-30% of alcohols.

6. The mixed flotation agent according to claim 5, characterized in that: The amines include one or more of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, and dodecyltrimethylammonium chloride.

7. The mixed flotation agent according to claim 5, characterized in that: The fatty acids / salts include one or more of linoleic acid, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid.

8. The mixed flotation agent according to claim 5, characterized in that: The alcohols include one or more of methanol, ethanol, propanol, n-butanol, etc.

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