Method for the flotation enrichment of rubidium and / or cesium in minerals

Abstract

The present application belongs to the field of mineral flotation, and particularly relates to a method for enriching rubidium and / or cesium in a mineral by flotation, wherein a target mineral containing at least one target element of rubidium and / or cesium is mixed with a flotation reagent containing a collector of formula 1 to perform flotation, and a flotation concentrate enriched with the target element is collected. 10 ~C 18 The alkyl group, M is H, Na, K or ammonium ion. The present application shows that the collector of formula 1 is used innovatively, which can realize synergy based on the combination of intramolecular-COO and R-N- in the alpha position, so as to adapt to the collection characteristics of rubidium and / or cesium minerals, and excellent collection and enrichment effect of rubidium and / or cesium minerals can be obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mineral flotation, and particularly relates to a flotation enrichment method containing rubidium and / or cesium. BACKGROUND

[0002] Rubidium and cesium are important metals, and have an irreplaceable important position in high-tech fields such as aerospace, electronic information and biological medicine. In existing industrial production, for lithium china clay resources containing rubidium and cesium, a pre-desliming-flotation combined process is generally used to obtain lithium concentrate containing rubidium and cesium. However, this process system has obvious limitations: first, the process flow design is dominated by lithium recovery, and the comprehensive recovery of associated rubidium and cesium metals is not considered enough; second, the existing collector selection and desliming process parameters cannot fully meet the characteristics of rubidium and cesium minerals; third, the overall recovery efficiency is low, and the resource utilization rate needs to be improved.

[0003] From the perspective of mineralogy, lepidolite, muscovite and sericite all belong to the family of layered silicate minerals, and their surface physical and chemical properties are very similar, which leads to significant selectivity challenges in the flotation separation process. Rubidium and cesium elements are usually in the form of isomorphism to replace potassium elements in the lattice of mica or feldspar, and this unique occurrence state makes it difficult to achieve effective enrichment by using traditional physical beneficiation methods.

[0004] The current technical system has the following problems that need to be highlighted: 1. separation selectivity bottleneck: the existing collector has insufficient selectivity adsorption ability for lepidolite, which easily leads to gangue mineral entrainment; 2. lack of exclusive reagent: there is a lack of efficient and economical exclusive recovery reagent for rubidium and cesium; 3. process complexity: multiple stages of grinding-flotation or combined chemical treatment are required, energy consumption is high, and especially the adaptability to fine-grained disseminated ores is poor; 4. environmental pressure: rubidium and cesium extraction relies on smelting processes such as roasting-leaching, which has a large environmental load; 5. resource waste: rubidium and cesium in tailings are not effectively recovered, and the comprehensive utilization rate is low; 6. environmental pollution risk: the toxicity problem of amine and other flotation reagents is prominent, and tailings residual reagents may cause secondary pollution; 7. three waste treatment problems: a large amount of acid wastewater and fluorine-containing pollutants are generated in the process of chemical extraction of lithium, rubidium and cesium.

[0005] From the perspective of mineral paragenetic relationship, rubidium and cesium are often closely associated with various minerals such as lithium mica, cesium tourmaline, potassium feldspar, etc., and the occurrence forms are complex and diverse. In addition, weathering and argillization phenomena are common in ores, which brings great difficulties to comprehensive recovery. At present, three types of collectors are mainly used in mica flotation: anionic type (such as sodium oleate, 731 oxidized paraffin soap, etc.), cationic type (such as dodecylamine, coconut amine, etc.) and combined collector. For example, the patent document with publication number CN117797954A discloses a method for synchronous flotation and recovery of lithium, rubidium and cesium in lithium-containing porcelain stone ore. The method first crushes and grinds the lithium-containing porcelain stone ore, then removes the slime, and then obtains lithium, rubidium and cesium concentrates through a flotation process of one roughing, two cleanings and two scavengings. The tailings are further ground and subjected to a flotation process of one roughing, two cleanings and two scavengings to obtain potassium feldspar concentrate and final tailings. The collector used in the flotation is a mixture obtained by mixing pentamethyldiethylenetriamine, naphthenic acid soap, di-n-octylamine and diethyl phosphite in a certain proportion. For another example, the patent document with publication number CN109939834A discloses a composite collector and its application in flotation of extremely low-grade rubidium-containing ore. The composite collector is composed of coconut amine and sodium dodecyl sulfate (SDS).

[0006] Although these reagents show good performance in lithium ore collection, the comprehensive recovery effect of co-associated rubidium and cesium is not satisfactory. In addition, the design of the desliming process and the regulation of the fluid environment in the existing flotation process are not fully optimized, which is difficult to adapt to the flotation characteristics of rubidium and cesium carrier minerals, resulting in a long-term low recovery rate of rubidium and cesium. SUMMARY

[0007] In view of the technical deficiencies existing in the current flotation of rubidium and cesium, the present application aims to provide a method for flotation enrichment of rubidium and / or cesium in minerals, which is designed to effectively float rubidium and / or cesium in minerals.

[0008] The grade of rubidium and / or cesium in minerals is extremely low, and it is usually recovered together as an additional component. In the prior art, there are few flotation enrichment methods specifically for rubidium and / or cesium. To solve this problem, the present application proposes the following solutions after in-depth research:

[0009] The method for flotation enrichment of rubidium and / or cesium in minerals mixes the target minerals containing at least one target element of rubidium and / or cesium with a flotation reagent containing a collector of formula 1, and then performs flotation to obtain a flotation concentrate enriched with the target element.

[0010] Formula 1;

[0011] In formula 1, R is an alkyl group of C 10 ~C 18 , and M is H, Na, K or ammonium ion.

[0012] The research of the present application shows that the collector of formula 1 is innovatively used, which can realize synergy based on the combination of intramolecular -COO and R-N- at the alpha position thereof, thus being able to adapt to the collection characteristics of rubidium and / or cesium in minerals, and excellent collection and enrichment effects of rubidium and / or cesium can be obtained.

[0013] In the present application, the grade of the target element in the selected mineral can be adjusted as needed, for example, can be 0.1wt.%~0.25wt.%.

[0014] In the present application, R is a linear alkyl group of C 12 ~C 14 .

[0015] The formula 1 can be obtained by substitution reaction of formula 2 and formula 3.

[0016] Formula 2;

[0017] Formula 3;

[0018] R in formula 2 is the same as formula 1;

[0019] M in formula 3 is the same as formula 1, and X is halogen (for example, Cl or Br).

[0020] The collector further comprises a collector of formula 2. In the collector, the molar content of formula 2 is less than 50%; further can be 30%~50%.

[0021] In the present application, the concentration of the collector in the flotation process can be 15~45mg / L, further can be 20~40mg / L.

[0022] In the present application, the amount of formula 1 collector used in the flotation process is 40~400g / t; further can be 200~350g / t, and further can be 280~320g / t.

[0023] In the present application, the flotation reagent further comprises at least one of a foaming agent and a pH regulator.

[0024] In the present application, the pH of the flotation process is 3~11; further can be 3.5~10, and considering the effect and environmental factors, further can be preferably 6.5~7.5.

[0025] The present application also provides a flotation reagent for implementing the method.

[0026] Beneficial effects

[0027] The present application innovatively studies and shows that the use of formula 1 as a collector can achieve synergy based on the combination of intramolecular -COO and R-N- in the alpha position thereof, thus being able to adapt to the collection characteristics of rubidium and / or cesium, and achieving excellent collection and enrichment effect of rubidium and / or cesium. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 Infrared spectrum of formula 1A prepared for example 1;

[0029] Figure 2 NMR spectrum of formula 1A prepared for example 1;

[0030] Figure 3 Infrared spectrum of formula 1B prepared for example 4;

[0031] Figure 4 NMR spectrum of formula 1B prepared for example 4;

[0032] Figure 5 Single mineral flotation flowchart of rubidium and cesium carrier minerals for example 5, example 6;

[0033] Figure 6 Flotation flowchart of rubidium and cesium-containing porcelain clay ore after desliming for example 7 in Jiangxi; DETAILED DESCRIPTION

[0034] In order to make the technical problems, technical solutions and advantages to be solved by the present application clearer, specific embodiments will be described in detail below with reference to the accompanying drawings, but the protection scope of the present application is not limited to the following specific embodiments.

[0035] Unless otherwise defined, all professional terms used herein have the same meaning as generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present application.

[0036] The formula 1 collector of the present application can be obtained by simple substitution reaction of formula 2 and formula 3, or can be purchased as a commercial product.

[0037] In the present application, the temperature of the flotation process is room temperature (for example, 20±5℃) unless otherwise stated.

[0038] As an optional solution, optional typical compounds of formula 1 include, for example:

[0039] Formula 1A: ;

[0040] Formula 1B: ;

[0041] Example 1

[0042] Take 18.91 g of dodecylamine and 40 mL of ethanol in a reaction bottle, stir and dissolve, then dissolve sodium chloroacetate (molar ratio of dodecylamine to sodium chloroacetate is 1:1.1) in 15 mL of water, after dissolving, add it to the reaction bottle, stir and react at 60°C for 6h, after the reaction is completed, a colorless transparent solution is obtained, which is cooled at 4°C to obtain a white solid, after filtration and constant temperature drying, formula 1A is obtained. The obtained product is purified and characterized by infrared spectrum and nuclear magnetic resonance structure, the infrared spectrum is shown in Figure 1 , the infrared spectrum analysis is shown in Table 1; the nuclear magnetic resonance 1 H spectrum is shown in Figure 2 .

[0043] .

[0044] Example 2

[0045] Preparation of formula 1A:

[0046] Take 9.45 g of dodecylamine and 20 mL of ethanol in a reaction bottle, stir and dissolve, then dissolve sodium chloroacetate (molar ratio of dodecylamine to sodium chloroacetate is 1:0.95) in 10 mL of water, after dissolving, add it to the reaction bottle, stir and react at 70°C for 8h, after the reaction is completed, a colorless transparent solution is obtained, which is cooled at 4°C to obtain a white solid, after filtration and constant temperature drying, a collector containing formula 1A is obtained.

[0047] Example 3

[0048] Preparation of formula 1A collector complex mixture:

[0049] Take 18.91 g of dodecylamine and 20 mL of ethanol in a reaction bottle, stir and dissolve, then dissolve sodium chloroacetate (molar ratio of dodecylamine to sodium chloroacetate is 1:0.5) in 20 mL of water, after dissolving, add it to the reaction bottle, stir and react at 60°C for 6h, after the reaction is completed, a colorless transparent solution is obtained, which is a complex mixture containing formula 1A and dodecylamine.

[0050] Example 4: Preparation of formula 1B collector:

[0051] Take 22.23 g of tetradecylamine and 50 mL of ethanol in a reaction bottle, stir and dissolve, then dissolve sodium chloroacetate (molar ratio of tetradecylamine to sodium chloroacetate is 1:1.05) in 20 mL of water, after dissolving, add it to the reaction bottle, stir and react at 60°C for 6h, after the reaction is completed, a colorless transparent solution is obtained, which is cooled at 4°C to obtain a white solid, after filtration and constant temperature drying, formula 1B is obtained. The obtained product is characterized by infrared spectrum structure, the infrared spectrum is shown in Figure 3 , the infrared spectrum analysis is shown in Table 2; the nuclear magnetic resonance 1 H spectrum is shown in Figure 4 .

[0052] .

[0053] Example 5

[0054] The flotation recovery of rubidium and cesium carrier minerals (carrier minerals are mica minerals) under different dosage conditions of formula 1A (collector prepared in Example 1) is studied, and the Rb2O and Cs2O grades in the minerals are 0.82% and 0.16%, respectively.

[0055] The process flow as shown in Figure 5 is used for the flotation of rubidium and cesium carrier minerals, wherein the collector is formula 1A, the flotation machine stirring speed is 1992 r / min, the pulp pH is 7.0, and the flotation of rubidium and cesium carrier minerals with a particle size of 0.038-0.074 mm is carried out for 3 min. When the concentration of formula 1A collector in the pulp is 20 mg / L, the flotation recovery rate of rubidium and cesium minerals is 92.38%; when the concentration of the collector in the pulp is 30 mg / L, the flotation recovery rate of rubidium and cesium minerals is 95.67%; and when the concentration of the collector in the pulp is 40 mg / L, the flotation recovery rate of rubidium and cesium minerals is 95.74%.

[0056] Example 6

[0057] Compared with Example 5, the difference lies in that the flotation recovery of rubidium and cesium carrier minerals (carrier minerals are mica) under different pH conditions is studied.

[0058] The process flow as shown in Figure 5 is used for the flotation of rubidium and cesium carrier minerals, wherein the collector is formula 1A, the flotation machine stirring speed is 1992 r / min, the collector dosage is 40 mg / L, and the flotation of rubidium and cesium carrier minerals with a particle size of 0.038-0.074 mm is carried out for 3 min. When the pulp pH is 4, the flotation recovery rate of rubidium and cesium minerals is 98.39%; when the pulp pH is 8, the flotation recovery rate of rubidium and cesium minerals is 95.41%; and when the pulp pH is 10, the flotation recovery rate of rubidium and cesium minerals is 95.25%.

[0059] From Examples 5 and 6, it can be seen that the collector of the present application can obtain good rubidium and cesium enrichment collecting ability under a wide pH condition of 3-10; especially under the pH condition of 6.5-7.5 which is friendly to industry, excellent rubidium and cesium enrichment ability can also be obtained.

[0060] Comparative Example 1

[0061] Compared with Example 5, the difference lies only in that the flotation is carried out by replacing the formula 1A collector with comparative collector a and comparative collector b, and the difference in operation and parameters is the same as Example 5, and the experimental groups are as follows:

[0062] Group A: comparative collector a ( ) replace formula 1A as collector:

[0063] When the concentration of the comparative collector a is 20 mg / L, the flotation recovery rate of the rubidium cesium mineral is 13.41%; when the concentration of the collector is 30 mg / L, the flotation recovery rate of the rubidium cesium mineral is 13.54%; when the concentration of the collector is 40 mg / L, the flotation recovery rate of the rubidium cesium mineral is 14.67%.

[0064] Group B: using comparative collector b ( ) replace formula 1A as collector:

[0065] When the concentration of the comparative collector b is 20 mg / L, the flotation recovery rate of the rubidium cesium mineral is only 13.98%; when the concentration of the collector is 30 mg / L, the flotation recovery rate of the rubidium cesium mineral is only 18.67%; when the concentration of the collector is 40 mg / L, the flotation recovery rate of the rubidium cesium mineral is only 18.09%.

[0066] Comparative example 2

[0067] Compared with example 6, the difference is only that the comparative collector a and the comparative collector b are used to replace the formula 1A collector for flotation, and the difference in operation and parameters is the same as that in example 6, and the experimental groups are respectively:

[0068] Group A: using comparative collector a to replace formula 1A as collector:

[0069] When the pH of the ore pulp is 4, the flotation recovery rate of the rubidium cesium mineral is only 7.82%; when the pH of the ore pulp is 8, the flotation recovery rate of the rubidium cesium mineral is only 27.80%; when the pH of the ore pulp is 10, the flotation recovery rate of the rubidium cesium mineral is only 63.71%.

[0070] Group B: using comparative collector b to replace formula 1A as collector:

[0071] When the pH of the ore pulp is 4, the flotation recovery rate of the rubidium cesium mineral is only 6.08%; when the pH of the ore pulp is 8, the flotation recovery rate of the rubidium cesium mineral is only 5.62%; when the pH of the ore pulp is 10, the flotation recovery rate of the rubidium cesium mineral is only 1.83%.

[0072] It can be seen that the flotation recovery rate of the rubidium cesium mineral of the collector 1A or 1B of the present application and the comparative collector a and the comparative collector b is significantly improved, which can prove that the combination of the special structure described in the present application can realize synergy and optimize the collection of rubidium cesium.

[0073] Example 7

[0074] The flotation application of the collector of the present application in a porcelain clay ore containing rubidium cesium after desliming in Jiangxi:

[0075] A certain deslimed porcelain clay ore containing rubidium and cesium in Jiangxi was treated by the flotation process shown in Table 1. Figure 6 The content of Rb2O and Cs2O in the raw ore was 0.19% and 0.038% respectively, the grinding fineness was controlled to be 70% of -0.074 mm, sodium hexametaphosphate was used as the depressant, and the collector in Table 3 was used for flotation, the temperature was 20℃, the time was 10 min, and the pH was 7. The flotation results are shown in Table 3.

[0076] ;

[0077] As can be seen from Table 3, the collector in Example 2 can also obtain similar collecting ability as that in Example 1 at a lower dosage, which proves that the combination scheme in Example 3 can enhance the collecting ability of rubidium and cesium to a certain extent. In addition, compared with the comparative collector c in Example 1, the grade of Rb2O and Cs2O in the concentrate is increased by 0.12 and 0.017 percentage points respectively, and the corresponding metal recovery rate is increased by 4.58 and 2.24 percentage points respectively, and the flotation recovery rate of rubidium and cesium metal is significantly improved.

[0078] The above is the preferred embodiment of the present application. It should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which should also be considered within the scope of protection of the present application.

Claims

1. A method for flotation enrichment of rubidium and / or cesium in minerals, characterized in that, The candidate mineral containing at least one target element of rubidium and / or cesium is mixed with a flotation reagent containing a collector of formula 1 and subjected to flotation to obtain a flotation concentrate enriched with the target element. Formula 1; In Equation 1, R is C 10 ~C 18 The alkyl group, where M is a H, Na, K or ammonium ion.

2. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 1, characterized in that, The grade of the target element in the mineral to be selected is 0.1 wt.% to 0.25 wt.%.

3. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 1, characterized in that, Formula 1 is obtained by substitution reactions of Formulas 2 and 3; Formula 2; Formula 3; In Equation 2, R is the same as in Equation 1; In Equation 3, M is the same as in Equation 1, and X is a halogen.

4. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 1 or 3, characterized in that, The R mentioned is C 12 ~C 14 Straight-chain alkyl groups.

5. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 4, characterized in that, The collector also includes the collector of formula 2.

6. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 5, characterized in that, In the collector, the molar content of Formula 2 is less than 50%.

7. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 1, characterized in that, During the flotation process, the amount of collector of Formula 1 is 40~400g / t.

8. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 1, characterized in that, The flotation reagents also include at least one of the following: a frother and a pH adjuster.

9. The method for flotation enrichment of rubidium and / or cesium in minerals as described in claim 1, characterized in that, The pH range for the flotation process is 3 to 11.

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