Collecting agent, composite flotation reagent and method for flotation separation of scheelite and calcium-containing gangue

Abstract

The invention belongs to the field of scheelite flotation, and particularly discloses a collecting agent, a composite flotation reagent and a method for flotation separation of scheelite and calcium-containing gangue, and the flotation separation comprises the steps that the flotation reagent containing the collecting agent is adopted for flotation of mixed minerals containing the scheelite and the calcium-containing gangue, and the flotation reagent containing the collecting agent is adopted for flotation of the mixed minerals containing the scheelite and the calcium-containing gangue; scheelite concentrate and calcium-containing gangue tailings are obtained; the collecting agent comprises at least one of a collecting agent a # imgabs0 # and a collecting agent b # imgabs1 #; the R1 and the R2 are independently alkyl groups of C4-C12; m is H, Na, K or NH4. The collecting agent disclosed by the invention has obvious collecting selectivity on scheelite which is a calcium-containing mineral, and meanwhile, the collecting agent has excellent collecting capacity.

Description

Technical Field

[0001] The invention belongs to the flotation reagent technology in the field of mineral processing, and in particular relates to the flotation field of scheelite. Background Art

[0002] Fluorite, calcite and scheelite are common calcium-containing minerals that are widely distributed in nature and have various uses. As an important industrial mineral, fluorite is not only the main raw material of the fluoridation industry, but also widely used in metallurgy, glass, ceramics and other fields. In addition, due to its excellent optical properties, fluorite is also used in the manufacture of optical instruments and military equipment. Scheelite is the main source of tungsten resources in the world and is widely used in cemented carbide, high temperature resistant materials and other high-tech fields. With the continuous development of industrialization and science and technology, my country's demand for scheelite and fluorite continues to increase, making the development and efficient utilization of calcium-containing mineral resources particularly important.

[0003] Flotation process is one of the core technologies for efficient utilization of calcium-containing mineral resources. Its core principle is to achieve mineral separation based on the difference in physical and chemical properties of mineral surfaces. In the flotation process, the selection and use of flotation reagents play a vital role in the sorting effect, especially the flotation collector is the key factor affecting the success of flotation. However, since the crystal surfaces of fluorite, scheelite and calcite all contain calcium ions, their flotation behaviors are very similar, which brings great difficulties to the separation of minerals. At present, the commonly used collector is mainly oleic acid. Although oleic acid has good collection ability, it is almost impossible to achieve effective separation of fluorite, scheelite and calcite. In addition, oleic acid also has the disadvantages of poor water solubility and sensitivity to water quality and temperature, which makes the flotation index unstable and the product grade low. In order to improve the sorting effect, it is usually necessary to introduce inhibitors or other complex process conditions at this stage, but this not only increases the production cost of flotation, but also has certain negative impacts on the environment. Therefore, it is of great significance to develop a new collector that can not only efficiently sort the three calcium-containing minerals but also has excellent collection performance to improve flotation efficiency and reduce costs.

[0004] There are also some flotation methods for calcium-containing minerals in the prior art. For example, the Chinese patent document with publication number CN112371347A discloses a method for beneficiating scheelite, wherein the collector includes saponified oleic acid, hydroxy oleic acid, sulfonated oleic acid and an emulsifier, wherein the mass ratio of the sum of hydroxy oleic acid and sulfonated oleic acid to saponified oleic acid is (2.5-10):(1-5). For another example, the Chinese patent document with publication number CN118719329A discloses a combined reagent for flotation of scheelite, which includes a combined depressant PSS / ATMP and a combined collector DBOA / S465.

[0005] In summary, there is still a lack of efficient and highly selective collectors for calcium-containing minerals in the existing flotation industry. Continuing to use traditional fatty acid collectors often makes it difficult to significantly improve the separation efficiency of calcium-containing minerals, resulting in unsatisfactory flotation effects of calcium-containing minerals and insufficient development and utilization of tungsten and fluorine resources. Summary of the invention

[0006] In view of the technical difficulty that existing collectors are difficult to meet the flotation requirements of calcium-containing minerals, the present invention provides a method for flotation separation of scheelite and calcium-containing gangue, aiming to effectively improve the collection capacity and selectivity of scheelite while significantly simplifying the flotation process based on a new collector.

[0007] The second purpose of the present invention is to provide a collector and a flotation agent for flotation separation of scheelite and calcium-containing gangue.

[0008] Both scheelite and calcium-containing gangue have excellent natural floatability, and it is difficult to obtain ideal flotation selectivity of scheelite and calcium-containing gangue with existing conventional fatty acid collectors. In addition, conventional fatty acid collectors such as oleic acid show shortcomings such as poor water solubility and sensitivity to water quality and temperature during the flotation process, resulting in unstable flotation indicators and low product grade, which is difficult to meet the needs of efficient separation. In order to improve the sorting effect, at this stage, the flotation process is usually optimized by introducing inhibitors or other complex process conditions. However, on the one hand, this method significantly increases the production cost of flotation, and on the other hand, the complex process conditions also have a certain negative impact on the environment, restricting the development of green mineral processing technology. In order to solve the above problems, this study, after in-depth analysis of the surface chemical properties of minerals and the shortcomings of traditional processes, proposed a solution for the development of new flotation agents, aiming to improve the stability and selectivity of flotation separation, while reducing adverse effects on the environment and production costs. To solve this problem, the present invention has been studied in depth and provides the following solutions:

[0009] A method for flotation separation of scheelite and calcium-containing gangue, wherein a flotation reagent comprising a collector is used to flotate a mixed mineral comprising scheelite and calcium-containing gangue to obtain scheelite concentrate and calcium-containing gangue tailings; the collector comprises at least one of a collector a and a collector b, wherein the collector a is a compound having formula 1 and a salt thereof, and the collector b is a compound having formula 2 and a salt thereof;

[0010]

[0011] The R1 and R2 are independently C4~C 12 wherein M is H, Na, K or NH4.

[0012] The present invention shows that the combination of α-CON-CONO (1) and α-COO-SO3 can unexpectedly achieve the combined synergy of the intramolecular structure, optimize the flotation separation selectivity of scheelite and calcium-containing gangue, improve the capture capacity of scheelite, and reduce the accompanying flotation of calcium-containing gangue.

[0013] In the present invention, the alkyl group is a straight chain or branched chain alkyl group. 10 of alkyl.

[0014] In the present invention, the functional fragments of Formula 1 and Formula 2 and the ortho-structural relationship between the two are the key to constructing a special capture domain of scheelite and improving the flotation selectivity of scheelite and calcium-containing gangue. The research of the present invention also shows that the innovative combination of Formula 1 and Formula 2 can further optimize the flotation separation selectivity of scheelite and calcium-containing gangue based on the intramolecular and intermolecular joint synergy of the two. Preferably, in the collector, the weight ratio of collector a and collector b is 1 to 5:1 to 5; preferably 2 to 4:1, and more preferably 2 to 2.5:1. The research of the present invention also shows that at the preferred ratio, the intermolecular synergy of Formula 1 and Formula 2 can be further achieved, which can further enhance the flotation separation selectivity of scheelite and calcium-containing gangue.

[0015] In the present invention, the amount of the collector in the flotation stage is 50 g / t or more, and can be further 50 to 150 g / t in consideration of cost; further, it can be 70 to 120 g / t. The flotation reagent of the present invention, in addition to the collector of the present invention, other components and amounts can be adjusted based on conventional principles and means.

[0016] In the present invention, the flotation reagent further comprises a pH adjuster.

[0017] In the present invention, the pH adjuster includes at least one of calcium oxide, sodium carbonate, sodium bicarbonate, sodium hydroxide and calcium hydroxide. After the pH adjuster acts, the pH of the flotation stage is 8 to 12, preferably 10 to 11.

[0018] The flotation method of the present invention benefits from the use of the collector, which not only has an excellent targeting effect on scheelite, but also has strong foaming properties, and can obtain good flotation effects without using additional flotation agents or other additional flotation components.

[0019] In the present invention, in addition to selecting the collector of the present invention, the other operations, parameters and equipment of the flotation method can be reasonably adjusted according to conventional principles and methods.

[0020] The flotation separation method of the present invention has simple flotation components and significantly simplified flotation process. For example, it can obtain excellent separation selectivity of scheelite and calcium-containing gangue based on single-stage roughing.

[0021] The present invention also provides a collector for flotation of calcium-containing minerals. Preferably, the collector comprises at least one of the collector a and the collector b. Preferably, the collector is a binary composite collector comprising collector a and collector b. When the weight ratio of the collector a to the collector b in the binary composite collector is 1 to 5:1 to 5, and can further be 2 to 4:1.

[0022] The present invention also provides a flotation reagent for flotation of calcium-containing minerals, wherein the flotation reagent comprises the collector of the present invention.

[0023] Furthermore, the flotation reagent is a flotation reagent composed of the collector and the pH regulator.

[0024] Beneficial Effects

[0025] The present invention shows that the coupling control of the structures of Formula 1 and Formula 2 can achieve intramolecular synergy, optimize the targeting ability and selectivity of scheelite, and enhance the capture ability and selectivity of scheelite.

[0026] The present invention has mild flotation conditions, simple flotation procedures, and low flotation reagent dosage, and meets the requirements of industrial flotation applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 1 is a flotation flow chart of an embodiment. DETAILED DESCRIPTION

[0028] In Formula 1 and Formula 2 described in the present invention, the alkyl group may be a straight chain or branched chain alkyl group, and the M may be H, which is partially or completely converted into an ionic type according to the difference in pH during the flotation stage. In addition, the present invention may also directly use an agent in which M is an ionic type.

[0029] In the present invention, the compound of formula 1 is typically exemplified by formula 1-A, and its specific structure is:

[0030]

[0031] The compound of formula 2 is typically exemplified by formula 2-A, and its specific structure is:

[0032]

[0033] Comparative structural compounds, the specific structure is:

[0034]

[0035]

[0036] The flotation ore described in the present invention can be an ore containing scheelite, fluorite and calcite of any grade. However, in order to further verify the flotation effect of the collector of the present invention, an ore sample artificially mixed with only three single minerals is selected for flotation experiment.

[0037] In the following cases, the dosage unit of the reagent is g / t, which refers to the gram weight of the flotation reagent added per ton of the mineral to be selected.

[0038] The present invention is based on conventional flotation methods and principles, and uses the collector of the present invention to carry out flotation experiments on ore. As one of the optional implementation schemes, the specific flotation operation process is as follows:

[0039] Example

[0040] like Figure 1 As shown, a roughing flotation process is used to verify the effect of the collector of the present invention. The specific operation steps are:

[0041] Step 1, grinding: 50g of scheelite, fluorite and calcite were weighed in each grinding experiment, and the single minerals were ground for 5 minutes using a horizontal ball mill to obtain fine particles, and finally sieved to obtain a particle size product of 0.038mm-0.074mm for flotation test.

[0042] Step 2, weigh 2g of mixed minerals (1g of scheelite + 1g of fluorite / calcite) in each group and place them in a 40ml flotation tank, add 30ml of deionized water, stir and slurry for 2min, then adjust the slurry pH to 10.5, add the given collector in each group, aerate for 5s (4min), scrape out the foam to obtain the flotation concentrate, take out the remaining ore sample in the flotation tank to obtain the flotation tailings, filter, dry, weigh, determine the WO3 grade, and calculate the recovery rate of each mineral, so as to evaluate the effect of the collector of the present invention.

[0043] Based on the above flotation operation steps, the collector and its dosage in each case were adjusted. The specific adjustment conditions and results were as follows:

[0044] Example 1 - Single Collector Solution

[0045] The collector is a single collector, the amount of collector is 100g / t, and the experimental groups are:

[0046] Group A: The collector is of formula 1-A;

[0047] Group B: The collector is Formula 2-A;

[0048] Comparative group a: the collector is comparative formula a;

[0049] Comparative group b: the collector is comparative formula b;

[0050] Comparative group c: the collector is comparative formula c;

[0051] Comparative group d: the collector is comparative formula d;

[0052] Comparative group e: the collectors are comparative formula c and comparative formula d in a molar ratio of 1:1;

[0053] Comparative group f: the collector is sodium oleate;

[0054] The results of each group are shown in Table 1:

[0055] Table 1

[0056]

[0057] From the results of Example 1, it can be seen that the use of the collectors of Formula 1 and Formula 2 of the present invention can effectively adapt to the characteristics of calcium-containing minerals and significantly improve the collection effect. Further, by comparing Group A in Example 1 with Comparative Groups a and b, it is shown that the special group and the position of the substituent in the collector of Formula 1 are key factors in improving the performance of the collector; by comparing Group B in Example 1 with Comparative Groups c, d, and f, it is shown that the synergistic effect of the sulfonic group and the carboxyl group in the collector of Formula 2 has a greater impact on the performance of the collector.

[0058] Example 2

[0059] Compared with Example 1, the only difference is that the composition and proportion of the collector are changed, the amount of the collector is 100g / t, and the experimental groups are:

[0060] Group A: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:1;

[0061] Group B: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:2;

[0062] Group C: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:4;

[0063] Group D: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 2:1;

[0064] Group E: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 4:1;

[0065] The results of each group are shown in Table 2:

[0066] Table 2

[0067]

[0068] From the comparison between Example 1 and Example 2, it is found that the combined use of Formula 1 and Formula 2, especially controlling the weight ratio of Formula 1: Formula 2 to 2 to 4:1, can further exert the synergistic effect of the reagents, is more suitable for the flotation characteristics of calcium-containing minerals, and can achieve better capture performance and selectivity.

[0069] Example 3

[0070] Compared with Example 2-D, the difference is that the amount of collector is changed. The experimental groups are:

[0071] Group A: The collector dosage is 60g / t;

[0072] Group B: The collector dosage is 80g / t;

[0073] Group C: The collector dosage is 120g / t;

[0074] Group D: The collector dosage is 140g / t;

[0075] The results of each group are shown in Table 3:

[0076] Table 3

[0077]

[0078] The results of Examples 2 and 3 show that even at a relatively low collector dosage, the combined use of Formula 1 and Formula 2 can still exhibit excellent capture capacity and selectivity for calcium-containing minerals.

[0079] Example 4

[0080] Compared with Example 3-C, the difference is that the pH value of the flotation process is changed. The experimental groups are:

[0081] Group A: slurry pH value is 8;

[0082] Group B: slurry pH value is 9;

[0083] Group C: slurry pH value is 10;

[0084] Group D: slurry pH value is 11;

[0085] Group E: slurry pH value is 12;

[0086] The results of each group are shown in Table 4:

[0087] Table 4

[0088]

[0089] The results of Example AE group show that when the pH value of the flotation stage is 8-12, preferably 10-11, the combined collector of Formula 1 and Formula 2 can exert the best collection ability and selectivity.

Claims

1. A method for flotation separation of scheelite and calcium-containing gangue, wherein a flotation agent containing a collector is used to flotate a mixed mineral containing scheelite and calcium-containing gangue to obtain scheelite concentrate and calcium-containing gangue tailings; characterized in that: The collector comprises at least one of collector a and collector b, wherein collector a is a compound having formula 1 and a salt thereof, and collector b is a compound having formula 2 and a salt thereof; The R1 and R2 are independently C4~C 12 wherein M is H, Na, K or NH4.

2. The method according to claim 1, characterized in that The R1 and R2 are independently C6~C 10 of alkyl.

3. The method according to claim 1, characterized in that The collector comprises collector a and collector b.

4. The method according to claim 3, characterized in that In the collector, the weight ratio of collector a to collector b is 1-5:1-5.

5. The method according to any one of claims 1 to 4, characterized in that: The amount of collector used in the flotation stage is 50 g / t or more, preferably 50 to 150 g / t, and more preferably 70 to 120 g / t.

6. The method according to claim 1, characterized in that The pH value in the flotation stage is 8-12, preferably 10-11.

7. The method according to claim 1, characterized in that The flotation process is a single-stage roughing process.

8. A collector for flotation separation of scheelite and calcium-containing gangue, characterized in that: The collector described in any one of claims 1 to 7; preferably, the weight ratio of collector a to collector b is 1 to 5:1 to 5; more preferably, the weight ratio of collector a to collector b is 2 to 4:

1.

9. A composite flotation agent for flotation separation of scheelite and calcium-containing gangue, characterized in that: It is the flotation agent described in the method according to any one of claims 1 to 7.

10. The composite flotation agent for flotation separation of scheelite and calcium-containing gangue as claimed in claim 9, characterized in that: The invention is composed of the collector and the pH regulator.

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