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

Abstract

The present invention belongs to the field of scheelite flotation, and specifically discloses a collector, a composite flotation agent and a method for flotation separation of scheelite and calcium-containing gangue, wherein the flotation separation steps are: using a flotation agent containing a collector to float a mixed mineral containing scheelite and calcium-containing gangue to obtain scheelite concentrate and calcium-containing gangue tailings; the collector includes at least one of collector a#imgabs0# and collector b#imgabs1#; R1 and R2 are independently C4~C 12 wherein M is H, Na, K or NH4. The collector of the present invention has obvious capture selectivity for calcium-containing mineral scheelite and excellent capture capacity.

Description

Technical field:

[0001] The invention belongs to the flotation agent technology in the field of mineral processing, and particularly relates to the flotation field of scheelite. Background technology:

[0002] Fluorite, calcite, and scheelite are common calcium-containing minerals that are widely distributed in nature and have diverse uses. As a key industrial mineral, fluorite is not only a primary raw material in the fluorination industry but is also widely used in metallurgy, glass, ceramics, and other fields. Furthermore, due to its excellent optical properties, fluorite is also used in the manufacture of optical instruments and military equipment. Scheelite, the world's primary source of tungsten resources, is widely used in cemented carbides, high-temperature resistant materials, and other high-tech fields. With the continuous development of industrialization 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 is one of the core technologies currently used to efficiently utilize calcium-containing mineral resources. Its core principle is to separate minerals based on differences in their surface physical and chemical properties. During flotation, the selection and use of flotation reagents plays a crucial role in separation performance, with collectors, in particular, being a key factor influencing flotation success. However, because fluorite, scheelite, and calcite all contain calcium ions on their crystal surfaces, their flotation behaviors are very similar, making mineral separation extremely challenging. Currently, oleic acid is the most commonly used collector. While oleic acid has good collecting capacity, it is nearly incapable of effectively separating fluorite, scheelite, and calcite. Furthermore, oleic acid suffers from drawbacks such as poor water solubility and sensitivity to water quality and temperature, resulting in unstable flotation performance and low product grade. Currently, improving separation performance often requires the introduction of inhibitors or other complex process conditions, which not only increases flotation production costs but also has certain negative environmental impacts. Therefore, developing a novel collector that can efficiently separate these three calcium-containing minerals while also exhibiting excellent collecting properties is crucial for improving flotation efficiency and reducing costs.

[0004] There are also some existing flotation methods for calcium-containing minerals. For example, Chinese patent publication No. CN112371347A discloses a scheelite beneficiation method, in which the collector comprises saponified oleic acid, hydroxy oleic acid, sulfonated oleic acid, and an emulsifier, wherein the mass ratio of the sum of the hydroxy oleic acid and sulfonated oleic acid to the saponified oleic acid is (2.5-10):(1-5). For another example, Chinese patent publication No. CN118719329A discloses a scheelite flotation reagent combination comprising a combined depressant PSS / ATMP and a combined collector DBOA / S465.

[0005] In summary, the current flotation industry is still lacking efficient and highly selective collectors for calcium-containing minerals. Continuing to use traditional fatty acid collectors often fails to significantly improve the separation efficiency of calcium-containing minerals, resulting in suboptimal calcium mineral flotation results and insufficient development and utilization of tungsten and fluorine resources. Summary of the invention:

[0006] In response to 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 for scheelite and calcium-containing gangue with existing conventional fatty acid collectors. Not only that, conventional fatty acid collectors such as oleic acid exhibit 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 makes it 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 provided the following solutions after in-depth research:

[0009] A method for flotation separation of scheelite and calcium-containing gangue, comprising flotation of a mixed mineral comprising scheelite and calcium-containing gangue using a flotation reagent comprising a collector to obtain scheelite concentrate and calcium-containing gangue tailings; the collector comprising 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;

[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 (Formula 1) and α-COO-SO3 can unexpectedly achieve a combined synergistic effect within the molecular structure, thereby optimizing the flotation separation selectivity of scheelite and calcium-containing gangue, improving the collection capacity of scheelite, and reducing 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 Formulas 1 and 2 and their ortho-positioned structural relationship are key to constructing a specific capture domain for scheelite, improving the flotation selectivity of scheelite and calcium-containing gangue. Research in the present invention also demonstrates that the innovative combination of Formulas 1 and 2 can further optimize the flotation separation selectivity of scheelite and calcium-containing gangue based on their intramolecular and intermolecular synergy. Preferably, the weight ratio of collector a to collector b in the collector is 1-5:1-5; preferably 2-4:1, and more preferably 2-2.5:1. Research in the present invention also demonstrates that at this preferred ratio, the intermolecular synergy of Formulas 1 and 2 can be further achieved, further enhancing the flotation separation selectivity of scheelite and calcium-containing gangue.

[0015] In the present invention, the amount of collector used in the flotation stage is 50 g / t or more. Considering cost, it can be further increased to 50-150 g / t, and further increased to 70-120 g / t. The flotation reagent of the present invention, in addition to the collector, can be adjusted based on conventional principles and methods.

[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 in 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 achieve good flotation effects without using additional flotation components such as additional frothers.

[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 not only has simple flotation components but also significantly simplifies the flotation process. For example, it can obtain excellent separation selectivity of scheelite and calcium-containing gangue based on a single-stage roughing process.

[0021] The present invention also provides a collector for the 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 collector a to collector b in the binary composite collector is 1-5:1-5, or further can be 2-4:1.

[0022] The present invention also provides a flotation agent for flotation of calcium-containing minerals, wherein the flotation agent 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's research shows that the coupled 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 flotation conditions of the present invention are mild, the flotation procedure is simple, and the amount of flotation reagent used is low, which meets the requirements of industrial flotation applications. Description of the drawings:

[0027] Figure 1 1 is a flotation flow chart of an embodiment. Specific implementation method:

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

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

[0030]

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

[0032]

[0033] Comparative structural compound, its 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 was selected for flotation experiment.

[0037] In the following cases, the dosage unit of the reagents 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 conduct 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 was used to verify the effect of the collector of the present invention. The specific operation steps are:

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

[0042] Step 2: 2 g of mixed minerals (1 g of scheelite + 1 g of fluorite / calcite) were weighed from each group and placed in a 40 ml flotation cell. 30 ml of deionized water was added and stirred for 2 min. The pH of the slurry was then adjusted to 10.5. The given collector for each group was added and aerated for 5 s. The foam was scraped off (4 min) to obtain a flotation concentrate. The remaining ore sample in the flotation cell was taken out to obtain a flotation tailing, which was filtered, dried, weighed, and the WO3 grade was determined. The recovery rate of each mineral was calculated to evaluate the effect of the collector of the present invention.

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

[0044] Example 1 - Single Collector Solution

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

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

[0047] Group B: 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 at 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] The results of Example 1 show that the use of the collectors of Formulas 1 and 2 of the present invention can effectively adapt to the characteristics of calcium-containing minerals and significantly improve the collection effect. Furthermore, by comparing Group A in Example 1 with Comparative Groups a and b, it is shown that the special groups and substituent positions in the collector of Formula 1 are key factors in improving the collector performance. By comparing Group B in Example 1 with Comparative Groups c, d, and f, it is shown that the synergistic effect of the sulfonic and carboxyl groups in the collector of Formula 2 has a significant impact on the collector performance.

[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 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: collector dosage is 60g / t;

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

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

[0074] Group D: 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 groups 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 is collector a, or includes 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; Formula 1 Formula 2 The R1 and R2 are independently C4~C 12 wherein M is H, Na, K or NH4.

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

3. The method according to claim 1, wherein The collector comprises collector a and collector b.

4. The method according to claim 3, wherein 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, wherein The amount of collector used in the flotation stage is above 50 g / t.

6. The method according to claim 5, wherein The dosage of collector in the flotation stage is 50~150 g / t.

7. The method according to claim 5, wherein The dosage of collector in the flotation stage is 70~120 g / t.

8. The method according to claim 1, wherein The pH value in the flotation stage is 8~12.

9. The method according to claim 1, wherein The pH value in the flotation stage is 10~11.

10. The method according to claim 1, wherein The flotation process is a single-stage roughing process.

11. A collector for flotation separation of scheelite and calcium-containing gangue, characterized in that: The collector comprising collector a and collector b as described in any one of claims 1 to 10.

12. The collector for flotation separation of scheelite and calcium-containing gangue according to claim 11, characterized in that: In the collector, the weight ratio of collector a to collector b is 1-5:1-5.

13. The collector for flotation separation of scheelite and calcium-containing gangue according to claim 12, characterized in that: In the collector, the weight ratio of collector a to collector b is 2~4:

1.

14. A composite flotation agent for flotation separation of scheelite and calcium-containing gangue, characterized in that: The flotation reagent according to any one of claims 1 to 10, wherein the collector comprises collector a and collector b.

15. The composite flotation agent for flotation separation of scheelite and calcium-containing gangue according to claim 14, characterized in that: The invention is composed of the collector and the pH regulator.

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