Collector, flotation agent and method for flotation of scheelite

Abstract

The present invention belongs to the field of scheelite flotation and specifically discloses a collector, flotation reagent, and method for flotating scheelite. The method for flotating scheelite comprises flotating a mineral containing scheelite and a flotation reagent containing the collector to obtain a scheelite concentrate. The collector comprises at least one compound selected from the formulas A#imgabs0# and B#imgabs1#; R1 and R2 are independently C2-C8 alkyl groups; and M is H, Na, K, or NH4. The collector exhibits significant selectivity for the calcium-containing mineral scheelite and excellent collection capacity.

Description

Technical Field

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

[0002] Fluorite, scheelite, and calcite are important calcium-containing minerals widely used in industry. Fluorite is not only a metallurgical flux and a hydrofluoric acid raw material, but also, due to its optical properties, is used in high-end equipment and ceramics. Scheelite, as a key source of cemented carbide and high-temperature materials, holds an irreplaceable position in industry and defense. With my country's increasing demand for these mineral resources, the efficient development and utilization of these resources has become increasingly urgent.

[0003] Flotation is an important technology for separating calcium-containing minerals, which can achieve selective separation by using the difference in mineral surface properties. Collectors are key reagents that directly affect the separation effect. However, since the crystal surfaces of fluorite, scheelite and calcite all contain Ca 2 + , resulting in similar flotation behaviors and making separation more difficult. While commonly used collectors such as oleic acid have some collection effectiveness, their selectivity is poor and they are affected by water quality and temperature, leading to complex processes and low economic returns. To address this, the industry typically resorts to inhibitors or complex treatment processes, but these methods increase costs and place a greater environmental burden. Therefore, developing a new, highly selective collector is key to improving flotation efficiency and promoting green mineral utilization.

[0004] Several existing flotation methods target calcium-containing minerals. For example, Chinese Patent Publication No. CN114985114A discloses a flotation inhibitor for scheelite. It specifically describes the use of quinic acid, an organic inhibitor, as a flotation inhibitor for scheelite and other calcium-containing minerals. It further describes the addition of metal ions to form metal-quinic acid complexes, thereby enhancing the inhibitory effect on other calcium-containing minerals. Another example is Chinese Patent Publication No. CN119076233A, which discloses a combined flotation inhibitor for the flotation separation of fluorite and calcium-containing gangue minerals. The combined flotation inhibitor is composed of water glass, iminodisuccinic acid, and carboxymethyl cellulose.

[0005] In summary, the flotation industry currently lacks efficient and highly selective collectors for calcium-containing minerals. Traditionally used fatty acid collectors have limited performance in improving the separation efficiency of calcium-containing minerals, making it difficult to significantly improve flotation results, thus restricting the full development and utilization of tungsten and fluorine resources. Summary of the Invention

[0006] In view of the problem that the existing scheelite capture selectivity is not ideal, the present invention proposes a method for flotation of scheelite, aiming to improve the capture capacity and selectivity of scheelite.

[0007] A second object of the present invention is to provide a collector and a flotation agent for flotation of scheelite.

[0008] Scheelite and other calcium-containing minerals have good natural floatability, but the separation selectivity of a single flotation step is not ideal. To address this problem, the present invention has conducted in-depth research and provides the following improvement scheme:

[0009] A method for flotation of scheelite, comprising flotation of an ore containing scheelite and a flotation agent containing a collector to obtain a scheelite concentrate, wherein the collector comprises at least one compound of formula A or formula B;

[0010]

[0011] The R1 and R2 are independently C2-C8 alkyl groups; and the M is H, Na, K or NH4.

[0012] The research of the present invention shows that the CONNCONNCO symmetrical domain in formula A and the PO3CN and CONCO domains in formula B can unexpectedly have excellent targeted recognition effects on scheelite, which can significantly improve the capture efficiency and sorting selectivity.

[0013] Research conducted in the present invention indicates that the collector comprises at least a compound of Formula A; further comprising compounds of Formula A and Formula B; and further, the weight ratio of the compounds of Formula A to Formula B in the collector is 0.2 to 5:1, and most preferably 2 to 4:1. Studies have shown that the collector of Formula A exhibits superior targeting and selectivity for scheelite compared to that of Formula B. However, combining Formula A and Formula B, particularly in a preferred ratio, unexpectedly further enhances molecular synergy, further enhancing the targeting and selectivity for scheelite.

[0014] In the present invention, the amount of collector used in the flotation stage is at least 50 g / t. Considering cost, it can be further 50 to 200 g / t, further preferably 60 to 150 g / t, and most preferably 75 to 105 g / t. The collector of the present invention can achieve excellent scheelite targeting and selectivity at a relatively low dosage.

[0015] In the present invention, the flotation reagent further comprises a pH adjuster.

[0016] In the present invention, the pH adjuster includes at least one of sodium bicarbonate, calcium oxide, sodium carbonate, calcium hydroxide, and sodium hydroxide. After the pH adjuster acts, the pH in the flotation stage is 8.5 to 11.5, preferably 9.5 to 10.5.

[0017] In the present invention, the minerals to be separated also include other calcium-containing minerals, which are enriched in the tailings after flotation. These other calcium-containing minerals include at least one of fluorite and calcite. Scheelite and other calcium-containing minerals have similar flotation characteristics, making separation difficult with existing processes. However, the flotation process described in the present invention can achieve selective separation of scheelite and other calcium-containing minerals.

[0018] The present invention benefits from the use of the collector, which can simplify the flotation process and reagents, thereby obtaining ideal scheelite flotation capacity and selectivity.

[0019] For example, the reagent of the present invention, in addition to containing a collector and a pH adjuster, can omit conventional flotation reagents such as inhibitors and frothers. In addition, the flotation step of the present invention can be a single-stage roughing process.

[0020] The present invention also provides a collector for flotation of scheelite, which is the collector of the present invention; further comprising compounds of formula A and formula B. Furthermore, in the collector, the weight ratio of the compounds of formula A to formula B is 0.2 to 5:1, more preferably 2 to 4:1.

[0021] The present invention also provides a flotation agent for flotation of scheelite, which is the flotation agent described in the method of the present invention;

[0022] Preferably, the flotation reagent is composed of a collector and a pH adjuster.

[0023] Beneficial effects

[0024] The present invention's research shows that the synergistic coupling of the structures of Formula A and Formula B can achieve a synergistic effect between molecules, effectively improve the targeted recognition ability and sorting selectivity of scheelite, and enhance its capture performance.

[0025] The flotation process of the present invention is simple, the conditions are mild, and the dosage of the reagent is low, which fully meets the practical application requirements of industrial flotation. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 1 is a flotation flow chart of an embodiment. DETAILED DESCRIPTION

[0027] In the present invention, the compound of formula A is typically represented by formula A-1, and its specific structure is:

[0028]

[0029] The compound of formula B is exemplified by formula B-1, and its specific structure is:

[0030]

[0031] Comparative structural compound, its specific structure is:

[0032]

[0033] The present invention is applicable to ore containing scheelite, fluorite and calcite of any grade as flotation ore. In order to more intuitively verify the flotation performance of the collector of the present invention, the experiment specifically selected ore samples artificially prepared from three single minerals for flotation testing.

[0034] In the following cases, the unit of reagent dosage is g / t, which means the mass (grams) of flotation reagent added per ton of ore to be processed.

[0035] The present invention is based on traditional flotation methods and theories and uses the collector to conduct flotation tests on ore. As an optional implementation scheme, the specific operating steps are as follows:

[0036] Example

[0037] like Figure 1 As shown, the performance of the collector of the present invention is verified through a roughing flotation process. The specific operation steps are as follows:

[0038] Step 1: Grinding

[0039] For each experiment, 30g of scheelite, fluorite, and calcite were weighed and ground individually in a horizontal ball mill for 5 minutes to produce a fine particle product. The final product, which was screened, had a particle size range of 0.038mm-0.074mm and was used for subsequent flotation experiments.

[0040] Step 2: Flotation

[0041] For each experiment, 2g of mixed minerals (1g scheelite + 1g fluorite or calcite) were weighed and placed in a 40ml flotation cell. 35ml of deionized water was added and stirred for 2 minutes. The slurry pH was then adjusted to 10, the designated collector was added, aerated for 5 seconds, and flotation was performed for 4 minutes. The froth was scraped off to obtain the flotation concentrate, and the remaining ore sample in the flotation cell was removed as the flotation tailings. The concentrate and tailings were filtered, dried, and weighed, and the WO3 grade was determined. The recovery rate of each mineral was calculated to evaluate the effectiveness of the collector.

[0042] Based on the above flotation operation, the type and dosage of collector were adjusted to test each case. The specific adjustment conditions and results are as follows:

[0043] Example 1 - Single Collector Solution

[0044] The collector is a single collector, and the amount of collector is 80g / t. The experimental groups are:

[0045] Group A: Collector is Formula A-1;

[0046] Group B: Collector is formula B-1;

[0047] Comparative group a: the collector is the comparative example a;

[0048] Comparative group b: the collector is comparative example b;

[0049] Comparative group c: the collector is comparative example c;

[0050] Comparative group d: the collector is the comparative example d;

[0051] Comparative group e: the collector is oxidized paraffin soap;

[0052] The results of each group are shown in Table 1:

[0053] Table 1

[0054]

[0055]

[0056] The experimental results of Example 1 show that the collectors of Formulas A and B of the present invention are fully adapted to the characteristics of calcium-containing minerals and significantly improve the collection efficiency. Further comparison of Group A in Example 1 with Controls a and b shows that the special groups and substituent positions in the collector of Formula A are key factors affecting the collection performance. Comparison of Group B in Example 1 with Controls c and d shows that the special groups in the collector of Formula B play a significant role in improving the collector performance.

[0057] Example 2

[0058] Compared with Example 1, the only difference is that the type of collector is changed and the amount of collector is 80g / t. The experimental groups are:

[0059] Group A: The collectors are Formula A-1 and Formula B-1 in a weight ratio of 1:4;

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

[0061] Group C: The collectors are Formula A-1 and Formula B-1 in a weight ratio of 4:1;

[0062] The results of each group are shown in Table 2:

[0063] Table 2

[0064]

[0065] By comparing Example 1 and Example 2, it can be found that the combined use of Formula A and Formula B, especially at a ratio of 2 to 4:1, can further enhance the synergistic effect of the reagents and is more suitable for the flotation characteristics of scheelite and (fluorite and calcite), thereby achieving better collection performance and sorting selectivity.

[0066] Example 3

[0067] Compared with Example 2-B, the difference is that the amount of collector is changed. The experimental groups are:

[0068] Group A: collector dosage is 60g / t;

[0069] Group B: collector dosage is 100g / t;

[0070] Group C: collector dosage is 120g / t;

[0071] Group D: collector dosage is 150g / t;

[0072] The results of each group are shown in Table 3:

[0073] Table 3

[0074]

[0075] In addition, the results of Example 2 and Example 3 show that even when the amount of collector is low, the combined use of Formula A and Formula B can still exhibit good capture ability and selectivity for calcium-containing minerals.

[0076] Example 4

[0077] Compared with Example 3-C, the difference is that the pH value of the flotation stage is changed. The experimental groups are:

[0078] Group A: flotation pH value is 9;

[0079] Group B: flotation pH value was 9.5;

[0080] Group C: flotation pH value was 10;

[0081] Group D: flotation pH value was 10.5;

[0082] Group E: flotation pH value was 11;

[0083] The results of each group are shown in Table 4:

[0084] Table 4

[0085]

[0086] By comparing the results of Example 4, it can be found that when the flotation pH value is between 8.5 and 11.5, especially between 9.5 and 10.5, the composite reagent exerts the best collection performance and sorting selectivity.

Claims

1. A method for flotation of scheelite, characterized in that: The ore to be processed containing scheelite is floated with a flotation agent containing a collector to obtain a scheelite concentrate, wherein the collector comprises at least one compound of Formula A or Formula B; Formula A Formula B The R1 and R2 are independently C2~C8 alkyl; the M is H, Na, K or NH4.

2. The method according to claim 1, wherein The collector contains at least the compound of formula A.

3. The method according to claim 2, wherein The collector comprises compounds of formula A and formula B.

4. The method according to claim 3, wherein The weight ratio of the compound of formula A to the compound of formula B is 0.2~5:

1.

5. The method according to claim 1, wherein The amount of collector used in the flotation stage is above 50 g / t.

6. The method according to claim 5, wherein The amount of collector used in the flotation stage is 50~200 g / t.

7. The method according to claim 6, wherein The dosage of collector in the flotation stage is 60~150 g / t.

8. The method according to claim 7, wherein The dosage of collector in the flotation stage is 75~105 g / t.

9. The method according to claim 1, wherein The flotation reagent also includes a pH adjuster.

10. The method according to claim 9, wherein The pH adjuster includes at least one of sodium bicarbonate, calcium oxide, sodium carbonate, calcium hydroxide, and sodium hydroxide.

11. The method according to claim 1, wherein The pH value in the flotation stage is 8.5~11.

5.

12. The method according to claim 11, wherein The pH value in the flotation stage is 9.5~10.

5.

13. The method according to any one of claims 1 to 12, wherein The minerals to be selected also contain other calcium-containing minerals, which are enriched in the tailings after flotation; the other calcium-containing minerals include at least one of fluorite and calcite.

14. A collector for flotation of scheelite, characterized in that: The collector according to any one of claims 1 to 13.

15. A flotation agent for flotation of scheelite, characterized in that: The flotation agent according to any one of claims 1 to 13.

16. The flotation reagent for flotation of scheelite according to claim 15, characterized in that: It is a flotation reagent composed of a collector and a pH adjuster.

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