Collecting agent, flotation reagent and method for scheelite flotation

Abstract

The invention belongs to the field of scheelite flotation, and particularly discloses a collecting agent, a flotation reagent and a method for scheelite flotation, and the method for scheelite flotation comprises the step that flotation is conducted on to-be-selected minerals containing scheelite and the flotation reagent containing the collecting agent, and scheelite concentrate is obtained. The collecting agent comprises at least one compound in a formula A # imgabs 0 # and a formula B # imgabs 1 #; r1 and R2 are independently alkyl groups of C2-C8; 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 field of mineral processing, and in particular relates to the flotation field of scheelite. Background Art

[0002] Fluorite, scheelite and calcite are important calcium-containing minerals widely used in the industrial field. Fluorite is not only a metallurgical flux and a raw material for hydrofluoric acid, but also used in high-end equipment and ceramic products due to its optical properties. As an important source of cemented carbide and high-temperature materials, scheelite has an irreplaceable position in industry and national defense. With the increasing demand for such mineral resources in my country, efficient development and utilization are particularly urgent.

[0003] Flotation is an important technology for separating calcium-containing minerals, which can achieve selective separation through the difference in mineral surface characteristics. Collectors are key reagents that directly affect the separation effect. However, since the crystal surfaces of fluorite, scheelite and calcite contain Ca 2 + , making their flotation behaviors similar and making separation more difficult. Currently, commonly used collectors such as oleic acid have a certain collection effect, but their selectivity is poor. At the same time, they are affected by water quality and temperature, which leads to complicated processes and low economic benefits. For this reason, the industry usually relies on inhibitors or complex treatment processes, but these methods increase costs and increase the environmental burden. Therefore, the development of a new type of highly selective collector has become the key to improving flotation efficiency and promoting the use of green minerals.

[0004] There are also some flotation methods for calcium-containing minerals in the prior art. For example, the Chinese patent document with publication number CN114985114A discloses a depressant for the flotation of scheelite, specifically recording that the organic depressant quinic acid is used as a depressant for the flotation of scheelite and other calcium-containing minerals, and further recording that metal ions are added to form a metal-quinic acid complex, thereby enhancing the depressant effect on other calcium-containing minerals. For another example, the Chinese patent document with publication number CN119076233A discloses a combined depressant for the flotation separation of fluorite and calcium-containing gangue minerals, specifically recording a combined flotation depressant composed of water glass, iminodisuccinic acid and carboxymethyl cellulose.

[0005] In summary, the current flotation industry 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 and are difficult to significantly improve the flotation effect, 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 capture selectivity of scheelite is not ideal, the present invention proposes a method for flotation of scheelite, aiming to improve the capture capacity and selectivity of scheelite.

[0007] The 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, and the separation selectivity of the single-stage flotation step is not ideal. In view of this problem, the present invention has conducted in-depth research and provided 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 symmetric 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] The present invention shows that the collector contains at least a compound of formula A; further contains compounds of formula A and formula B; further, in the collector, the weight ratio of the compounds of formula A and formula B is 0.2 to 5:1, and most preferably 2 to 4:1. Studies have shown that the collector of formula A has better targeting ability and selectivity for scheelite than that of formula B, but combining formula A and formula B, especially combining them in a preferred ratio, can unexpectedly further achieve intermolecular synergy, and can further enhance the targeting ability and selectivity of scheelite.

[0014] In the present invention, the amount of the collector used in the flotation stage is 50 g / t or more, and considering the cost, it can be 50 to 200 g / t; further, it can be 60 to 150 g / t; and most preferably, it can be 75 to 105 g / t. The collector of the present invention can obtain excellent scheelite targeting ability 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 selected also include 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. Scheelite and other calcium-containing minerals have similar floating characteristics, and the separation of existing processes is difficult. However, the flotation process described in the present invention can achieve the separation selectivity 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 an inhibitor and a frother. In addition, the flotation step of the present invention can be a single-stage roughing.

[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 and formula B is 0.2 to 5:1, and 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 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 FIG. 2 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 typically listed as formula B-1, and its specific structure is:

[0030]

[0031] Comparative structural compounds, the 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, ore samples artificially prepared from three single minerals were specially selected for flotation test in the experiment.

[0034] In the following cases, the dosage of flotation reagent is expressed in 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 adopts the collector to carry out flotation test on ore. As an optional implementation scheme, the specific operation 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] In each experiment, 30g of scheelite, fluorite and calcite were weighed and ground separately for 5 minutes using a horizontal ball mill to prepare fine particles. The final product with a particle size range of 0.038mm-0.074mm was screened and used for subsequent flotation tests.

[0040] Step 2: Flotation

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

[0042] On the basis of the above flotation operation, each case was tested by adjusting the type and dosage of collector. The specific adjustment conditions and results are as follows:

[0043] Example 1 - Single Collector Solution

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

[0045] Group A: The collector is of formula A-1;

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

[0047] Comparative group a: the collector is 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 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] It can be seen from the experimental results of Example 1 that the collectors of Formula A and Formula B of the present invention can fully adapt to the characteristics of calcium-containing minerals and significantly improve the collection effect. Further comparison of Group A in Example 1 with Control Groups a and b shows that the special groups and substituent positions in the collector of Formula A are key factors affecting the collection performance; and the comparison of Group B in Example 1 with Control Groups c and d shows that the special groups in the collector of Formula B play an important role in improving the performance of the collector.

[0057] Example 2

[0058] Compared with Example 1, the only difference is that the type of collector is changed, the amount of collector is 80g / t, and 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 capture 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: The collector dosage is 60g / t;

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

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

[0071] Group D: The 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 show 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 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 selected containing scheelite and a flotation agent containing a collector are floated to obtain a scheelite concentrate, wherein the collector comprises at least one compound of formula A or formula B; The R1 and R2 are independently C2-C8 alkyl groups; and the M is H, Na, K or NH4.

2. The method according to claim 1, characterized in that The collector contains at least a compound of formula A.

3. The method according to claim 3, characterized in that The collector comprises compounds of formula A and formula B.

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

1.

5. The method according to claim 1, characterized in that The amount of collector used in the flotation stage is 50 g / t or more, preferably 50 to 200 g / t, more preferably 60 to 150 g / t, and most preferably 75 to 105 g / t.

6. The method according to claim 1, characterized in that The flotation reagent also includes a pH adjuster; Preferably, the pH adjuster includes at least one of sodium bicarbonate, calcium oxide, sodium carbonate, calcium hydroxide, and sodium hydroxide.

7. The method according to claim 1, characterized in that The pH in the flotation stage is 8.5 to 11.5, preferably 9.5 to 10.

5.

8. The method according to any one of claims 1 to 7, characterized in that: 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.

9. A collector for flotation of scheelite, characterized in that: It is the collector described in the method according to any one of claims 1 to 8.

10. A flotation agent for flotation of scheelite, characterized in that: The flotation agent described in any one of claims 1 to 8; Preferably, the flotation reagent is composed of a collector and a pH adjuster.

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