Collector, flotation reagent and method for flotation of ilmenite

Abstract

The present invention belongs to the field of flotation, and specifically relates to a collector for flotation of ilmenite, comprising a collector a having a structure of formula 1#imgabs0#, and / or a collector b having a structure of formula 2#imgabs1#; wherein R1 is C1~C 10 Alkyl, R2 is H, C1~C 10 Said R3 is C1~C 10 The alkyl group; the M a 、M b solely H, Na, K, or NH4. The present invention employs the collector a and / or collector b as collectors for ilmenite, exhibiting excellent capture selectivity and capable of efficiently and selectively targeting titanium in the ilmenite, thereby improving its capture capacity and selectivity. Furthermore, the collectors of the present invention are surprisingly well-suited to the flotation requirements of fine-grained ilmenite, achieving excellent titanium capture capacity and selectivity during the flotation of fine-grained ilmenite.

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 ilmenite. Background Art

[0002] With the increasing depletion of high-grade ilmenite resources, the currently available ilmenite ore is becoming "poor, fine, and mixed," making its development increasingly difficult. Consequently, mineral separation processes rely more heavily on fine grinding to achieve sufficient monomeric dissociation of the minerals. However, as the mineral particles become finer, the floatability of fine-grained ilmenite (mineral particles with a particle size of -38μm) also deteriorates, resulting in a weakening of the effectiveness of commonly used flotation collectors and a reduction in metal recovery rates. This not only results in a significant waste of resources, but also causes fine-grained ilmenite to enter the external environment with tailings, adversely impacting the environment. Therefore, improving the metal recovery rate of fine-grained ilmenite has become a pressing issue.

[0003] To improve the metal recovery rate of fine-grained ilmenite, the key is to enhance the capture effect of flotation collectors on fine-grained ilmenite. Therefore, developing new and efficient flotation collectors to reduce production costs and improve economic benefits is an important direction for improving the metal recovery rate of fine-grained ilmenite. Fatty acid collectors, such as oleic acid and its salts, are commonly used flotation collectors for ilmenite. In recent years, a large number of studies have been conducted on hydroxamic acid and hydrocarbylphosphonic acid collectors. For example, Chinese patent document publication number CN117732601A discloses a flotation agent combination of a short-chain fatty acid, phosphoric acid, and hydroxamic acid. Chinese patent document publication number CN117463510A discloses a solution for the flotation of fine-grained ilmenite using fatty acids. However, the capture ability of these agents for fine-grained ilmenite remains unsatisfactory, and there is a lack of dedicated collectors for fine-grained, difficult-to-treat ilmenite.

[0004] In summary, the current flotation process of "poor, fine and mixed" ilmenite lacks efficient and highly selective collectors. If conventional fatty acid collectors continue to be used, it will lead to problems such as low utilization of ilmenite metal resources and poor environmental protection. Summary of the Invention

[0005] In view of the problem that existing collectors have insufficient collection capacity for ilmenite, especially fine-grained ilmenite, and it is difficult to achieve a high flotation recovery rate, the present invention provides a collector for flotation of ilmenite, which aims to improve the collection and selectivity of ilmenite and make it suitable for the recovery rate requirements of flotation of ilmenite, especially fine-grained ilmenite.

[0006] The second object of the present invention is to provide a flotation agent comprising the collector for flotation of ilmenite.

[0007] The third object of the present invention is to provide a method for flotation of ilmenite using the collector and a flotation reagent containing the collector.

[0008] High-grade ilmenite is easy to achieve efficient and selective flotation recovery. However, due to the small number of adsorption sites on the surface of fine ilmenite that can effectively interact with reagents, the capture effect is greatly reduced. In addition, the fine ilmenite and gangue minerals form a complex intergrowth structure, which ultimately makes flotation significantly more difficult. To address this problem, the present invention proposes the following solutions:

[0009] A collector for flotation of ilmenite, comprising a collector a having a structure of Formula 1 and / or a collector b having a structure of Formula 2;

[0010]

[0011] The R1 is C1~C 10 Alkyl, R2 is H, C1~C 10 Said R3 is C1~C 10 Alkyl;

[0012] The M a 、M b H, Na, K or NH4 alone.

[0013] The present invention's innovative research demonstrates that using Collector A and / or Collector B as collectors for ilmenite exhibits excellent capture selectivity, efficiently and selectively targeting titanium in ilmenite, thereby improving its capture capacity and selectivity. Furthermore, the collectors of the present invention are surprisingly well-suited to the flotation requirements of fine-grained ilmenite, achieving excellent titanium capture capacity and selectivity during the flotation of fine-grained ilmenite.

[0014] In the present invention, the collector for flotation of ilmenite comprises the aforementioned collector a and collector b, wherein the content of collector a is greater than 10 wt.%, preferably greater than 20 wt.%, more preferably 10 to 80 wt.%, even more preferably 15 to 30 wt.%, and most preferably 18 to 22 wt.%. Studies have shown that at this preferred ratio, better synergy can be achieved, helping to further enhance the separation efficiency and selectivity of ilmenite and ferroilite from fine-grained minerals.

[0015] The present invention shows that the combination of collector a and collector b can help further enhance the ilmenite capture capacity and titanium-iron separation selectivity based on the intramolecular and intermolecular synergy of collectors a and b, especially for fine-grained ilmenite, which can also obtain excellent titanium capture performance and selectivity.

[0016] The present invention also provides a flotation agent for flotation of ilmenite, which comprises the collector of the present invention.

[0017] The flotation agent for flotation of ilmenite described in the present invention may contain other flotation components allowed to be added in the industry. For example, it may also contain at least one flotation aid selected from the group consisting of a pH regulator and a frother.

[0018] In the present invention, the pH adjuster can be a component known in the industry, for example, at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid. It should be noted that the selected pH adjuster, in addition to achieving pH regulation, can also have certain gangue inhibition effects.

[0019] The foaming agent includes, for example, 2 # At least one of oil, terpineol, methyl isobutyl carbinol, cresol oil, and polyethylene glycol ether.

[0020] In the present invention, the components of the flotation reagent are present independently of each other before use, or in a partially mixed or fully mixed form. In addition, the dosage of each component can also be reasonably adjusted according to the flotation requirements and efficiency.

[0021] The present invention also provides a method for flotation of ilmenite, which uses the collector as a collector to flotation ilmenite to obtain ilmenite concentrate.

[0022] In the present invention, the ilmenite can be any form and grade of ilmenite to be selected, but considering that the collector described in the present invention still has excellent capture performance and selectivity for fine-grained minerals compared to the existing technology, its use for fine-grained ilmenite may obtain better economic value than the existing technology.

[0023] In the present invention, the ilmenite flotation ore is fine-grained ilmenite, and the mass proportion of -38μm fine particles is greater than 40%.

[0024] Preferably, the titanium grade (TiO2 content) of the ilmenite is below 21 wt.% (for example, it can be 20.0 wt.% to 21.0 wt.%, and further can be 20.5 to 20.7 wt.%).

[0025] In the present invention, the collector of the present invention can be used for the flotation of the ilmenite based on existing conventional flotation equipment and ideas.

[0026] In the present invention, the amount of collector used in the flotation stage can be adjusted as needed, for example, it can be 2000-3000 g / t, further 2400-2600 g / t.

[0027] In the present invention, ilmenite ore can be floated based on the flotation reagent of the present invention to obtain ilmenite concentrate.

[0028] Furthermore, the flotation aid in the flotation reagent includes a pH regulator, wherein the amount of the pH regulator is 2000-2800 g / t, and further can be 2400-2600 g / t.

[0029] The flotation reagent may also contain a frother, and the amount thereof can be adjusted as needed, for example, 10 to 400 g / t, or further 20 to 150 g / t.

[0030] In the present invention, an optional flotation method specifically includes a desulfurization flotation step and a flotation process of performing roughing on the desulfurization flotation process, and further includes a two-stage concentration process of the roughing concentrate.

[0031] The reagents used in the desulfurization process include a pH regulator, a xanthate collector, and a foaming agent. The amount of the pH regulator can be 1000-1500 g / t; the amount of the xanthate collector can be 200-300 g / t; and the amount of the foaming agent can be 20-100 g / t.

[0032] In the roughing stage, the dosage of the pH adjuster is 300-800 g / t, and further can be 400-600 g / t; the dosage of the collector can be 1600-2200 g / t, and further can be 1700-1900 g / t.

[0033] The pH adjuster in the second concentrating stage is 300-800 g / t, and can be further 400-600 g / t; the collector is 100-500 g / t, and can be further 200-400 g / t.

[0034] Beneficial effects

[0035] The present invention studies have shown that the compounds of Formula 1 and / or Formula 2 have excellent specific capture capabilities for ilmenite. When used as collectors for ilmenite, they can effectively improve the capture rate and selectivity of ilmenite. In addition, the combination of Formula 1 and Formula 2 can further achieve intermolecular synergy, further enhance the flotation ability of ilmenite, and especially improve the flotation effect of fine-grained ilmenite. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the flotation flow chart of Example 1. DETAILED DESCRIPTION

[0037] In the present invention, the compound of formula 1 is typically represented by formula 1-A, and its specific structure is:

[0038]

[0039] The compound of formula 2 is exemplified by formula 2-A, and its specific structure is:

[0040]

[0041] Comparative structural compound, its specific structure is:

[0042]

[0043]

[0044] The mineral to be selected described in the present invention can be ilmenite of any grade. In order to further verify the collection ability of the collector of the present invention, the present invention particularly selects fine-grained ilmenite. For example, as an optional scheme, the fine-grained ilmenite selected below is the strong magnetic concentrate of the Panzhihua Iron and Steel Group Titanium Plant.

[0045] In the present invention, the collector of the present invention can be used to float the mineral based on conventional flotation means and principles. For example, as an optional embodiment, the flotation process can be as follows:

[0046] Example

[0047] The open circuit flotation test process was used to verify the effect of the collector of the present invention. Figure 1 This is the open circuit flotation flow chart. The steps are:

[0048] Step 1: Weigh 800 g of fine-grained ilmenite flotation ore (the mass proportion of -38 μm fine particles is greater than 40%, and the TiO2 grade is 20.55±0.1 wt.%).

[0049] Step 2: In the desulfurization flotation operation, the order of adding drugs is pH regulator sulfuric acid and sulfide ore collector xanthate. The dosage and slurry mixing time are as follows: Figure 1 After the addition of chemicals, desulfurization flotation is carried out for 5 minutes to obtain sulfur concentrate.

[0050] Step 3: In the ilmenite flotation operation, the order of adding the reagents is pH regulator (such as sulfuric acid) and ilmenite collector (see the following cases), the dosage and slurry mixing time are as follows: Figure 1 After the addition of chemicals, the ilmenite is subjected to open-circuit flotation through 5-minute roughing, 5-minute concentrating I, and 5-minute concentrating Ⅰ, to obtain four products: titanium concentrate, middlings 1, middlings 2, and tailings.

[0051] Step 4. Results and Analysis. Each open-circuit flotation test was repeated multiple times. The results in the examples are the averages of each result from 3-5 repetitions. Aside from the use of different collectors, all other conditions, such as reagent dosage, temperature, slurry preparation, and flotation time, were identical in each implementation case. The TiO2 grade / recovery of the titanium concentrate obtained from the two experimental sets was used to compare the collection effectiveness of the collector of the present invention.

[0052] In the above Figure 1 Based on the flotation, the collector and conditions of each case were adjusted. The steps and results were as follows:

[0053] Example 1 - Single Collector Solution

[0054] The collector is a single collector, and the experimental groups are:

[0055] Group A: The collector is Formula 1-A;

[0056] Group B: Collector is Formula 2-A;

[0057] Comparative group a: the collector is formula 3-A;

[0058] Comparative group b: the collector is formula 4-A;

[0059] Comparative group c: the collector is formula 5-A;

[0060] Comparative group d: the collector is sodium oleate;

[0061] The results of each group are shown in Table 1:

[0062] Table 1

[0063]

[0064]

[0065] It can be seen from Example 1 that the use of Formula 1-A and Formula 2-A described in the present invention as collectors can adapt to the characteristics of fine-grained ilmenite and achieve a more ideal collection effect.

[0066] Example 2 - Binary Collector Solution

[0067] The collector is a binary composite collector, and the experimental groups are:

[0068] Group A: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:1;

[0069] Group B: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:2;

[0070] Group C: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 2:1;

[0071] Comparative group a: the collectors are Formula 1-A and Formula 4-A in a weight ratio of 1:1;

[0072] Comparative group b: the collectors are Formula 2-A and Formula 3-A in a weight ratio of 1:1;

[0073] The results of each group are shown in Table 2:

[0074] Table 2

[0075]

[0076]

[0077] It can be seen from Examples 1 and 2 that the combination of Formula 1 and Formula 2 can further enhance the synergy, and the formula of Group B (Formula 1-A and Formula 2-A with a weight ratio of 1:2) has the best flotation effect, can better adapt to the characteristics of fine-grained ilmenite, and can obtain a more ideal collection effect.

[0078] Example 3 - Binary Collector Formula Optimization Scheme

[0079] In the case of adjusting the ratio of combined collectors, the experimental groups are:

[0080] Group A: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:3;

[0081] Group B: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:4;

[0082] Group C: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:5;

[0083] Group D: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:6;

[0084] The results of each group are shown in Table 3:

[0085] Table 3

[0086]

[0087]

[0088] It can be seen from Examples 1 to 3 that optimizing the compounding ratio of Formula 1 and Formula 2 can further enhance the synergy and further improve the collection effect of fine-grained ilmenite. The best collector formula obtained is Formula 1-A and Formula 2-A with a weight ratio of 1:4.

[0089] Example 4

[0090] Compared with the group B of Example 3, the only difference is that the amount of the collector is changed. The experimental groups are:

[0091] Group A: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:4. The collector dosages for roughing, concentrating I, and concentrating Ⅰ are 1600 g / t, 300 g / t, and 300 g / t, respectively.

[0092] Group B: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:4. The dosages of the collectors for roughing, concentrating I, and concentrating Ⅰ are 2000 g / t, 300 g / t, and 300 g / t, respectively.

[0093] Group C: The collectors are Formula 1-A and Formula 2-A in a weight ratio of 1:4. The collector dosages for roughing, concentrating I, and concentrating Ⅰ are 2200 g / t, 300 g / t, and 300 g / t, respectively.

[0094] The results of each group are shown in Table 4:

[0095] Table 4

[0096]

[0097] It can be seen from Examples 3 and 4 that the combination of Formula 1 and Formula 2 has an excellent collection effect on fine-grained ilmenite even at a lower collector dosage. When the collector dosage is high, more gangue will be mixed into the flotation concentrate, reducing its selectivity, resulting in a lower grade of titanium concentrate and a lower metal recovery rate. Therefore, the optimal collector dosage is 1800 g / t, 300 g / t and 300 g / t for roughing, concentrating I and concentrating Ⅰ, respectively.

Claims

1. A method for flotation of ilmenite, comprising flotation of ilmenite with a collector to obtain ilmenite concentrate; wherein: The collector comprises a collector a having a structure of formula 1, and / or a collector b having a structure of formula 2; Formula 1 Formula 2 The R1 is C1~C 10 Alkyl, R2 is H, C1~C 10 Said R3 is C1~C 10 Alkyl; The M a 、M b H, Na, K or NH4 alone.

2. The method according to claim 1, wherein The collector comprises the collector a and the collector b, wherein the content of the collector a is above 10 wt.%.

3. The method according to claim 2, wherein The content of collector a is 10~80wt.%.

4. The method according to claim 3, wherein The content of collector a is 15~30wt.%.

5. The method according to claim 4, wherein The content of collector a is 18~22wt.%.

6. The method according to claim 1, wherein The ilmenite flotation ore is fine-grained ilmenite, and the mass proportion of -38μm fine particles is greater than 40%.

7. The method according to claim 1, wherein The dosage of collector in the flotation stage is 2000~3000 g / t.

8. The method according to claim 7, wherein The dosage of collector in the flotation stage is 2400~2600 g / t.

9. The method according to any one of claims 1 to 8, wherein The flotation reagents in the flotation process further include at least one flotation aid selected from the group consisting of a pH regulator and a frother.

10. The method according to claim 9, wherein The pH regulator includes at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid; The foaming agent includes 2 # At least one of oil, terpineol, methyl isobutyl carbinol, cresol oil, and polyethylene glycol ether.

11. The method according to claim 10, wherein The flotation aid in the flotation reagent includes a pH regulator, and the amount of the pH regulator is 2000-2800 g / t.

12. The method according to claim 11, wherein The dosage of pH regulator is 2400~2600 g / t.

13. A collector for flotation of ilmenite, characterized in that: The collector comprising the collector a and the collector b described in any one of claims 1 to 12.

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