Collecting agent, flotation reagent and method for flotation of ilmenite

Abstract

The invention belongs to the field of mineral flotation, and particularly relates to a collecting agent, a flotation reagent and a method for flotation of ilmenite, the collecting agent comprises at least one of a collecting agent a, a collecting agent b and a collecting agent c, the collecting agent a is a component with a formula 1 # imgabs 0 # structure, and the collecting agent b is a component with a formula 2 # imgabs 1 # structure; and the collecting agent c is a component with a structure as shown in a formula 3 # imgabs2 #. Researches show that an adopted collecting agent a and / or a collecting agent b can serve as a high-selectivity collecting agent of the ilmenite and have / has the high collecting capacity for the ilmenite, in addition, the collecting agent a and / or the collecting agent b do not have the collecting capacity for gangue minerals such as titanaugite and can be suitable for flotation separation of the ilmenite and the gangue minerals such as the titanaugite, and therefore the flotation separation efficiency of the ilmenite and the gangue minerals such as the titanaugite is improved. And high-grade titanium concentrate is obtained.

Description

Technical Field

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

[0002] Titanium is widely used in fields such as aerospace, chemical engineering, and energy. Ilmenite (FeTiO3) is an important mineral source for extracting titanium. However, natural ilmenite often coexists with other ferromagnesian minerals, such as titanaugite ((Ca,Mg,Fe,Ti)(Al,Si)2O6). Titanaugite and ilmenite have certain similarities in surface properties, making it difficult to achieve efficient separation using traditional flotation methods, which severely restricts the comprehensive utilization of titanium resources. Traditional flotation collectors, such as fatty acids and their soaps, phosphate esters, etc., although having a certain collecting ability for ilmenite under certain conditions, often have poor selectivity. These collectors are easily adsorbed on the surfaces of both ilmenite and titanaugite, resulting in a large amount of titanaugite entering the ilmenite concentrate and reducing the concentrate grade. In addition, traditional collectors also have disadvantages such as strong foaming ability and being easily affected by water quality, further increasing the difficulty of flotation separation.

[0003] Therefore, the development of new, highly efficient, and selective flotation collectors for ilmenite is of great practical significance and economic value for improving the utilization rate of titanium resources and reducing production costs. Fatty acid collectors are commonly used flotation collectors for ilmenite, and in recent years, the development of some new collectors has also been carried out. For example, the patent document with the publication number CN118663424A discloses a highly selective hydroxamic acid collector, the patent document with the publication number CN119281515A discloses the preparation of a higher fatty acid collector and its flotation application in ilmenite and gangue minerals, and the patent document with the publication number CN116213129A discloses a composite styrene phosphoric acid collector for the flotation process of ilmenite. However, the separation effect of the above agents on ilmenite flotation is still not ideal, and there is a lack of highly selective collectors for the separation of ilmenite and gangue minerals. Summary of the Invention

[0004] Aiming at the problem that the collecting ability and selectivity of existing ilmenite flotation collectors are not ideal, the present invention provides a collector for flotation of ilmenite, aiming to improve the collecting ability and collecting selectivity of ilmenite.

[0005] The second object of the present invention is to provide a flotation agent for flotation of ilmenite containing the above collector.

[0006] The third object of the present invention is to provide a method for flotation of ilmenite using the above collector and flotation agent.

[0007] A collector for flotation of ilmenite, comprising at least one of collector a, collector b, and collector c. Among them, collector a is a component with the structure of Formula 1, collector b is a component with the structure of Formula 2; collector c is a component with the structure of Formula 3;

[0008]

[0009] R1, R2, and R3 are H, alkyl with 1 - 5 carbon atoms, alkoxy with 1 - 5 carbon atoms, halogen, nitro, or trifluoromethyl; X is alkylene with 1 - 5 carbon atoms;

[0010] M is H, Na, K, or NH4.

[0011] Research in this invention shows that collectors a - c can be used as highly selective collectors for ilmenite, having a strong collecting ability for ilmenite. In addition, collectors a - c do not have a collecting ability for gangue minerals such as titanaugite, and can be adapted to the flotation separation of ilmenite and gangue minerals such as titanaugite to obtain high - grade ilmenite concentrate.

[0012] Preferably, R1, R2, and R3 are alkoxy with 1 - 5 carbon atoms. Research in this invention shows that collectors with preferred substituents can further adapt to the characteristics of ilmenite and help to further enhance the collecting ability.

[0013] Preferably, at least collector a is included in the collector. Research shows that collector a can obtain better separation selectivity between ilmenite and titanaugite compared to collectors b and c.

[0014] Preferably, the collector comprises collector a and collector b with a mass ratio of 10 - 100:50 - 100; preferably 10 - 70:

[0015] 60 - 100; more preferably 10 - 40:60 - 90; most preferably 25 - 35:65 - 75. Research shows that the combined use of collector a and collector b is the key to improving the separation performance of ilmenite, and further optimization of the mass ratio of the two collectors is beneficial to improving the selectivity of the composite collector for ilmenite.

[0016] This invention also provides a flotation reagent for flotation of ilmenite, which contains the above - mentioned collector.

[0017] The flotation reagent for flotation of ilmenite may further contain at least one flotation aid allowed to be added in the flotation system, such as an inhibitor, a pH regulator, a foaming agent, a hydrocarbon component, etc.

[0018] As an alternative, the flotation reagent in this invention is a reagent containing the collector, a pH regulator, a hydrocarbon component, and a foaming agent.

[0019] In the present invention, the pH regulator may be conventional components such as acids and bases.

[0020] The foaming agent described in the present invention is any component capable of foaming, such as fusel oil, terpineol, methyl isobutyl carbinol, polyethylene glycol ether and the like.

[0021] Preferably, the hydrocarbon component is an alkane with C4 - C 22 and is preferably at least one of gasoline, kerosene, diesel oil, and kerosene.

[0022] In the present invention, adding a certain amount of hydrocarbon component to the flotation system helps to improve the flotation effect of the collector and can also reduce the dosage of the foaming agent.

[0023] In the present invention, the proportion of the components in the flotation reagent can be reasonably adjusted according to the flotation requirements of the minerals.

[0024] The present invention also provides a method for flotation of ilmenite. The ore to be selected containing ilmenite is roughened with a flotation reagent containing the collector described in the present invention to obtain a rougher concentrate of ilmenite.

[0025] In the present invention, the ore to be selected is a mixed mineral containing ilmenite and titanaugite; through the roughening, ilmenite therein is selectively collected;

[0026] Preferably, the ore to be selected is the mineral after desulfurization treatment of the ilmenite raw ore.

[0027] In the present invention, during the roughening process, the dosage of the collector is 30 - 3000 g / t; considering the cost, it can be further preferably 50 - 150 g / t.

[0028] For the method for flotation of ilmenite described in the present invention, the flotation reagent may be a flotation reagent containing the collector, pH regulator, hydrocarbon component, and foaming agent.

[0029] Furthermore, the components in the flotation reagent can be reasonably adjusted according to the mineral characteristics and the flotation reagent. For example, the dosage of the hydrocarbon component is 1 - 50 g / t, and can be further 5 - 20 g / t. The dosage of the foaming agent is 1 - 50 g / t, and can be further 5 - 25 g / t.

[0030] Preferably, the roughening pH is 7.0 - 9.0, and can be further 7.5 - 8.5; at the preferred pH, it has a better ilmenite collecting ability and selectivity.

[0031] In the present invention, the rough concentrate of ilmenite is beneficiated to obtain ilmenite concentrate. The middlings in the beneficiation process can be returned to the previous flotation process. In the present invention, the flotation reagents in the beneficiation process can be adjusted as needed. For example, they can be reagents containing a foaming agent, and further can be only a foaming agent.

[0032] In the present invention, the tailings of rough selection can be further scavenged. The scavenged tailings are the final tailings, and the scavenged concentrate can be returned to the rough selection process.

[0033] Beneficial effects:

[0034] 1. Through selective chelation, collectors a to c form stable coordination complexes with the iron (Fe) and titanium (Ti) active sites on the surface of ilmenite. This chelation mechanism significantly enhances the affinity of the collectors for ilmenite, thereby enhancing its selectivity. Conversely, such collectors interact weakly with the active sites on the surface of gangue minerals such as titanaugite, showing low selectivity, providing a theoretical basis for the efficient separation of ilmenite from gangue minerals.

[0035] 2. The combined use of collector a and collector b can produce a significant intermolecular synergistic effect. This effect stems from the interaction between the two collector molecules, which may include hydrogen bonds, van der Waals forces, etc. The synergistic effect can enhance the adsorption strength of the collectors on the mineral surface, increase its coverage rate, thereby reducing the total dosage of collectors while maintaining or even increasing the flotation recovery rate of ilmenite, effectively reducing the cost of flotation reagents.

[0036] 3. Further adding hydrocarbon components to the flotation reagents can further regulate the interfacial properties of the pulp and further enhance the collecting ability of the collectors for ilmenite and the separation selectivity of ilmenite and iron.

[0037] 4. The flotation process flow proposed in the present invention is relatively short and simplified, and the dosage of required reagents is low. It not only reduces the beneficiation cost, but also significantly reduces the pressure of beneficiation wastewater treatment, conforms to the development trend of green beneficiation, and has good environmental friendliness. Description of the drawings

[0038] Figure 1 It is the single-mineral flotation experiment flow chart of Example 1.

[0039] Figure 2 It is the result of the single-mineral flotation experiment.

[0040] Figure 3 It is the 1H NMR spectrum (upper figure) and 13C NMR spectrum (lower figure) of Formula 1-B.

[0041] Figure 4 It is the 1H NMR spectrum (see Figure a therein) and 13C NMR spectrum (see Figure b therein) of Formula 2-A.

[0042] Figure 5 It is the flow chart of the flotation process in Example 2. Detailed implementation manners

[0043] In the present invention, taking the compounds of Formula 1 as examples of Formula 1-A and Formula 1-B, their specific structures are:

[0044]

[0045]

[0046] The synthesis route of Formula 1 is as follows:

[0047]

[0048] For example, the steps of its synthesis are as follows:

[0049] Step 1: Dissolve NH₂OH·HCl in an appropriate amount of water. Slowly add a sodium carbonate or sodium hydroxide solution until the solution is alkaline (pH is 9.5 ± 0.3).

[0050] Step 2: Dissolve raw material A in an appropriate amount of ether or other suitable organic solvents (dichloromethane or tetrahydrofuran), and then add the solution of Step 1. At the same time, cool the reaction system with an ice bath, and maintain the reaction temperature at 0 - 5 °C. After the dropping is completed, restore to room temperature and continue to stir the reaction for a period of time (usually 2 - 3 hours) until the reaction is complete.

[0051] Step 3: Post-treatment of the reaction: Transfer the reaction mixture to a separatory funnel. Extract the aqueous phase with an organic solvent such as ether or dichloromethane for multiple times, and combine the organic phases. Wash the organic phase with saturated brine to remove water-soluble impurities, and then dry the organic phase with anhydrous sodium sulfate. The final product is obtained after drying.

[0052] Taking the compound of Formula 2 as an example of Formula 2-A, its specific structure is:

[0053]

[0054] The synthesis route of this type of medicament is as follows:

[0055] The preparation method of Formula 2 is similar to that of Formula 1. The main difference is that the following raw material B is used to replace the raw material A.

[0056]

[0057] Taking the compound of Formula 3 as an example of Formula 3-A, its specific structure is:

[0058]

[0059] Its synthesis method is similar to that of Formula 1, only select Replace raw material A as the raw material.

[0060] Compare the structural compound, and its specific structure is:

[0061]

[0062] The candidate minerals described in the present invention can be ilmenite minerals of any grade. In order to further verify the collecting ability of the collector of the present invention, single-mineral flotation experiments of ilmenite and titanaugite, as well as actual ore experiments in the titanium separation plant of Pangang Group, were carried out in the present invention.

[0063] In the following examples of the present invention, the actual ore can be subjected to conventional desulfurization treatment as needed. For example, in order to further verify the flotation advantage of the medicament of the present invention, in the following cases, the actual ore containing ilmenite and titanaugite is pre-treated by desulfurization flotation to obtain desulfurized minerals, and then the desulfurized minerals are used as candidate minerals for the collector described in the present invention to participate in the subsequent flotation of ilmenite. The conditions for desulfurization flotation treatment can be conventional. For example, the medicaments for desulfurization flotation can include inhibitors (such as water glass), sulfur collectors (such as xanthates, and further butyl xanthate), and foaming agents (such as No. 2 oil); among them, the dosage of the inhibitor can be 10-30 g / t, the dosage of the sulfur collector can be 450-550 g / t, the dosage of the foaming agent can be 10-30 g / t, and the pH of the desulfurization flotation treatment can be 3-4.

[0064] In the present invention, the titanium grade of the desulfurized minerals (also referred to as candidate minerals containing ilmenite and titanaugite in the following cases) can be between 5% and 10%.

[0065] Example 1:

[0066] Flotation separation of ilmenite and titanaugite under the composite collector system:

[0067] The composite collector in this example: Formula 1-A and Formula 2-A The weight ratio of Formula 1-A and Formula 2-A is 3:7.

[0068] Adopt Figure 1 The shown process, and the specific operation is: Pour 2 g of a single pure mineral ore (ilmenite and titanaugite) sample into a 45 mL flotation cell, add a pH adjuster to adjust the pulp pH, add 40 mL of deionized water, and then add the composite collector of this example. The dosage of the composite collector is 2×10 -4 mol / L, stir for 3 min, add 1 microliter of terpineol, stir for 2 min, start scraping foam, scrape foam for 2 min, the concentrate and tailings are filtered and dried and then weighed respectively, and the recovery rate is calculated. Each group of experiments is carried out in three parallel groups, and the average value is taken. Figure 2Recovery rates of ilmenite and titanaugite under different pH conditions in Example 1.

[0069] Comparative Example 1:

[0070] Compared with Example 1, the difference is only that the composite collector is changed to the traditional ilmenite collector sodium oleate. The specific experimental results are shown in Figure 2 .

[0071] As Figure 2 shown, the composite reagent in this example has selective collecting ability for ilmenite throughout the pH range. Under the optimal pH condition (pH = 8.5), ilmenite can be efficiently collected (recovery rate exceeds 90%), while the recovery rate of titanaugite is lower than 20% at this time, and the difference in recovery rates between ilmenite and titanaugite is greater than 60%. Compared with the traditional sodium oleate collector (the recovery rate of ilmenite is lower than 60% in all cases), it is proved that the composite collector in this example has good flotation performance for ilmenite.

[0072] Example 2:

[0073] Take 300 g of the ore to be selected containing ilmenite and titanaugite (85% of the ore particles have a particle size less than 0.074 mm), and conduct a flotation experiment in a 0.5 L flotation machine using the Figure 5 process shown. After pouring the ore into a 0.5 L flotation cell, stir to fully disperse the pulp. Pour the ilmenite rough concentrate into a 0.5 L flotation cell and stir to fully disperse the pulp. Subsequently, use flotation reagents for roughing treatment to obtain the rough concentrate and the rough tailings. Conduct three-stage cleaning on the rough concentrate (the roughing foam product) for cleaning treatment to obtain the ilmenite concentrate;

[0074] The flotation reagents in the roughing stage include a pH regulator, a collector, a hydrocarbon component, and a foaming agent. Among them, the pH regulator is sodium carbonate, and the pH regulator is used to adjust the pulp pH to 8.5. The collectors (in the following groups, each group of collectors is 90 g / t), the hydrocarbon component (in this case, kerosene, with a dosage of 10 g / t), and the foaming agent No. 2 oil 10 g / t;

[0075] In the cleaning stage, the dosage of the foaming agent No. 2 oil is sequentially added 10 g / t, 10 g / t, and 5 g / t each time for cleaning. The final ilmenite concentrate and middlings 1 - 3 are obtained.

[0076] The collectors for each group are respectively:

[0077] Group A: The collector is Formula 1 - A

[0078] Group B: The collector is Formula 2 - A

[0079] Group C: The collector is Formula 1 - B

[0080] Group D: The collector is Formula 3-A

[0081] Control group a: The collector is Comparative Formula C

[0082] Control group b: The collector is sodium oleate;

[0083] Control group c: Comparative Formula A

[0084] Control group d: Comparative Formula B

[0085] The results of each group are shown in Table 1:

[0086] Table 1

[0087]

[0088]

[0089] It can be seen from the experimental results of each group in Example 2 that:

[0090] By adding and comparing the structures of collectors a to c, a better recovery rate of ilmenite can be obtained. Among them, the conjugate system of collector a can exhibit better performance.

[0091] Example 3:

[0092] Compared with Example 2, the difference is only that the following combined collectors are used for the experiment, and the total collector dosage and other operating conditions are the same as those in Example 2. The experimental groups are respectively:

[0093] Group A: The collectors are Formula 1-A and Formula 2-A, and their ratio is 10:90 by weight;

[0094] Group B: The collectors are Formula 1-A and Formula 2-A, and their ratio is 20:80 by weight;

[0095] Group C: The collectors are Formula 1-A and Formula 2-A, and their ratio is 30:70 by weight;

[0096] Group D: The collectors are Formula 1-A and Formula 2-A, and their ratio is 40:60 by weight;

[0097] The dosage of the total collector and the flotation conditions are the same as those in Example 2.

[0098] The results of each group are shown in Table 2:

[0099] Table 2

[0100]

[0101] It can be seen from the experimental results of each group in Example 3 that:

[0102] It can be seen from Experimental Groups A to D that different ratios of the collectors of Formula 1-A and Formula 2-A can affect the flotation effect of ilmenite through intramolecular synergistic effects. The preferred collectors are Formula 1-A and Formula 2-A, and the ratio of 30:70 by weight can obtain the optimal flotation effect of ilmenite.

[0103] Example 4:

[0104] Compared with Group C in Example 3, the difference is only that the composition and dosage of the flotation reagents for rough selection are changed. The experimental groups are as follows:

[0105] Group A: The hydrocarbon component is replaced with gasoline, with a dosage of 15 g / t; the dosage of the collector is 80 g / t, and the dosage of the frother is 15 g / t;

[0106] Group B: The hydrocarbon component is replaced with diesel oil, with a dosage of 10 g / t; the dosage of the collector is 100 g / t, and the dosage of the frother is 10 g / t;

[0107] Group C: No hydrocarbon component is added;

[0108] The results of each group are shown in Table 3:

[0109] Table 3

[0110]

[0111]

[0112] 1. Using the alkane mixture (Groups A, B) can obtain a better ilmenite recovery rate than not using the alkane mixture (Group C).

[0113] 2. The preferred alkane mixture is the C12 - C15 hydrocarbon mixture (kerosene), which can obtain a better flotation effect than the same type of alkane mixture.

[0114] Example 5:

[0115] Compared with Group C in Example 3, the difference is only that the pulp pH during flotation is adjusted, and the pulp pH of the experimental groups is 7 / 8 / 9.

[0116] Group A: The pulp pH during the rough selection of ilmenite flotation is 7;

[0117] Group B: The pulp pH during the rough selection of ilmenite flotation is 9;

[0118] The results of each group are shown in Table 4:

[0119] When rough selecting ilmenite, a pulp pH of 8 can achieve a better ilmenite recovery rate than other pulp pH values.

[0120] Table 4

[0121]

[0122] Based on the above results, it is shown that the ilmenite collector of the present invention realizes the efficient separation and enrichment of ilmenite and titanaugite.

Claims

1. A collector for flotation of ilmenite, characterized in that, Comprising at least one of collector a, collector b, and collector c, wherein collector a is a component having the structure of Formula 1, collector b is a component having the structure of Formula 2; collector c is a component having the structure of Formula 3; R1, R2, and R3 are H, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen, a nitro group, or a trifluoromethyl group; X is an alkylene group having 1 to 5 carbon atoms; M is H, Na, K, or NH4.

2. The collector for flotation of ilmenite according to claim 1, characterized in that, The collector described above includes collector a and collector b with a mass ratio of 10 to 100:50 to 100; preferably 10 to 70:60 to 100; more preferably 10 to 40:60 to 90; most preferably 25 to 35:65 to 75.

3. A flotation reagent for ilmenite flotation, characterized in that, Comprising the collector according to any one of claims 1 to 2.

4. The flotation reagent for ilmenite flotation according to claim 3, characterized in that, It further comprises at least one of an inhibitor, a pH regulator, a foaming agent, and a hydrocarbon component.

5. The flotation reagent for ilmenite flotation according to claim 4, wherein, The flotation reagent described above contains a pH regulator, a hydrocarbon component, and a foaming agent; Among them, the hydrocarbon component is an alkane with C4 to C 22 ; preferably at least one of gasoline, kerosene, diesel, and kerosene.

6. A method for flotation of ilmenite, characterized in that, The mineral to be selected containing ilmenite is roughened using a flotation reagent comprising the collector according to any one of claims 1 to 4 to obtain a rougher concentrate of ilmenite.

7. The method for flotation of ilmenite according to claim 6, characterized in that, The mineral to be selected is a mixed mineral containing ilmenite and titanaugite; through the above-mentioned roughening, ilmenite therein is selectively collected; Preferably, the mineral to be selected is a mineral obtained by desulfurizing ilmenite ore.

8. The method for flotation of ilmenite according to claim 6, characterized in that, During the roughening process, the dosage of the collector is 30 to 3000 g / t; more preferably 50 to 150 g / t.

9. The method for flotation of ilmenite according to any one of claims 6 to 8, characterized in that, The flotation reagent is the flotation reagent according to claim 5; Preferably, the dosage of the inhibitor is 1 to 50 g / t; the dosage of the hydrocarbon component is 1 to 50 g / t; Preferably, the roughening pH is 7.0 to 9.

0.

10. The method for flotation of ilmenite according to any one of claims 6 to 8, characterized in that, The rougher concentrate of ilmenite is beneficiated to obtain a concentrate of ilmenite; Preferably, the flotation reagent in the beneficiation stage is a reagent containing a foaming agent.

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