Ilmenite collector and preparation method and application thereof

Abstract

The application belongs to the field of mineral flotation, and particularly discloses a titanium-iron ore collector and preparation and application thereof. The titanium-iron ore collector has a structural formula of formula 1. Researches show that the structure field constructed by formula 1 can target iron and titanium sites of the iron-titanium ore with high selectivity, can efficiently and selectively collect the titanium-iron ore, and can improve the collection rate and selectivity of the titanium-iron ore.

Description

Technical Field

[0001] This invention relates to the field of ilmenite collection, and more specifically to the field of ilmenite collectors. Background Technology

[0002] Ilmenite is an oxide mineral of iron and titanium and is the main ore for titanium refining. Flotation is a key step in removing gangue from the mineral, improving the grade of titanium concentrate, and thus improving the resource recovery of titanium.

[0003] Existing collectors for ilmenite mainly include fatty acids, hydroxamic acid, arsenoic acid, and phosphonic acid collectors. For example, Chinese patent document CN120381933A discloses a collector, flotation reagent, and method for flotating ilmenite, wherein the collector includes at least one of collector a, collector b, and collector c, wherein collector a has the following formula ( ) The components with the structure ) and the collector b having the formula 2 ( The components with the structure ); the collector c is a component with the structure of formula 3 ( ) components of the structure.

[0004] For example, patent document CN105583084A discloses a flotation collector comprising 0.40-0.55 parts oleic acid, 0.20-0.40 parts oxidized paraffin soap, 0.05-0.10 parts emulsifier, and 0.10-0.20 parts C7-9 hydroxamic acid. As another example, patent document CN114832950A discloses a highly efficient collector for ilmenite and its preparation method, comprising 58-62% rosin, 18-20% sodium bisulfite, 11-13% ethanolamine, and 7-9% alkyl sulfonate. Furthermore, patent document CN118788491A discloses an ultrafine-grained ilmenite flotation collector and its application, which includes 48%~70% octadecenoic acid, 14%~24% fatty alcohol polyoxyethylene ether carboxylic acid ester, 2%~5% polypropylene glycol, 5%~8% octanoyl oxyoxime acid, and 9%~15% fatty alcohol phosphate potassium salt.

[0005] In summary, various types of ilmenite collectors have been reported in the existing technology, but most of the existing collectors require the combined use of multiple types of collectors, resulting in relatively high reagent costs; in addition, the use of complex collectors is not conducive to the subsequent efficient processing of the concentrate. Summary of the Invention

[0006] In view of the problems existing in the prior art, the primary objective of this invention is to provide a novel ilmenite collector, which aims to provide a novel collector with excellent ilmenite collecting ability and selectivity.

[0007] The second objective of this invention is to provide a method for preparing the ilmenite collector and its application in ilmenite flotation.

[0008] An ilmenite collector having the structural formula of Formula 1:

[0009] Formula 1;

[0010] In Equation 1, R represents C4~C 24 The hydrocarbon group or oxygen-containing hydrocarbon group; M is Na or K.

[0011] This invention innovatively demonstrates that the structural domains constructed using Formula 1 can selectively target the iron and titanium sites of ilmenite, enabling efficient and selective harvesting of ilmenite and improving its recovery rate and selectivity.

[0012] In this invention, in Formula 1, R is C4~C 24 Alkyl or oxygen-containing alkyl groups, C6~C 16 aryl or C5~C 16 Five- or six-membered cyclic hydrocarbon groups;

[0013] Preferably, R is C6~C 14 Alkyl groups; more preferably C8~C 12 Alkyl groups. Collectors of Formula 1 with preferred substituents exhibit superior targeting ability and selectivity for ilmenite, achieving excellent collection rates and selectivity at lower reagent dosages.

[0014] In this invention, the alkyl group can be a straight-chain or branched alkyl group.

[0015] The present invention also provides a method for preparing the ilmenite collector described above, wherein the raw materials shown in Formula 2 are reacted with MOH and CS2 to obtain the ilmenite collector described in Formula 1.

[0016] Formula 2;

[0017] In Equation 2, R is the same as in Equation 1; in MOH, M is the same as in Equation 1.

[0018] In this invention, the solvent for the reaction includes at least one of water, methanol, ethanol, or propanol; preferably methanol.

[0019] In this invention, the molar ratio of Formula 2, MOH, and CS2 is 1:1~2:1~2; considering cost, it can be further 1:1~1.1:1~1.1.

[0020] In this invention, the reaction temperature is -20℃ to 40℃, and can be further 5℃ to 15℃, and the reaction time is 0.5 to 8 hours, and can be further 1 to 3 hours.

[0021] The present invention also provides an application of the aforementioned ilmenite collector, using it as a collector for the flotation of ilmenite.

[0022] In this invention, the mineral to be floated, which contains ilmenite, and the flotation reagent containing collector of formula 1 can be mixed and floated to separate and obtain ilmenite concentrate.

[0023] In this invention, the pH of flotation is 1.5 to 10.5; more preferably 6 to 9; and even more preferably 7.5 to 8.5. At the preferred pH, the intramolecular synergistic effect of collector formula 1 can be further enhanced, and the targeting effect on the iron and titanium sites of ilmenite can be further enhanced, thereby improving the collection rate and selectivity.

[0024] In this invention, the amount of collector used in the flotation process is 0.2~1500g / t, for example, it can be 500~1000g / t.

[0025] In this invention, a frother may be added to the flotation system.

[0026] The foaming agent can be any component with foaming ability, such as MIBC. Its dosage can be adjusted appropriately as needed.

[0027] Beneficial effects

[0028] This invention provides a novel collector of Formula 1, which can unexpectedly selectively target and adapt to the iron and titanium sites of ilmenite, effectively improving the recovery rate and selectivity of ilmenite. Attached Figure Description

[0029] Figure 1 The proton NMR spectrum of Formula 1A synthesized in Example 1;

[0030] Figure 2 The proton NMR spectrum of Formula 1B synthesized in Example 2;

[0031] Figure 3 The infrared spectrum of Equation 1A;

[0032] Figure 4 The infrared spectrum of Equation 1B; Detailed Implementation

[0033] The following examples are intended to further illustrate the invention, but not to limit the scope of protection of the invention. All parts and percentages in the examples refer to mass unless otherwise specified. The flotation processes for the minerals in the examples are conventional processes, except that the collector of Formula 1 of the present invention is used instead of the conventional flotation collector.

[0034] Synthetic Example 1: Formula 1A ( Synthesis of )

[0035] Add formula 2A to 60 mL of methanol solvent. 6.58 g (0.02 mol) was stirred to fully dissolve the product in a solvent. KOH (0.02 mol) and CS2 (0.02 mol) were added below 10 °C, and the mixture was stirred thoroughly for 2 h. After the reaction was complete, the crude product of Formula 1A was obtained by direct filtration. Then, it was recrystallized using methanol as a solvent to obtain Formula 1A. Its nuclear magnetic resonance (NMR)... 1 H NMR see Figure 1 .

[0036] Synthetic Example 2: Formula 1B ( Synthesis of )

[0037] Add formula 2B (to 60 mL of methanol solvent) 7.70 g (0.02 mol) was stirred to fully dissolve the product in a solvent. KOH (0.02 mol) and CS2 (0.02 mol) were added below 10 °C, and the mixture was stirred thoroughly for 2 h. After the reaction was complete, the crude product of formula 1B was obtained by direct filtration. Then, it was recrystallized using methanol as a solvent to obtain formula 1B. Its nuclear magnetic resonance (NMR)... 1 H NMR see Figure 2 .

[0038] Other compounds of the same type can be synthesized using this method.

[0039] The proton and infrared spectra of Formula 1A and Formula 1B are shown below. Figures 1-4 The results are shown in Tables 1 and 2.

[0040]

[0041]

[0042] Application Example 1: Ilmenite Flotation

[0043] The concentration of the collector (Formula 1A) is 1.5 × 10⁻⁶. -6 With a mol / L concentration, pulp pH of 8, frother methyl isobutyl methanol (MIBC) concentration of 30 mg / L, and N2 gas flow rate of 200 mL / min, ilmenite with a particle size of -0.076 mm to +0.038 mm was floated for 3 minutes, and the flotation recovery rate of ilmenite was 92.52%.

[0044] Application Example 2

[0045] Compared to Application Example 1, the only difference is that the collector used is replaced with Formula 1B, and its concentration in the flotation pulp is controlled at 7 × 10⁻⁶. -7The concentration was mol / L, and all other operations and parameters were the same as in Example 1. The flotation recovery rate of ilmenite was 98.37%.

[0046] Application Example 3

[0047] Compared to Application Example 1, the only difference is that the pulp pH was adjusted to 7; all other operations and parameters are the same as in Example 1. The flotation recovery rate of ilmenite was 91.05%.

[0048] Application Example 4

[0049] Compared to Application Example 1, the only difference is that the pulp pH was adjusted to 9; all other operations and parameters were the same as in Example 1. The flotation recovery rate of ilmenite was 86.95%.

[0050] Application Example 5

[0051] Compared to Application Example 1, the only difference is that the concentration of the collector (Formula 1A) is 1.0 × 10⁻⁶. -6 The concentration was mol / L, and all other operations and parameters were the same as in Example 1. The flotation recovery rate of ilmenite was 87.49%.

[0052] Application Example 6: Flotation of Artificial Mixtures of Ilmenite and Titanium Spodumene

[0053] The concentration of the collector (Formula 1A) is 1.5 × 10⁻⁶. -6 With a pulp pH of 8, a frother concentration of 30 mg / L methyl isobutyl methanol (MIBC), and an N2 gas flow rate of 200 mL / min, an artificial mixture of ilmenite and pyroxene (mass ratio 1:1) with a particle size of -0.076 mm to +0.038 mm was floated for 3 minutes. At this time, the flotation recoveries of ilmenite and pyroxene were 95.23% and 44.71%, respectively.

[0054] Application Example 7

[0055] Compared to Application Example 6, the only difference is that the concentration of the collector (Formula 1A) is 1.0 × 10⁻⁶. -6 The concentration was mol / L, and all other operations and parameters were the same as in Example 6. At this point, the flotation recoveries of ilmenite and pyroxene were 83.31% and 41.62%, respectively.

[0056] Application Example 8

[0057] Compared to Application Example 6, the only difference is that the collector used is replaced with Formula 1B, and its concentration in the flotation pulp is controlled at 7 × 10⁻⁶. -7 The flotation concentration was mol / L, and all other operations and parameters were the same as in Example 6. At this point, the flotation recoveries of ilmenite and pyroxene were 96.97% and 47.19%, respectively.

[0058] Comparative Application Example 1

[0059] Compared with Application Example 1, the only difference is that comparative formula A is used. It was used as a collector, and all other operations and parameters were the same as in Example 1.

[0060] The result was that the flotation recovery rate of ilmenite was 64.24%.

[0061] Comparative Application Example 2

[0062] Compared with Application Example 1, the only difference is that comparative formula B is used. It was used as a collector, and all other operations and parameters were the same as in Example 1.

[0063] The result was that the flotation recovery rate of ilmenite was 29.33%.

[0064] Comparative Application Example 3

[0065] Compared to Application Example 1, the only difference is that comparative formula C is used. It was used as a collector, and all other operations and parameters were the same as in Example 1.

[0066] The result was that the flotation recovery rate of ilmenite was 65.32%.

[0067] Comparative Application Example 4

[0068] Compared with Application Example 1, the only difference is that the collector is replaced with Comparative Formula B and Comparative Formula C with a molar ratio of 1:1, and the total collector concentration and other operations and parameters are the same as in Example 1.

[0069] The result was that the flotation recovery rate of ilmenite was 46.63%.

[0070] Comparative Application Example 5

[0071] Compared to Application Example 1, the only difference is that comparative D ( It was used as a collector, and all other operations and parameters were the same as in Example 1.

[0072] The result was that the flotation recovery rate of ilmenite was 84.36%.

[0073] Comparative Application Example 6

[0074] Compared to Application Example 1, the only difference is that comparative E is used. It was used as a collector, and all other operations and parameters were the same as in Application Example 1.

[0075] The result was that the flotation recovery rate of ilmenite was 77.16%.

[0076] Comparative Application Example 7

[0077] Compared with Application Example 6, the only difference is that Comparative Formula A is used. It was used as a collector, and other operations and parameters were the same as in Application Example 6.

[0078] The results showed that the flotation recoveries of ilmenite and ilmenite were 61.91% and 32.21%, respectively.

[0079] Application Example 9: Flotation of Actual Ilmenite Ore

[0080] -0.15mm ilmenite with a titanium dioxide content of 17% was fed into the flotation raw ore. After one roughing stage (flotation for 4 minutes) at a pulp pH of approximately 7.0, ilmenite flotation rough concentrate was obtained. The experimental conditions and results are shown in Table 3. This indicates that the ilmenite flotation rough concentrate obtained using the collector of Formula 1 of this invention has significantly higher titanium dioxide grade and recovery rate, demonstrating outstanding performance.

[0081]

[0082] In summary, this invention provides a novel Formula 1 collector that, based on structural intramolecular synergy, can unexpectedly and selectively target the iron and titanium sites of ilmenite, effectively improving the recovery rate and selectivity of ilmenite.

Claims

1. A collector for ilmenite, characterized in that, It has the structural formula of Equation 1: Formula 1; In Equation 1, R represents C4~C 24 The hydrocarbon group or oxygen-containing hydrocarbon group; M is Na or K.

2. The ilmenite collector as described in claim 1, characterized in that, In Equation 1, R is C4~C 24 Alkyl or oxygen-containing alkyl groups, C6~C 16 aryl or C5~C 16 Five- or six-membered cyclic hydrocarbon groups; Preferably, R is C6~C 14 Alkyl groups.

3. A method for preparing the ilmenite collector according to claim 1 or 2, characterized in that, The raw materials shown in Formula 2 are reacted with MOH and CS2 to obtain the ilmenite collector described in Formula 1. Formula 2; In Equation 2, R is the same as in Equation 1; in MOH, M is the same as in Equation 1.

4. The method for preparing the ilmenite collector as described in claim 3, characterized in that, The solvent for the reaction includes at least one of water, methanol, ethanol, or propanol; methanol is preferred.

5. The method for preparing the ilmenite collector as described in claim 3, characterized in that, The molar ratio of Equation 2, MOH, and CS2 is 1:1~2:1~2.

6. The method for preparing the ilmenite collector according to any one of claims 3 to 5, characterized in that, The reaction temperature is -20℃ to 40℃, and the reaction time is 0.5 to 8 hours.

7. The application of the ilmenite collector according to any one of claims 1 to 2, characterized in that, It is used as a collector in the flotation of ilmenite.

8. The application of the ilmenite collector as described in claim 7, characterized in that, The pH for flotation is 1.5 to 10.

5.

9. The application of the ilmenite collector as described in claim 8, characterized in that, The pH for flotation is 6-9.

10. The application of the ilmenite collector as described in claim 7, characterized in that, The amount of collector used in the flotation process is 0.2~1500g / t.

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