Preparation method and application of ilmenite collecting agent

Abstract

The invention provides a preparation method and application of an ilmenite collecting agent, and the ilmenite collecting agent comprises, by mass concentration, 4%-12% of higher fatty acid, 15%-30% of a complexing agent, 5%-7.5% of sodium hydroxide, 1%-3% of a surfactant and 47.5%-75% of water. Wherein the higher fatty acid is modified oleic acid or a mixture of oleic acid and modified oleic acid; the modified oleic acid is 9-hydroxy octadecenoic acid or 10-hydroxy octadecenoic acid. The modified oleic acid is prepared from concentrated sulfuric acid, oleic acid and a sodium hydroxide solution. And the freezing point of the collecting agent is increased through the modified oleic acid, and the low-temperature resistance is improved. And when the pH is 2.5, the recovery rate of titanium dioxide reaches 60% or above after the collecting agent is added, and the acid resistance of the collecting agent is improved. The surfactant can stabilize foam, wet the mineral surface and reduce the mineral surface tension. The complexing agent can provide high selectivity and collecting capacity, and the technical problem that titanium concentrate and gangue minerals are difficult to efficiently separate through a conventional flotation reagent is solved. The preparation method is simple and easy for large-scale production.

Description

Technical Field

[0001] The invention relates to the field of mineral processing, and in particular to a preparation method and application of an ilmenite collector. Background Art

[0002] Most of the titanium in nature exists in the form of ilmenite, and my country is one of the world's largest ilmenite producers, with proven ilmenite reserves ranking second in the world. However, with the mining of ilmenite, conventional flotation agents are increasingly difficult to efficiently separate titanium concentrate and gangue minerals. Therefore, the research and application of ilmenite flotation agents is of great significance. Summary of the invention

[0003] The main purpose of the present invention is to provide a preparation method and application of an ilmenite collector to solve the technical problem that conventional flotation reagents are difficult to efficiently separate titanium concentrate and gangue minerals.

[0004] To achieve the above purpose, the present invention provides an ilmenite collector, which comprises, by mass concentration, 4%-12% higher fatty acid, 15%-30% complexing agent, 5%-7.5% sodium hydroxide, 1%-3% surfactant and 47.5%-75% water.

[0005] Wherein, the higher fatty acid is modified oleic acid or a mixture of oleic acid and modified oleic acid; the modified oleic acid is 9-hydroxyoctadecenoic acid or 10-hydroxyoctadecenoic acid.

[0006] According to an embodiment of the present application, the higher fatty acid is a mixture of oleic acid and modified oleic acid, wherein in the mixture, the mass ratio of the oleic acid to the modified oleic acid is 3:1 to 1:1.

[0007] According to an embodiment of the present application, the complexing agent is at least one of isooctyl phosphate, phenylphosphonic acid, and benzohydroxamic acid.

[0008] According to an embodiment of the present application, the surfactant is at least one of coconut acid diethanolamide and fatty alcohol polyoxyethylene ether sodium sulfate.

[0009] According to an embodiment of the present application, the method for preparing the modified oleic acid comprises:

[0010] Weigh a certain amount of oleic acid, concentrated sulfuric acid, solid sodium hydroxide and water.

[0011] The concentrated sulfuric acid is added to the oleic acid, and after reacting for 1 hour, a sodium hydroxide solution is added; wherein the sodium hydroxide solution is obtained by dissolving solid sodium hydroxide in water.

[0012] Then, the temperature is raised to 70° C. and the reaction is carried out at a constant temperature for 2 hours to obtain the modified oleic acid.

[0013] According to an embodiment of the present application, the concentrated sulfuric acid and the oleic acid are mixed for 1-3 hours.

[0014] According to an embodiment of the present application, a method for preparing an ilmenite collector comprises:

[0015] Weigh a predetermined weight of raw material according to mass concentration.

[0016] Water, higher fatty acids and complexing agents are mixed and stirred to form a mixed solution.

[0017] Sodium hydroxide was added to the mixed solution to adjust the pH.

[0018] The collector is prepared by adding a surfactant and mixing uniformly.

[0019] According to an embodiment of the present application, the mixed solution after pH adjustment is weakly alkaline, wherein the pH range is 8.0-10.5.

[0020] The present invention also provides an application of an ilmenite collector, comprising the steps of:

[0021] A collector is added to the flotation solution of ilmenite to obtain titanium concentrate.

[0022] The mass ratio of the added amount of the collector to the ilmenite is 3:1000.

[0023] According to an embodiment of the present application, the method for preparing the flotation solution of ilmenite comprises:

[0024] The ilmenite ore is ground and slurried, and then a flotation agent is added, wherein the flotation agent includes dilute sulfuric acid, sodium fluorosilicate and diesel.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The product of oleic acid hydroxylation reaction is used as a collector for flotation of ilmenite, which can improve the solubility and dispersibility of the collector, increase the foaming performance of the collector, expand the coverage area of ​​the agent, and enhance the hydrophobicity of the mineral surface. The flotation results show that at a pH of 2.5, the recovery rate of titanium dioxide in ilmenite after adding the collector is more than 60%, indicating that the acid resistance of the collector is improved. At the same time, due to the addition reaction in the oleic acid hydroxylation reaction, the double bonds in the oleic acid are broken, thereby increasing the freezing point of the modified oleic acid and increasing the ability to resist low temperatures. The combination of surfactants, complexing agents, oleic acid, and modified oleic acid has a good synergistic effect. Among them, the introduction of surfactants can stabilize the foam and wet the mineral surface, reducing the surface tension of the mineral. The addition of complexing agents provides high selectivity and collection capacity, solving the technical problem that conventional flotation agents are difficult to efficiently select titanium concentrates and gangue minerals. The preparation method is simple and easy to scale up. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0028] Figure 1 It is a reaction equation of modified oleic acid according to one embodiment of the present application.

[0029] Figure 2 It is a schematic diagram of the flotation steps of one embodiment of the present application.

[0030] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with the implementation methods and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] It should be noted that all directional indications (such as up, down, etc.) in the embodiments of the present invention are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0033] In addition, in the present invention, the descriptions of "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features.

[0034] Furthermore, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in the field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0035] The applicant has found through research that one of the main reasons why conventional flotation agents are increasingly difficult to efficiently separate titanium concentrate and gangue minerals is that the traditional ilmenite collectors are not strong enough in acid resistance and low temperature resistance. Therefore, the flotation effect is poor when the temperature is low in winter; the weak acid resistance leads to the collector being easily ineffective when the flotation pH is in the range of 2.5-4, making it difficult to efficiently separate titanium concentrate and gangue minerals.

[0036] Based on this, the main purpose of the present invention is to provide a preparation method and application of an ilmenite collector to solve the technical problem that conventional flotation agents are difficult to efficiently separate titanium concentrate and gangue minerals.

[0037] To achieve the above purpose, the present invention provides an ilmenite collector, which comprises, by mass concentration, 4%-12% higher fatty acid, 15%-30% complexing agent, 5%-7.5% sodium hydroxide, 1%-3% surfactant and 47.5%-75% water.

[0038] Wherein, the higher fatty acid is modified oleic acid or a mixture of oleic acid and modified oleic acid; the modified oleic acid is 9-hydroxyoctadecenoic acid or 10-hydroxyoctadecenoic acid.

[0039] In some embodiments, the higher fatty acid is a mixture of oleic acid and modified oleic acid, wherein, in the mixture, the mass ratio of the oleic acid to the modified oleic acid is 3:1 to 1:1 (preferably, 2:1).

[0040] In some embodiments, the complexing agent is at least one of isooctyl phosphate, phenylphosphonic acid, and benzohydroxamic acid.

[0041] In some embodiments, the surfactant is at least one of coconut oil diethanolamide and sodium polyoxyethylene fatty alcohol ether sulfate.

[0042] In some embodiments, the method for preparing the modified oleic acid comprises:

[0043] Weigh a certain amount of oleic acid, concentrated sulfuric acid, solid sodium hydroxide and water.

[0044] In the modified oleic acid, the mass ratio of oleic acid: concentrated sulfuric acid: solid sodium hydroxide: water is 39: (5-10): (6-12): (39-50).

[0045] The concentrated sulfuric acid is added to the oleic acid, and after reacting for 1 hour, a sodium hydroxide solution is added; wherein the sodium hydroxide solution is obtained by dissolving solid sodium hydroxide in water.

[0046] Then, the temperature is raised to 70°C and the reaction is carried out at a constant temperature for 2 hours to obtain the modified oleic acid. If heating is used, a jacketed reactor may be used and stirring is required during the constant temperature reaction. The reaction equation of the modified oleic acid is as follows: Figure 1 shown.

[0047] In some embodiments, the concentrated sulfuric acid and the oleic acid are mixed for 1-3 hours.

[0048] In some embodiments, a method for preparing an ilmenite collector comprises:

[0049] Weigh a predetermined weight of raw material according to mass concentration.

[0050] Mix water, higher fatty acid and complexing agent and stir them evenly to form a mixed solution, such as mixing in a reactor.

[0051] Sodium hydroxide was added to the mixed solution to adjust the pH.

[0052] The collector is prepared by adding a surfactant and mixing uniformly.

[0053] In some embodiments, the mixed solution after pH adjustment is weakly alkaline, wherein the pH range is 8.0-10.5. Since surfactants are easily denatured under acidic conditions, the pH is adjusted to alkaline before adding the surfactant.

[0054] The present invention also provides an application of an ilmenite collector, comprising the steps of:

[0055] A collector is added to the flotation solution of ilmenite to obtain titanium concentrate.

[0056] The mass ratio of the added amount of the collector to the ilmenite is 3:1000.

[0057] In some embodiments, the method for preparing the flotation solution of ilmenite comprises:

[0058] The ilmenite ore is ground and slurried, and then a flotation agent is added, wherein the flotation agent includes dilute sulfuric acid, sodium fluorosilicate and diesel.

[0059] For further understanding of the present invention, examples are given below:

[0060] Example 1

[0061] An ilmenite collector is prepared by the following method:

[0062] Weigh 150kg of phenylphosphonic acid, 100kg of isooctyl phosphate, 60kg of oleic acid, 20kg of modified oleic acid, 20kg of coconut oil diethanolamide, 62.5kg of solid sodium hydroxide, and 577.5kg of water respectively. Add the weighed water into the reactor, start stirring, pour the weighed higher fatty acids and complexing agent into the reactor and stir evenly, then add sodium hydroxide to adjust the pH to weak alkalinity, and finally add a surfactant and stir evenly to obtain the product.

[0063] Example 2

[0064] An ilmenite collector is prepared by the following method:

[0065] Weigh 150kg of phenylphosphonic acid, 100kg of isooctyl phosphate, 50kg of oleic acid, 30kg of modified oleic acid, 20kg of sodium sulfate of fatty alcohol polyoxyethylene ether, 75kg of solid sodium hydroxide, and 565kg of water respectively. Add the weighed water into the reactor, start stirring, pour the weighed higher fatty acids and complexing agent into the reactor and stir evenly, then add sodium hydroxide to adjust the pH to weak alkalinity, and finally add a surfactant and stir evenly to obtain the product.

[0066] Example 3

[0067] An ilmenite collector is prepared by the following method:

[0068] Weigh 100kg of phenylphosphonic acid, 100kg of isooctyl phosphate, 50kg of benzohydroxamic acid, 40kg of oleic acid, 40kg of modified oleic acid, 20kg of coconut oil diethanolamide, 71.5kg of solid sodium hydroxide, and 568.5kg of water respectively. Add the weighed water into the reactor, start stirring, pour the weighed higher fatty acids and complexing agent into the reactor and stir evenly, then add sodium hydroxide to adjust the pH to weak alkalinity, and finally add a surfactant and stir evenly to obtain the product.

[0069] Example 4

[0070] An ilmenite collector is prepared by the following method:

[0071] Weigh 100kg of phenylphosphonic acid, 50kg of isooctyl phosphate, 100kg of benzohydroxamic acid, 40kg of oleic acid, 40kg of modified oleic acid, 20kg of coconut oil diethanolamide, 69kg of solid sodium hydroxide, and 561kg of water respectively. Add the weighed water into the reactor, start stirring, pour the weighed higher fatty acids and complexing agent into the reactor and stir evenly, then add sodium hydroxide to adjust the pH to weak alkalinity, and finally add a surfactant and stir evenly to obtain the product.

[0072] Comparative Example 1

[0073] Compared with Example 1, only the modified oleic acid is not contained.

[0074] The ilmenite collectors obtained in Examples 1 to 4 and Comparative Example 1 were used to flotate the same batch of ilmenite samples (the original ore contained 17.85% titanium dioxide) divided into several portions at room temperature 25°C and low temperature 10°C. A unified standard method was used during flotation, including grinding, slurry adjustment, adding corresponding reagents (dilute sulfuric acid, sodium fluorosilicate, diesel), and adding corresponding collectors. Finally, the titanium dioxide content and recovery rate in the titanium concentrate obtained by flotation were calculated and statistically analyzed. Among them, the flotation steps are as follows: Figure 2 shown.

[0075] The statistical data of titanium dioxide content and recovery rate in titanium concentrate obtained by flotation at 25°C are shown in Table 1.

[0076] Group Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Titanium concentrate yield (%) 23.03 23.14 22.50 22.66 9.48 Titanium dioxide content in titanium concentrate (%) 48.13 48.01 47.81 47.70 47.52 Titanium dioxide recovery rate from titanium concentrate (%) 62.11 62.24 60.26 60.56 25.23 Tailings yield (%) 61.06 60.46 61.30 61.28 60.72 Tailings titanium dioxide content (%) 4.78 4.73 5.11 5.22 6.62 Tailings titanium dioxide recovery rate (%) 16.35 16.02 17.55 17.92 22.52

[0077] Table 1

[0078] It can be seen from the data in Table 1 that compared with the comparative example, the titanium dioxide content and recovery rate in the titanium concentrate obtained by flotation at 25°C are greatly improved in the embodiment. At the same time, after 4 concentration processes, when the corresponding pH is 2.5, the corresponding titanium dioxide recovery rate of the iron concentrate in Examples 1 to 4 is more than 60%, while that in Comparative Example 1 is only 25.23%, indicating that the addition of modified oleic acid in Examples 1 to 4 significantly improves the acid resistance of the collector and provides a wider pH adaptation range. At the same time, the titanium concentrate yield of the embodiment is significantly improved compared with Comparative Example 1, which can greatly reduce the operating load of the mine concentration section.

[0079] The statistical data of titanium dioxide content and recovery rate in titanium concentrate obtained by flotation at 10℃ are shown in Table 2.

[0080] Group Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Titanium concentrate yield (%) 22.15 22.12 21.94 21.83 5.18 Titanium dioxide content in titanium concentrate (%) 48.21 48.15 47.95 47.93 47.76 Titanium dioxide recovery rate from titanium concentrate (%) 59.83 59.68 58.93 58.62 13.86 Tailings yield (%) 63.81 62.96 62.59 63.12 68.12 Tailings titanium dioxide content (%) 5.22 5.31 5.35 5.41 9.57 Tailings titanium dioxide recovery rate (%) 18.66 18.73 18.76 19.13 36.52

[0081] Table 2

[0082] It can be seen from the data in Table 2 that: Taking Example 1 as an example, the recovery rate of titanium dioxide in tailings increased by 2.31% under the condition of low temperature 10°C compared with the condition of normal temperature 25°C, with a growth rate of 14.13%. In Comparative Example 1 without the addition of modified oleic acid, the recovery rate of titanium dioxide in tailings increased by 14.0% under the condition of low temperature 10°C compared with the condition of normal temperature 25°C, with a growth rate of 62.17%. The recovery rate of titanium dioxide in tailings obtained by flotation in Examples 1 to 4 increased less, while the recovery rate of titanium dioxide in tailings obtained by flotation in Comparative Example 1 without the addition of modified oleic acid increased more, indicating that the modified oleic acid in the ilmenite collector of the present invention improves the low temperature resistance of the collector and obtains good flotation indicators under low temperature conditions.

[0083] The above technical solutions of the present invention are only preferred embodiments of the present invention, and the patent scope of the present invention is not limited thereto. All equivalent structural changes made by using the contents of the present invention specification and drawings under the technical concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. An ilmenite collector, characterized in that: In terms of mass concentration, the collector comprises 4%-12% higher fatty acid, 15%-30% complexing agent, 5%-7.5% solid sodium hydroxide, 1%-3% surfactant and 47.5%-75% water; Wherein, the higher fatty acid is modified oleic acid or a mixture of oleic acid and modified oleic acid; the modified oleic acid is 9-hydroxyoctadecenoic acid or 10-hydroxyoctadecenoic acid.

2. The ilmenite collector according to claim 1, characterized in that: The higher fatty acid is a mixture of oleic acid and modified oleic acid, wherein in the mixture, the mass ratio of the oleic acid to the modified oleic acid is 3:1 to 1:

1.

3. The ilmenite collector according to claim 1, characterized in that: The complexing agent is at least one of isooctyl phosphate, phenylphosphonic acid and benzohydroxamic acid.

4. The ilmenite collector according to claim 1, characterized in that: The surfactant is at least one of coconut oil diethanolamide and fatty alcohol polyoxyethylene ether sodium sulfate.

5. The ilmenite collector according to claim 1, characterized in that: The preparation method of the modified oleic acid comprises: Weigh a certain amount of oleic acid, concentrated sulfuric acid, solid sodium hydroxide and water; Add the concentrated sulfuric acid to the oleic acid, react for 1 hour, and then add a sodium hydroxide solution; wherein the sodium hydroxide solution is obtained by dissolving solid sodium hydroxide in water; Then, the temperature is raised to 70° C. and the reaction is carried out at a constant temperature for 2 hours to obtain the modified oleic acid.

6. The ilmenite collector according to claim 5, characterized in that: The concentrated sulfuric acid and the oleic acid are mixed for 1-3 hours.

7. A method for preparing an ilmenite collector according to any one of claims 1 to 6, characterized in that: include: Weigh a predetermined weight of raw materials according to mass concentration; Mix water, higher fatty acid and complexing agent and stir evenly to form a mixed solution; adding sodium hydroxide to the mixed solution to adjust the pH; The collector is prepared by adding a surfactant and mixing uniformly.

8. The method for preparing an ilmenite collector according to claim 7, characterized in that: The mixed solution after pH adjustment is weakly alkaline, wherein the pH range is 8.0-10.

5.

9. An application of an ilmenite collector, characterized in that the steps include: Adding a collector to the flotation solution of ilmenite to obtain titanium concentrate; The mass ratio of the added amount of the collector to the ilmenite is 3:1000.

10. The use of the ilmenite collector according to claim 9, characterized in that: The method for preparing the flotation solution of ilmenite comprises: The ilmenite ore is ground and slurried, and then a flotation agent is added, wherein the flotation agent includes dilute sulfuric acid, sodium fluorosilicate and diesel.

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