Composite flotation collecting agent and method for flotation recovery of titanium-containing minerals from acid leaching titanium slag

Abstract

The invention discloses a composite flotation collecting agent and a method for flotation recovery of titanium-containing minerals from acid leaching titanium slag. The composite flotation collecting agent is composed of naphthenic hydroxamic acid, sodium dodecyl benzene sulfonate and coconut oil amine, and the mass ratio of the naphthenic hydroxamic acid to the sodium dodecyl benzene sulfonate to the coconut oil amine is (10-15): (5-10): (1-3). The invention further provides a method for recovering the titanium-containing minerals from the acid-leached titanium slag through flotation. The method is used for recovering the titanium-containing minerals from the acid-leached titanium slag. The flotation process comprises one-time roughing and five-time concentration, middlings are sequentially returned, a closed-loop process is formed, and titanium concentrate and tailings are obtained. According to the method, the titanium-containing minerals in the acid leaching titanium slag are recycled through the flotation method, the process is simple, industrial application is easy, and reduction and resource utilization of the solid waste are achieved.

Description

Technical Field

[0001] The present invention relates to the field of mineral processing, and in particular to a composite flotation collector and a method for flotation recovery of titanium-containing minerals from acid-leached titanium slag. Background Art

[0002] Steel is a crucial engineering material in the global economy. Its production, using vanadium-titanium magnetite as a raw material, inevitably produces large quantities of titanium-containing slag. Its primary components are TiO2, CaO, SiO2, and Al2O3, among others. If not properly handled, these slags can have adverse environmental impacts. Low-TiO2 titanium slag can be added to Portland cement as an admixture without significant performance differences. However, high-TiO2 titanium slag, if directly incorporated into cement, can significantly impact the properties of the final cement product. Therefore, pyrometallurgical or hydrometallurgical methods are often employed to recycle these slags. Pyrometallurgical methods include high-temperature carbonization-low-temperature selective chlorination, alloying extraction processes, and selective precipitation separation techniques. Hydrometallurgical methods involve leaching titanium slag with sulfuric or hydrochloric acid to recover the titanium. This process inevitably generates large amounts of waste acid. Currently, the acid-leached titanium slag is typically neutralized with alkaline substances such as lime and then stored. Therefore, methods are needed to reduce the volume of this waste and recycle it as a resource. Compared with metallurgical processes, flotation has the advantages of low energy consumption, low cost, simple operation, and environmental friendliness. By designing a reasonable separation process and flotation reagents, it is expected to achieve effective recovery of titanium from titanium slag. Among the traditional flotation reagents for separating titanium-containing minerals such as ilmenite and rutile, phosphonic acid and arsenic acid collectors are highly toxic, while single collectors such as fatty acids and hydroxamic acids have shortcomings such as poor selectivity or poor collection performance. In addition, lead ions or copper ions are usually added as activators during flotation, which increases environmental pressure. Therefore, it is necessary to develop new, efficient, and environmentally friendly flotation reagents and corresponding separation processes to achieve efficient recovery of titanium resources from acid-leached titanium slag. Summary of the Invention

[0003] One of the purposes of the present invention is to provide a composite flotation collector for recovering titanium-containing minerals from acid-leached titanium slag, which can efficiently and environmentally recycle titanium resources in the acid-leached titanium slag.

[0004] A second object of the present invention is to provide a method for flotation recovery of titanium-containing minerals from acid-leached titanium slag using a composite flotation collector.

[0005] The invention provides a composite flotation collector, which consists of cycloalkyl hydroxamic acid, sodium dodecylbenzenesulfonate and coconut amine; wherein the mass ratio of cycloalkyl hydroxamic acid, sodium dodecylbenzenesulfonate and coconut amine is (10-15): (5-10): (1-3).

[0006] The present invention also provides a method for flotation recovery of titanium-containing minerals from acid-leached titanium slag using the composite flotation collector, specifically: the acid-leached titanium slag ore is subjected to one roughing and five cleanings, and the middlings are returned in sequence, that is, the tailings of cleaning I are returned to the roughing as middlings, the tailings of cleaning II are returned to cleaning I as middlings, the tailings of cleaning III are returned to cleaning II as middlings, the tailings of cleaning IV are returned to cleaning III as middlings, and the tailings of cleaning V are respectively returned to cleaning IV as middlings, forming a closed-circuit process to obtain titanium concentrate and tailings.

[0007] Furthermore, the acid-leached titanium slag ore is a paste with a pH of 7 to 8, and particles with a diameter of less than 74 μm account for 75 to 85%.

[0008] Furthermore, the mass concentration of solid particles in the flotation pulp in roughing, concentrating I, concentrating II, concentrating III, concentrating IV and concentrating V is 25% to 35%; the adjusting agent used is sulfuric acid, the pH of the pulp is adjusted to 4 to 5, and the stirring and slurrying time is 3 to 5 minutes.

[0009] Furthermore, the inhibitor used in roughing, concentrating I, concentrating II, concentrating III, concentrating IV and concentrating V is a composition including sodium silicate and sodium edetate, and the mass ratio of the two is (4-8):1.

[0010] Furthermore, the collector used in roughing, cleaning I, cleaning II, cleaning III, cleaning IV and cleaning V is the composite flotation collector.

[0011] Furthermore, the regulator, inhibitor and collector are added to the roughing, fine selection I, fine selection II and fine selection III in sequence. After each agent is added, the mixture is stirred for 2 to 3 minutes, the aeration time is 1 to 2 minutes, and the scraping time is 3 to 5 minutes.

[0012] Only adjuster is added to Selected IV and Selected V. After adding, stir for 2 to 3 minutes, aerate for 1 to 2 minutes, and scrape for 3 to 5 minutes.

[0013] Furthermore, the dosage of the inhibitor is selected to be 4000-6000 g / t, and the dosage of the collector is selected to be 500-1200 g / t.

[0014] Furthermore, the dosage of inhibitor for Select I, Select II and Select III is 2000-3000 g / t, and the dosage of collector is 400-800 g / t.

[0015] Furthermore, no inhibitor or collector is added to the selected fractions IV and V, i.e. blank flotation.

[0016] The dosage of reagents in the above flotation process is expressed in g / t based on the mass of the original ore.

[0017] Principle of the present invention:

[0018] The present invention addresses the issue of acid-leached titanium slag neutralized with lime. Acid leaching of the titanium slag, obtained by high-temperature smelting of raw materials such as ilmenite, destroys its lattice structure and alters its surface properties. Furthermore, neutralization with lime produces a large amount of gypsum, which differs significantly from natural minerals. Using a single collector makes it difficult to achieve a good separation effect on the titanium-containing minerals in the slag. The combined flotation reagents described in the present invention include cycloalkyl hydroxamic acid, which exhibits excellent selectivity and effectively adsorbs onto the titanium sites of the target mineral, rendering it hydrophobic. Sodium dodecylbenzenesulfonate exhibits excellent collecting properties and forms a stable solid-liquid-gas three-phase interface, allowing the titanium-containing minerals to float hydrophobically. Coconut amine regulates the slurry environment, acting as a dispersant to increase the solubility of the reagent in the slurry and promote its adsorption on the mineral surface. It also regulates the foam layer, improving flotation efficiency. The inhibitors, composed of sodium silicate and sodium ethylenediaminetetraacetic acid, exhibit a strong inhibitory effect on calcium-containing minerals such as gypsum, contributing to improved concentrate grade. Under the synergistic effect of the above three reagents and inhibitors, titanium-containing minerals in acid-leached titanium slag can be effectively selected and a relatively ideal grade and recovery rate can be obtained.

[0019] Beneficial effects of the present invention:

[0020] (1) The present invention designs a composite flotation collector for recovering titanium-containing minerals from acid-leached titanium slag and designs a corresponding flotation process, thereby achieving effective recovery of titanium resources from such solid waste resources while also reducing environmental pressure.

[0021] (2) The various agents in the composite flotation collector of the present invention have a synergistic effect, overcoming the problems of poor selectivity or weak collecting ability of a single collector; cycloalkyl hydroxamic acid has good selectivity and can be effectively adsorbed on the surface of titanium-containing minerals; sodium dodecylbenzenesulfonate has good collecting performance, making the target mineral hydrophobic and floating; coconut amine acts as an emulsifier to regulate the pulp environment, enhance the dissolution of the agent in the pulp and the adsorption on the mineral surface, and improve the flotation effect;

[0022] (3) The present invention designs a corresponding flotation process based on the composite collector, which is simple in process, easy to operate, and easy to implement in engineering. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of the process of the present invention. DETAILED DESCRIPTION

[0024] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, they will be described in detail below with reference to specific embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0025] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0026] The process flow chart of the present invention is as follows Figure 1 The specific steps are shown in the embodiment.

[0027] Example 1

[0028] The acid-leached titanium slag used in this example has a TiO2 content of 5.99%, a Fe2O3 content of 13.88%, and a CaO content of 34.20%. The flotation process includes one roughing operation and five cleaning operations. The middlings are sequentially returned to the previous flotation operation, forming a closed-circuit process.

[0029] During roughing, the pulp concentration was controlled at 30%, the stirring and slurrying time was 5 minutes, sulfuric acid was added to adjust the pulp pH to 4-5, and after the pH stabilized, an inhibitor (composed of sodium silicate and sodium ethylenediaminetetraacetic acid in a mass ratio of 5:1, the same in this embodiment below) was added in an amount of 4000 g / t; after stirring for 3 minutes, a composite collector (composed of cycloalkyl hydroxamic acid, sodium dodecylbenzenesulfonate, and coconut amine in a mass ratio of 10:5:1, the same in this embodiment below) was added in an amount of 1000 g / t; after stirring for 3 minutes, aeration was started, and the aeration time was 1 minute; then, foaming was scraped for 5 minutes, and the foam product was used for the next selection.

[0030] The concentration of the ore pulp of selection I is 30%. The pH value of the ore pulp is adjusted to 4-5. After the pH value stabilizes, an inhibitor is added at a dosage of 2000g / t. After stirring for 3 minutes, a composite collector is added at a dosage of 600g / t. After stirring for 3 minutes, aeration is started for 1 minute. Then, the foam is scraped for 5 minutes, and the foam product is used for the next selection.

[0031] The concentration of the ore pulp of selection II is 30%. The pH value of the ore pulp is adjusted to 4-5. After the pH value stabilizes, an inhibitor is added at a dosage of 2000g / t. After stirring for 3 minutes, a composite collector is added at a dosage of 400g / t. After stirring for 3 minutes, aeration is started for 1 minute. Then, the foam is scraped for 5 minutes, and the foam product is used for the next selection.

[0032] The concentration of the concentrated III ore pulp is 30%. The pH of the ore pulp is adjusted to 4-5. After the pH stabilizes, an inhibitor is added at a dosage of 1500g / t. After stirring for 3 minutes, a composite collector is added at a dosage of 400g / t. After stirring for 3 minutes, aeration is started for 1 minute. Then, the foam is scraped for 5 minutes, and the foam product is used for the next selection.

[0033] The concentration of the selected IV ore pulp is 30%, and the pH of the pulp is adjusted to 4-5. After stirring for 3 minutes, aeration begins, and the aeration time is 1 minute; then scraping and foaming for 3 minutes, and the foam product is used for the next selection.

[0034] The concentration of the concentrated V ore pulp is 30%, and the pH of the pulp is adjusted to 4-5. After stirring for 3 minutes, aeration begins, and the aeration time is 1 minute; then scraping and foaming for 3 minutes, and the foam product is used as the final concentrate.

[0035] The obtained concentrate product was analyzed and tested, and the results showed that the concentrate yield was 11.29%, the TiO2 content was 40.50%, and the Fe2O3 content was 47.26%; the titanium recovery rate was 76.33%, and the Fe2O3 recovery rate was 38.44%, indicating that the composite collector and flotation process used in the present invention can effectively recover titanium-containing minerals in acid-leached titanium slag.

[0036] Example 2

[0037] The acid-leached titanium slag used in this example has a TiO2 content of 5.87%, a Fe2O3 content of 13.65%, and a CaO content of 34.26%. The flotation process includes one roughing operation and five cleaning operations. The middlings are sequentially returned to the previous flotation operation, forming a closed-circuit process.

[0038] During roughing, the pulp concentration was controlled at 30%, the stirring and slurrying time was 5 minutes, sulfuric acid was added to adjust the pulp pH to 4-5, and after the pH stabilized, an inhibitor (composed of sodium silicate and sodium ethylenediaminetetraacetic acid in a mass ratio of 5:1, the same in this embodiment below) was added in an amount of 4000 g / t; after stirring for 3 minutes, a composite collector (composed of cycloalkyl hydroxamic acid, sodium dodecylbenzenesulfonate, and coconut amine in a mass ratio of 15:3:1, the same in this embodiment below) was added in an amount of 1000 g / t; after stirring for 3 minutes, aeration was started, and the aeration time was 1 minute; then, foaming was scraped for 5 minutes, and the foam product was used for the next selection.

[0039] The concentration of the ore pulp of selection I is 30%. The pH value of the ore pulp is adjusted to 4-5. After the pH value stabilizes, an inhibitor is added at a dosage of 2000g / t. After stirring for 3 minutes, a composite collector is added at a dosage of 600g / t. After stirring for 3 minutes, aeration is started for 1 minute. Then, the foam is scraped for 5 minutes, and the foam product is used for the next selection.

[0040] The concentration of the ore pulp of selection II is 30%. The pH value of the ore pulp is adjusted to 4-5. After the pH value stabilizes, an inhibitor is added at a dosage of 2000g / t. After stirring for 3 minutes, a composite collector is added at a dosage of 400g / t. After stirring for 3 minutes, aeration is started for 1 minute. Then, the foam is scraped for 5 minutes, and the foam product is used for the next selection.

[0041] The concentration of the concentrated III ore pulp is 30%. The pH of the ore pulp is adjusted to 4-5. After the pH stabilizes, an inhibitor is added at a dosage of 1500g / t. After stirring for 3 minutes, a composite collector is added at a dosage of 400g / t. After stirring for 3 minutes, aeration is started for 1 minute. Then, the foam is scraped for 5 minutes, and the foam product is used for the next selection.

[0042] The concentration of the selected IV ore pulp is 30%, and the pH of the pulp is adjusted to 4-5. After stirring for 3 minutes, aeration begins, and the aeration time is 1 minute; then scraping and foaming for 3 minutes, and the foam product is used for the next selection.

[0043] The concentration of the concentrated V ore pulp is 30%, and the pH of the pulp is adjusted to 4-5. After stirring for 3 minutes, aeration begins, and the aeration time is 1 minute; then scraping and foaming for 3 minutes, and the foam product is used as the final concentrate.

[0044] The obtained concentrate product was analyzed and tested, and the results showed that the concentrate yield was 9.41%, the TiO2 content was 42.76%, and the Fe2O3 content was 48.51%; the titanium recovery rate was 68.55%, and the Fe2O3 recovery rate was 33.44%, indicating that the composite collector and flotation process used in the present invention can effectively recover titanium-containing minerals in acid-leached titanium slag.

[0045] Comparative Example 1

[0046] Compared with Example 1, only cycloalkyl hydroxamic acid was used as a collector, and the total amount of cycloalkyl hydroxamic acid was unchanged. All other experimental conditions and operating procedures were identical. Analysis and testing of the resulting concentrate product showed a concentrate yield of 4.13%, a TiO2 content of 26.89%, and an Fe2O3 content of 30.51%. The titanium recovery rate was 18.54%, and the Fe2O3 recovery rate was 9.08%. The titanium grade and recovery rate of the concentrate were significantly lower than those in Example 1.

[0047] Comparative Example 2

[0048] Compared with Example 1, only sodium dodecylbenzenesulfonate was used as a collector, and the total amount remained unchanged. Other experimental conditions and operating procedures were identical. The resulting concentrate product was analyzed and tested. The results showed that the concentrate yield was 17.66%, the TiO2 content was 15.43%, and the Fe2O3 content was 22.91%. The titanium recovery rate was 45.49%, and the Fe2O3 recovery rate was 29.15%. The titanium grade and recovery rate of the concentrate were significantly lower than those in Example 1.

[0049] Comparative Example 3

[0050] Compared with Example 1, only cycloalkylhydroxamic acid and sodium dodecylbenzenesulfonate were used as collectors, with the same ratio and total amount as in Example 1. All other experimental conditions and operating procedures were identical. Analysis and testing of the resulting concentrate revealed a concentrate yield of 6.84%, a TiO2 content of 32.45%, and an Fe2O3 content of 34.73%. The titanium recovery rate was 37.05%, and the Fe2O3 recovery rate was 17.11%. The titanium grade and recovery rate of the concentrate were significantly lower than those in Example 1.

[0051] Comparative Example 4

[0052] Compared with Example 1, only cycloalkyl hydroxamic acid and coconut amine were used as collectors, with the same ratio and total amount as in Example 1. All other experimental conditions and procedures were identical. Analysis and testing of the resulting concentrate revealed a concentrate yield of 5.17%, a TiO2 content of 25.36%, and an Fe2O3 content of 32.81%. The titanium recovery rate was 21.89%, and the Fe2O3 recovery rate was 12.22%. The titanium grade and recovery rate of the concentrate were significantly lower than those in Example 1.

[0053] Comparative Example 5

[0054] Compared with Example 1, only sodium dodecylbenzenesulfonate and coconut amine were used as collectors, with the same ratio and total amount as in Example 1. Other experimental conditions and operating procedures were identical. The resulting concentrate product was analyzed and tested, and the results showed that the concentrate yield was 19.55%, the TiO2 content was 13.48%, and the Fe2O3 content was 21.74%. The titanium recovery rate was 44.00%, and the Fe2O3 recovery rate was 30.62%. The titanium grade and recovery rate of the concentrate were significantly lower than those in Example 1.

[0055] The results of Example 1 and Comparative Examples 1 to 5 show that the present invention is much more effective in recovering titanium-containing minerals from acid-leached titanium slag than the collectors using a single component or a combination of the two components in the comparative examples (since coconut amine alone does not have a collecting effect, the comparative example is not used alone for illustration). This also demonstrates the synergistic effect of the components in the composite collector provided by the present invention.

Claims

1. A composite flotation collector, characterized in that: The composite flotation collector consists of cycloalkyl hydroxamic acid, sodium dodecylbenzenesulfonate and coconut amine.

2. The composite flotation collector according to claim 1, characterized in that The mass ratio of cycloalkyl hydroxamic acid, sodium dodecylbenzenesulfonate and coconut amine is (10-15): (5-10): (1-3).

3. A method for flotation recovery of titanium-containing minerals from acid-leached titanium slag using the composite flotation collector according to any one of claims 1 or 2, characterized in that: Specifically, the acid-leached titanium slag ore is subjected to one roughing and five cleaning processes, and the middlings are returned in sequence, that is, the tailings of Cleaning I are returned as middlings to the roughing, the tailings of Cleaning II are returned as middlings to Cleaning I, the tailings of Cleaning III are returned as middlings to Cleaning II, the tailings of Cleaning IV are returned as middlings to Cleaning III, and the tailings of Cleaning V are returned as middlings to Cleaning IV, forming a closed-circuit process to obtain titanium concentrate and tailings; the collector used in the roughing, Cleaning I, Cleaning II, Cleaning III, Cleaning IV and Cleaning V is the composite flotation collector.

4. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: The acid-leached titanium slag ore is a paste with a pH value of 7 to 8, and particles with a particle size of less than 74 μm account for 75 to 85%.

5. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: The solid particle mass concentration of the flotation pulp in roughing, concentrating I, concentrating II, concentrating III, concentrating IV and concentrating V is 25% to 35%; the adjusting agent used is sulfuric acid, the pH of the pulp is adjusted to 4 to 5, and the stirring and slurrying time is 3 to 5 minutes.

6. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: The inhibitor used in roughing, concentrating I, concentrating II, concentrating III, concentrating IV and concentrating V is a composition comprising sodium silicate and sodium edetate, and the mass ratio of the two is (4-8):

1.

7. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: Adjusters, inhibitors and collectors are added to roughing, fine selection I, fine selection II and fine selection III in sequence. After adding each agent, stir for 2 to 3 minutes, aerate for 1 to 2 minutes, and scrape for 3 to 5 minutes; only adjusters are added to fine selection IV and fine selection V. After adding, stir for 2 to 3 minutes, aerate for 1 to 2 minutes, and scrape for 3 to 5 minutes.

8. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: The dosage of roughing inhibitor is 4000-6000g / t, and the dosage of collector is 500-1200g / t.

9. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: The dosage of inhibitor for Selected I, Selected II and Selected III is 2000-3000 g / t, and the dosage of collector is 400-800 g / t.

10. The method for flotation recovery of titanium-containing minerals from acid-leached titanium slag according to claim 3, characterized in that: Selected IV and Selected V are blank flotation without adding inhibitors and collectors.

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