Inhibitor composition for zirconium-titanium bulk concentrate and preparation method and application thereof

Abstract

The invention relates to the technical field of mineral separation, in particular to an inhibitor composition for zirconium-titanium bulk concentrate and a preparation method and application thereof, and the inhibitor composition is obtained by compounding organic acid, carboxymethyl starch, sodium fluosilicate and sodium hexametaphosphate. According to the inhibitor composition for the zirconium-titanium bulk concentrate, the zirconium-titanium bulk concentrate which is a difficult-to-treat material is subjected to effective flotation separation through the synergistic effect of multiple inhibitors, effective utilization of zirconium-titanium resources accumulated in middlings is achieved, and the overall recovery rate of coastal placer is increased.

Description

Technical Field

[0001] This application relates to the field of mineral processing technology, specifically to inhibitor compositions for zirconium-titanium mixed concentrates, their preparation methods, and applications. Background Technology

[0002] Zirconium, as an important strategic material, is widely used in nuclear industry, aerospace, chemical industry, ceramics and other fields due to its excellent high temperature resistance, corrosion resistance, wear resistance and low neutron absorption cross section. Zircon (ZrSiO4) is the main mineral raw material for extracting zirconium and its compounds. It often occurs in coastal sands with gangue minerals such as rutile and ilmenite. Effective separation of zirconium and titanium minerals is a key challenge in the beneficiation process of coastal sand deposits. Currently, in industry, the difference in surface conductivity between zircon and rutile is often used to separate zirconium-titanium concentrate using electrostatic separation equipment. However, the mineral characteristics of the zirconium-titanium concentrate produced by electrostatic separation are significantly different from those of typical titanium-bearing zircon sand deposits. Typical titanium-bearing zircon sand deposits usually have relatively uniform particle size distribution, high degree of liberation of individual minerals, and large differences in surface properties between the target mineral and gangue minerals, making them easy to separate using traditional beneficiation methods. However, the rutile and zircon in the zirconium-titanium concentrate produced by electrostatic separation are more crystalline in terms of density and particle size, making it difficult to separate them effectively using traditional physical beneficiation methods, thus forming a difficult-to-process material with high zirconium and titanium content.

[0003] Flotation is a simple and effective process for removing impurities such as monazite from zircon concentrate, making it a valuable means to improve the recovery and grade of zircon concentrate. However, existing flotation processes still face certain technical bottlenecks in the efficient separation of rutile and zircon. For the difficult-to-process zircon-titanium concentrate produced by electrostatic separation, existing flotation reagents cannot simultaneously and efficiently obtain rutile and zircon concentrates. Therefore, a highly selective and potent depressant is needed to effectively separate zircon and rutile. Summary of the Invention

[0004] The purpose of this application is to overcome the shortcomings of the prior art, provide an inhibitor composition for zirconium-titanium mixed concentrate, its preparation method and application, and utilize the synergistic effect between multiple inhibitors to effectively separate this difficult-to-process material, zirconium-titanium mixed concentrate, to achieve effective utilization of zirconium-titanium resources accumulated in middlings and improve the overall recovery rate of coastal sand mines.

[0005] The objective of this invention is achieved through the following technical solution: On the one hand, this application provides an inhibitor composition for zirconium-titanium mixed concentrate, the inhibitor composition being obtained by compounding organic acid, carboxymethyl starch, sodium fluorosilicate and sodium hexametaphosphate.

[0006] Furthermore, the weight ratio of the organic acid, the carboxymethyl starch, the sodium fluorosilicate, and the hexametaphosphate is (15~25):(15~25):(35~45):1.

[0007] Furthermore, the organic acid includes at least one of oxalic acid and citric acid.

[0008] On the other hand, this application provides a method for preparing the above-mentioned inhibitor composition for zirconium-titanium mixed concentrate, comprising the following steps: Take the organic acid, the carboxymethyl starch, the sodium fluorosilicate and the sodium hexametaphosphate, add water, and stir at 20~30℃ for 15~25 min to obtain the inhibitor composition; The total concentration of the inhibitor composition is 5-10%.

[0009] Furthermore, this application provides the application of the above-mentioned inhibitor composition for zirconium-titanium mixed concentrate or the inhibitor composition for zirconium-titanium mixed concentrate prepared by the above method in the flotation of zirconium-titanium mixed concentrate, including the following steps: S1. After adding a pH adjuster, the inhibitor composition and a collector to the zirconium-titanium mixed concentrate for roughing, zirconium rough concentrate and titanium rough concentrate are obtained; S2. The titanium crude concentrate is subjected to three cleaning processes using a pH adjuster and the inhibitor composition to obtain titanium concentrate; S3. Add a collector to the zircon rough concentrate for scavenging to obtain zircon concentrate, and return the scavenged concentrate to S1.

[0010] Furthermore, the zirconium-titanium mixed concentrate includes refractory ore produced during the electrostatic separation of coastal placer deposits, wherein the refractory ore contains 40% to 50% ZrO2 and 20% to 30% TiO2.

[0011] Furthermore, in S1, the pH adjuster includes sulfuric acid, and the collector includes a fatty acid collector.

[0012] Furthermore, in S2, the pH adjuster includes sulfuric acid.

[0013] Furthermore, in S3, the collector includes a fatty acid collector.

[0014] Furthermore, based on the weight of the zirconium-titanium mixed concentrate, in S1, the amount of the pH adjuster is 1000~1500 g / t, the amount of the inhibitor composition is 3000~4000 g / t, and the amount of the collector is 800~1000 g / t.

[0015] Furthermore, based on the weight of the titanium crude concentrate, in S2, during the first refining, the amount of the pH adjuster is 1500~2000 g / t, and the amount of the inhibitor composition is 400~800 g / t.

[0016] Furthermore, based on the weight of the titanium crude concentrate, in S2, during the second refining process, the amount of the pH adjuster used is 1500~2000 g / t.

[0017] Furthermore, in S2, the third selection is a blank drug selection.

[0018] Furthermore, based on the weight of the zirconium rough concentrate, in S3, the amount of the collector used is 200~500 g / t.

[0019] The principle of this application is: Organic acids can react with metal ions on the surface of zircon to form a complex film, reducing the surface activity of zircon and thus inhibiting its floatability. Carboxymethyl starch releases negatively charged carboxyl functional groups in aqueous solution. These negatively charged functional groups adsorb onto the positively charged zircon surface through electrostatic attraction or chemical bonding, making it easier for other inhibitors to adsorb. It can also form complexes with oxalic acid / citric acid to enhance the inhibitory effect. Sodium silicate decomposes in water to produce fluoride ions, which can react with zircon ions on the surface of zircon to form insoluble fluorides, further reducing the surface activity of zircon and enhancing the stability of the inhibitory film. Sodium hexametaphosphate, as a dispersant, can disperse mineral particles in the slurry and prevent them from agglomerating, thereby improving the efficiency of the inhibitor. It can also adsorb onto the surface of zircon to form a protective film, preventing the adsorption of collectors.

[0020] The beneficial effects of this application are: 1. This application uses a combination of organic acid, carboxymethyl starch, sodium fluorosilicate, and hexametaphosphate as a zircon depressant. This combination utilizes the synergistic effect among multiple depressants to achieve highly efficient suppression of zircon, thereby improving the separation effect of zircon and rutile. The combination of multiple depressants compensates for the shortcomings of a single depressant. Through the complexing effect of organic acid, the surface modification effect of carboxymethyl starch, the chemical reaction effect of sodium fluorosilicate, and the dispersing and protective effect of sodium hexametaphosphate, it can not only achieve zircon suppression in a short time, but also maintain the suppression effect throughout the entire flotation process, improving the selectivity and stability of flotation separation of zircon-titanium rough concentrate.

[0021] 2. This application uses a pH adjuster, an inhibitor composition and a collector in the flotation separation process. A flotation process consisting of one roughing, three cleaning and one scavenging can obtain high-grade rutile and zircon sand.

[0022] 3. This application utilizes a reverse flotation process consisting of one rougher, three cleaners, and one scavenger to achieve effective separation of rutile and zircon. The zircon and rutile grades can reach 61.05% and 82.09%, respectively, with recovery rates of 98.91% and 94.60%, respectively. Compared with single depressant schemes and conventional combined depressant schemes, this method exhibits better selective separation and is beneficial for separating difficult-to-process zircon-titanium mixed concentrates. Attached Figure Description

[0023] Figure 1 This is a process flow diagram of the flotation of zirconium-titanium mixed concentrate using an inhibitor composition, as described in this application. Detailed Implementation

[0024] The technical solution of this application is described in further detail below with reference to the accompanying drawings, but the scope of protection of this invention is not limited to the following description.

[0025] Example 1 The inhibitor composition was prepared according to the following steps: Weigh out oxalic acid, carboxymethyl starch, sodium fluorosilicate and sodium hexametaphosphate in a weight ratio of 20:20:35:1, add them directly to water, stir for 20 min at 25°C to prepare a combined solution with a total substance concentration of 10%, which is the inhibitor composition.

[0026] Using middlings from a coastal placer deposit obtained through electrostatic precipitation at a certain concentrator as the zirconium-titanium mixed concentrate to be processed, flotation was performed using the aforementioned inhibitor composition. The zirconium-titanium mixed concentrate contained 46.37% ZrO2 and 22.06% TiO2. The main mineral types were zircon, rutile, minor amounts of ilmenite, feldspar, quartz, and trace amounts of monazite. Specifically, the total zircon content was 69.23%, rutile 18.06%, ilmenite 7.73%, monazite 1.02%, and other gangue minerals 3.96%. The flotation process is as follows: S1. Based on the weight of the zirconium-titanium mixed concentrate, 1000 g / t of sulfuric acid, 4000 g / t of the inhibitor composition, and 800 g / t of fatty acid collector are added sequentially to the zirconium-titanium mixed concentrate. After each addition of the reagents, the mixture is stirred and reacted for 3 minutes. Then, roughing operation is performed to obtain titanium rough concentrate and zirconium rough concentrate. S2. Based on the weight of the titanium rough concentrate, add 1600 g / t of sulfuric acid and 500 g / t of the above-mentioned inhibitor composition to the titanium rough concentrate. Stir the reaction for 3 min after each addition of the reagent, and then perform fine selection I to obtain fine middlings 1 and fine concentrate 1. Fine middlings 1 is returned to S1. S3. Based on the weight of the titanium crude concentrate, add 1800 g / t of sulfuric acid to the refined concentrate 1 and stir for 3 min. Then proceed with refinement II to obtain refined middlings 2 and refined concentrate 2. Refined middlings 2 is returned to refinement I. S4. Based on the weight of the titanium crude concentrate, the refined concentrate 2 is subjected to refined treatment III without the addition of reagents to obtain refined middlings 3 and titanium concentrate. The refined middlings 3 is returned to refined treatment II. S5. Based on the weight of the zircon rough concentrate, add 300 g / t of fatty acid collector to the zircon rough concentrate and stir for 3 min. Then, perform scavenging to obtain scavenged ore and zircon concentrate. The scavenged ore is returned to S1.

[0027] The titanium and zirconium concentrates obtained after the flotation were sent to a qualified testing center to test the ZrO2 content using conventional chemical measurement methods and the TiO2 content using chemical titration. Then, the recovery rates of ZrO2 and TiO2 were calculated according to the grade and yield formulas, and the product indicators are shown in Table 1.

[0028] Table 1. Product Indicators of Titanium Concentrate and Zirconium Concentrate As can be seen from Table 1, the inhibitor composition and flotation process provided in this application can produce zircon concentrate with a ZrO2 grade of 61.05% and a ZrO2 recovery rate of 98.91%, and titanium concentrate with a TiO2 grade of 82.09% and a TiO2 recovery rate of 94.60%.

[0029] Example 2 The inhibitor composition was prepared according to the following steps: Weigh out oxalic acid, carboxymethyl starch, sodium fluorosilicate and sodium hexametaphosphate in a weight ratio of 25:25:45:1, add them directly to water, stir for 25 min at 20°C to prepare a combined solution with a total substance concentration of 5%, which is the inhibitor composition.

[0030] Using middlings from a coastal placer deposit obtained through electrostatic precipitation at a certain concentrator as the zirconium-titanium mixed concentrate to be processed, flotation was performed using the aforementioned inhibitor composition. The zirconium-titanium mixed concentrate contained 46.09% ZrO2 and 23.11% TiO2. The main mineral types were zircon, rutile, feldspar, quartz, and trace amounts of monazite. Specifically, the zircon content totaled 68.79%, rutile 23.11%, monazite 0.72%, and other gangue minerals 7.38%. The flotation process is as follows: S1. Based on the weight of the zirconium-titanium mixed concentrate, 1000 g / t of sulfuric acid, 4000 g / t of the inhibitor composition, and 850 g / t of fatty acid collector are added sequentially to the zirconium-titanium mixed concentrate. After each addition of the reagents, the mixture is stirred and reacted for 3 min. Then, roughing operation is performed to obtain titanium rough concentrate and zirconium rough concentrate. S2. Based on the weight of the titanium rough concentrate, add 1500 g / t of sulfuric acid and 600 g / t of the above-mentioned inhibitor composition to the titanium rough concentrate. Stir the reaction for 3 min after each addition of the reagent, and then carry out fine selection I to obtain fine middlings 1 and fine concentrate 1. Fine middlings 1 is returned to S1. S3. Based on the weight of the titanium crude concentrate, add 2000 g / t of sulfuric acid to the refined concentrate 1 and stir for 3 min. Then proceed with refinement II to obtain refined middlings 2 and refined concentrate 2. Refined middlings 2 is returned to refinement I. S4. Based on the weight of the titanium crude concentrate, the refined concentrate 2 is subjected to refined treatment III without the addition of reagents to obtain refined middlings 3 and titanium concentrate. The refined middlings 3 is returned to refined treatment II. S5. Based on the weight of the zircon rough concentrate, add 400 g / t of fatty acid collector to the zircon rough concentrate and stir for 3 min. Then, perform scavenging to obtain scavenged ore and zircon concentrate. The scavenged ore is returned to S1.

[0031] The titanium and zirconium concentrates obtained after the flotation were sent to a qualified testing center to test the ZrO2 content using conventional chemical measurement methods and the TiO2 content using chemical titration. Then, the recovery rates of ZrO2 and TiO2 were calculated according to the grade and yield formulas, and the product indicators are shown in Table 2.

[0032] Table 2 Product Indicators of Titanium Concentrate and Zirconium Concentrate As can be seen from Table 2, the inhibitor composition and flotation process provided in this application can produce zircon concentrate with a ZrO2 grade of 60.74% and a ZrO2 recovery rate of 96.12%, and titanium concentrate with a TiO2 grade of 78.11% and a TiO2 recovery rate of 91.46%.

[0033] Example 3 The inhibitor composition was prepared according to the following steps: Weigh out oxalic acid, carboxymethyl starch, sodium fluorosilicate and sodium hexametaphosphate in a weight ratio of 15:15:35:1, add them directly to water, stir at 30°C for 15 min to prepare a combined solution with a total substance concentration of 5%, which is the inhibitor composition.

[0034] Using middlings from a coastal placer deposit obtained through electrostatic precipitation at a certain concentrator as the zirconium-titanium mixed concentrate to be processed, flotation was performed using the aforementioned inhibitor composition. The zirconium-titanium mixed concentrate contained 42.96% ZrO2 and 26.42% TiO2. The main mineral types were zircon, rutile, minor amounts of calcite, amphibole, quartz, and trace amounts of monazite. Specifically, the total zircon content was 64.13%, rutile 26.42%, monazite 2.72%, and other gangue minerals 6.73%. The flotation process is as follows: S1. Based on the weight of the zirconium-titanium mixed concentrate, 1200 g / t of sulfuric acid, 3800 g / t of the inhibitor composition, and 1000 g / t of fatty acid collector are added sequentially to the zirconium-titanium mixed concentrate. After each addition of the reagents, the mixture is stirred and reacted for 3 minutes. Then, roughing operation is performed to obtain titanium rough concentrate and zirconium rough concentrate. S2. Based on the weight of the titanium rough concentrate, add 1500 g / t of sulfuric acid and 500 g / t of the above-mentioned inhibitor composition to the titanium rough concentrate. Stir the reaction for 3 min after each addition of the reagent, and then carry out fine selection I to obtain fine middlings 1 and fine concentrate 1. Fine middlings 1 is returned to S1. S3. Based on the weight of the titanium crude concentrate, add 2000 g / t of sulfuric acid to the refined concentrate 1 and stir for 3 min. Then proceed with refinement II to obtain refined middlings 2 and refined concentrate 2. Refined middlings 2 is returned to refinement I. S4. Based on the weight of the titanium crude concentrate, the refined concentrate 2 is subjected to refined treatment III without the addition of reagents to obtain refined middlings 3 and titanium concentrate. The refined middlings 3 is returned to refined treatment II. S5. Based on the weight of the zircon rough concentrate, add 500 g / t of fatty acid collector to the zircon rough concentrate and stir for 3 min. Then perform scavenging to obtain scavenged ore and zircon concentrate. The scavenged ore is returned to S1.

[0035] The titanium and zirconium concentrates obtained after the flotation were sent to a qualified testing center to test the ZrO2 content using conventional chemical measurement methods and the TiO2 content using chemical titration. Then, the recovery rates of ZrO2 and TiO2 were calculated according to the grade and yield formulas, and the product indicators are shown in Table 3.

[0036] Table 3 Product Indicators of Titanium Concentrate and Zirconium Concentrate As can be seen from Table 3, the inhibitor composition and flotation process provided in this application can produce zirconium concentrate with a ZrO2 grade of 62.37% and a ZrO2 recovery rate of 95.80%, and titanium concentrate with a TiO2 grade of 74.36% and a TiO2 recovery rate of 95.73%.

[0037] Example 4 The inhibitor composition was prepared according to the following steps: Weigh out oxalic acid, carboxymethyl starch, sodium fluorosilicate and sodium hexametaphosphate in a weight ratio of 20:20:40:1, add them directly to water, stir for 20 min at 25°C to prepare a combined solution with a total substance concentration of 5%, which is the inhibitor composition.

[0038] Using middlings from a coastal placer deposit obtained through electrostatic precipitation at a certain concentrator as the zirconium-titanium mixed concentrate to be processed, flotation was performed using the aforementioned inhibitor composition. The zirconium-titanium mixed concentrate contained 42.63% ZrO2 and 27.65% TiO2. The main mineral types were zircon, rutile, minor amounts of ilmenite, amphibole, quartz, and trace amounts of monazite. Specifically, the total zircon content was 62.62%, rutile 24.65%, ilmenite 5.76%, monazite 1.17%, and other gangue minerals 1.09%. The flotation process is as follows: S1. Based on the weight of the zirconium-titanium mixed concentrate, 1000 g / t of sulfuric acid, 3500 g / t of the inhibitor composition, and 1000 g / t of fatty acid collector are added sequentially to the zirconium-titanium mixed concentrate. After each addition of the reagents, the mixture is stirred and reacted for 3 minutes. Then, roughing operation is performed to obtain titanium rough concentrate and zirconium rough concentrate. S2. Based on the weight of the titanium rough concentrate, add 1500 g / t of sulfuric acid and 400 g / t of the above-mentioned inhibitor composition to the titanium rough concentrate. Stir the reaction for 3 min after each addition of the reagent, and then perform fine selection I to obtain fine middlings 1 and fine concentrate 1. Fine middlings 1 is returned to S1. S3. Based on the weight of the titanium crude concentrate, add 2000 g / t of sulfuric acid to the refined concentrate 1 and stir for 3 min. Then proceed with refinement II to obtain refined middlings 2 and refined concentrate 2. Refined middlings 2 is returned to refinement I. S4. Based on the weight of the titanium crude concentrate, the refined concentrate 2 is subjected to refined treatment III without the addition of reagents to obtain refined middlings 3 and titanium concentrate. The refined middlings 3 is returned to refined treatment II. S5. Based on the weight of the zircon rough concentrate, add 350 g / t of fatty acid collector to the zircon rough concentrate and stir for 3 min. Then perform scavenging to obtain scavenged ore and zircon concentrate. The scavenged ore is returned to S1.

[0039] The titanium and zirconium concentrates obtained after the flotation were sent to a qualified testing center to test the ZrO2 content using conventional chemical measurement methods and the TiO2 content using chemical titration. Then, the recovery rates of ZrO2 and TiO2 were calculated according to the grade and yield formulas, and the product indicators are shown in Table 4.

[0040] Table 4. Product Indicators of Titanium Concentrate and Zirconium Concentrate As can be seen from Table 4, the inhibitor composition and flotation process provided in this application can produce zirconium concentrate with a ZrO2 grade of 62.89% and a ZrO2 recovery rate of 98.46%, and titanium concentrate with a TiO2 grade of 80.13% and a TiO2 recovery rate of 96.40%.

[0041] As can be seen from the product indicators of Examples 1 to 4, although the raw material compositions of Examples 1 to 4 are different, resulting in certain differences in the product indicators obtained under the same mineral processing process, the overall mineral processing effect is good, and all of them can successfully achieve effective separation of titanium and zirconium in zirconium-titanium mixed concentrate.

[0042] Comparative Example 1 Comparative Example 1 used the same raw ore as Example 1, but the combined inhibitor was replaced with a single sodium fluorosilicate, and the dosage was the same as in Example 1. The final product indicators of titanium concentrate and zirconium concentrate are shown in Table 5.

[0043] Table 5. Product Indicators of Titanium Concentrate and Zirconium Concentrate Comparing Example 1 and Comparative Example 1, under the same conditions of other reagents, the combined inhibitor in Example 1 yielded a zirconium concentrate with a ZrO2 grade of 61.05% and a ZrO2 recovery rate of 98.91%, and a titanium concentrate with a TiO2 grade of 82.09% and a TiO2 recovery rate of 94.60%. Comparative Example 1 used sodium fluorosilicate as the inhibitor, which showed significantly poorer separation of the zirconium-titanium mixed concentrate. The zirconium concentrate had a ZrO2 grade of 49.09% and a recovery rate of 84.78%, while the titanium concentrate had a TiO2 grade of 48.62% and a recovery rate of 49.66%. These results indicate that traditional silicate inhibitors have strong inhibitory effects, but poor selectivity leads to the inhibition of most titanium. In other words, the combined inhibitor of this application possesses excellent inhibitory and selective properties.

[0044] Comparative Example 2 Comparative Example 2 used the same raw ore as Example 1, but the combined inhibitor was changed to sodium fluorosilicate and sodium hexametaphosphate in a weight ratio of 40:1, with the same dosage as in Example 1. The final product indicators of titanium concentrate and zirconium concentrate are shown in Table 6.

[0045] Table 6. Product Indicators of Titanium Concentrate and Zirconium Concentrate Comparing Example 1 and Comparative Example 2, under the same conditions of other reagents, the combined inhibitor in Example 1 yielded zirconium concentrate with a ZrO2 grade of 61.05% and a ZrO2 recovery rate of 98.91%, and titanium concentrate with a TiO2 grade of 82.09% and a TiO2 recovery rate of 94.60%. In Comparative Example 2, sodium fluorosilicate and sodium hexametaphosphate were used as inhibitors, but the separation effect of zirconium and titanium concentrates was still poor. The ZrO2 grade in the zirconium concentrate was 53.04% with a recovery rate of 92.94%, and the TiO2 grade in the titanium concentrate was 70.21% with a recovery rate of 63.10%. The results indicate that the selectivity of the silicate inhibitor is enhanced under the synergistic effect of sodium hexametaphosphate, but some titanium is still inhibited. In other words, the combined inhibitor of this application possesses both inhibitory and selective properties.

[0046] Comparative Example 3 Comparative Example 3 used the same raw ore as Example 1, but the combined inhibitor was changed to sodium fluorosilicate and acidified water glass in a weight ratio of 1:1, with the same dosage as in Example 1. The final product indicators of titanium concentrate and zirconium concentrate are shown in Table 7.

[0047] Table 7 Product Indicators of Titanium Concentrate and Zirconium Concentrate Comparing Example 1 and Comparative Example 3, under the same conditions of other reagents, the combined inhibitor in Example 1 yielded a zircon concentrate with a ZrO2 grade of 61.05% and a ZrO2 recovery rate of 98.91%, and a titanium concentrate with a TiO2 grade of 82.09% and a TiO2 recovery rate of 94.60%. Comparative Example 3, using sodium fluorosilicate and acidified water glass as inhibitors, showed poor performance in inhibiting zircon, with a ZrO2 grade of 56.78% and a recovery rate of 72.27% in the zircon concentrate, and a TiO2 grade of 45.68% and a recovery rate of 84.74% in the titanium concentrate. The results indicate that the combined inhibitor of silicate and acidified water glass has poor overall inhibitory performance, causing some zircon to float during the flotation of titanium concentrate. Although the grade of the zircon concentrate increased, the recovery rate decreased significantly, and the titanium concentrate grade was poor. In contrast, the combined inhibitor of this application exhibits better inhibitory performance and selectivity.

[0048] Comparative Example 4 Comparative Example 4 used the same raw ore as Example 4, but the combined inhibitor was replaced with a single sodium fluorosilicate, and the dosage was the same as in Example 4. The final product indicators of titanium concentrate and zirconium concentrate are shown in Table 8.

[0049] Table 8. Product Indicators of Titanium Concentrate and Zirconium Concentrate Comparing Example 4 and Comparative Example 4, under the same conditions of other reagents, the combined inhibitor in Example 4 yielded a zirconium concentrate with a ZrO2 grade of 62.89% and a ZrO2 recovery rate of 98.46%, and a titanium concentrate with a TiO2 grade of 80.13% and a TiO2 recovery rate of 96.40%. Comparative Example 4 used sodium fluorosilicate as the inhibitor, resulting in a ZrO2 grade of 48.72% and a recovery rate of 82.48% in the zirconium concentrate, and a TiO2 grade of 57.06% and a recovery rate of 57.50% in the titanium concentrate. These results indicate that traditional silicate inhibitors have strong inhibitory effects but poor selectivity, leading to the inhibition of most titanium. In contrast, the combined inhibitor of this application possesses excellent inhibitory and selective properties.

[0050] Comparative Example 5 Comparative Example 5 used the same raw ore as Example 4, but the combined inhibitor was changed to sodium fluorosilicate and sodium hexametaphosphate in a weight ratio of 40:1, with the same dosage as in Example 4. The final product indicators of titanium concentrate and zirconium concentrate are shown in Table 9.

[0051] Table 9. Product Indicators for Titanium Concentrate and Zirconium Concentrate Comparing Example 4 and Comparative Example 5, under the same conditions of other reagents, the combined inhibitor in Example 4 yielded a zircon concentrate with a ZrO2 grade of 62.89% and a ZrO2 recovery rate of 98.46%, and a titanium concentrate with a TiO2 grade of 80.13% and a TiO2 recovery rate of 96.40%. Comparative Example 4 used a 40:1 ratio of sodium fluorosilicate and sodium hexametaphosphate as inhibitors, yielding a zircon concentrate with a ZrO2 grade of 54.68% and a recovery rate of 98.63%, and a titanium concentrate with a TiO2 grade of 82.41% and a recovery rate of 69.53%. These results indicate that the selectivity of the silicate inhibitor is enhanced under the synergistic effect of sodium hexametaphosphate. However, due to the excessive inhibitory effect, some titanium is still inhibited. In contrast, the combined inhibitor of this application possesses both inhibitory and selective properties.

[0052] The above description is merely a preferred embodiment of this application. It should be understood that this application is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the concept described herein through the above teachings or the technology or knowledge in related fields. Modifications and variations made by those skilled in the art that do not depart from the spirit and scope of this invention should be within the protection scope of the appended claims.

Claims

1. An inhibitor composition for zirconium-titanium mixed concentrate, characterized in that, The inhibitor composition is obtained by compounding organic acid, carboxymethyl starch, sodium fluorosilicate and sodium hexametaphosphate.

2. The inhibitor composition for zirconium-titanium mixed concentrate according to claim 1, characterized in that, The weight ratio of the organic acid, the carboxymethyl starch, the sodium fluorosilicate, and the hexametaphosphate is (15~25):(15~25):(35~45):

1.

3. The depressant composition for zirconium-titanium mixed concentrates according to claim 1, characterized in that, The organic acid includes at least one of oxalic acid and citric acid.

4. A method of preparing an inhibitor composition for zirconium-titanium mixed concentrates as claimed in any one of claims 1 to 3, characterized in that, Includes the following steps: The organic acid, carboxymethyl starch, sodium fluorosilicate, and sodium hexametaphosphate were added to water and stirred at 20-30°C for 15-25 min to obtain the inhibitor composition. The total concentration of the inhibitor composition is 5-10%.

5. Use of the depressant composition for zirconium-titanium mixed concentrates according to any one of claims 1 to 3 or prepared according to the process of claim 4 in the flotation of zirconium-titanium mixed concentrates, characterized in that, Includes the following steps: S1. After adding a pH adjuster, the inhibitor composition and a collector to the zirconium-titanium mixed concentrate for roughing, zirconium rough concentrate and titanium rough concentrate are obtained; S2. The titanium crude concentrate is subjected to three cleaning processes using a pH adjuster and the inhibitor composition to obtain titanium concentrate; S3. Add a collector to the zircon rough concentrate for scavenging to obtain zircon concentrate, and return the scavenged concentrate to S1.

6. Use according to claim 5, characterized in that, The zirconium-titanium mixed concentrate includes refractory ore produced during the electrostatic separation of coastal placer deposits, wherein the refractory ore contains 40% to 50% ZrO2 and 20% to 30% TiO2.

7. Use according to claim 5, characterized in that, In S1, the pH adjuster includes sulfuric acid, and the collector includes a fatty acid collector; And / or, in S2, the pH adjuster includes sulfuric acid; And / or, in S3, the collector includes a fatty acid collector.

8. Use according to claim 5, characterized in that, Based on the weight of the zirconium-titanium mixed concentrate, in S1, the amount of the pH adjuster is 1000~1500 g / t, the amount of the inhibitor composition is 3000~4000 g / t, and the amount of the collector is 800~1000 g / t.

9. Use according to claim 5, characterized in that, Based on the weight of the titanium crude concentrate, in S2, during the first refining, the amount of the pH adjuster is 1500~2000 g / t, and the amount of the inhibitor composition is 400~800 g / t. And / or, based on the weight of the titanium crude concentrate, in S2, during the second refining, the amount of the pH adjuster used is 1500~2000 g / t; And / or, in S2, the third selection is a blank drug selection.

10. Use according to claim 5, characterized in that, Based on the weight of the zirconium crude concentrate, in S3, the amount of the collector used is 200~500 g / t.

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