Collecting agent composition for efficient flotation of garnet from low-grade titanium ore sand and application of collecting agent composition

Abstract

The invention relates to the technical field of mineral separation, in particular to a collecting agent composition for efficient flotation of garnet from low-grade titanium ore sand and application of the collecting agent composition, and the collecting agent composition is obtained by compounding an amine agent, a fatty acid agent and cyclohexane tetraacetic acid; wherein the amine medicament comprises a C12-C18 amine medicament, and the amine medicament comprises a C12-C18 amine medicament. The fatty acid medicament comprises sodium oleate, oxidized paraffin soap, naphthenic soap, oleic acid, stearic acid and other common fatty acid medicaments. The collecting agent composition breaks through the bottlenecks that an existing collecting agent is poor in selectivity and low in flotation recovery rate when garnet in titanium ore sand is subjected to flotation, and at least high-quality recovery of ilmenite in low-grade titanium ore sand is achieved.

Description

Technical Field

[0001] This application relates to the field of mineral processing technology, specifically to a collector composition for the efficient flotation of garnet from low-grade titanium ore sand and its application. Background Technology

[0002] Ilmenite, primarily composed of FeTiO3, is an important titanium resource widely used in metallurgy, chemicals, and pigments. Ilmenite can be smelted to produce titanium dioxide, an important white pigment with excellent hiding power, tinting strength, weather resistance, and chemical stability, widely used in coatings, plastics, papermaking, and inks. Furthermore, ilmenite can also be used to produce metallic titanium, which possesses excellent properties such as low density, high strength, and corrosion resistance, and is widely used in aerospace, chemical, and medical fields.

[0003] Titanium ore sands are a significant source of ilmenite, especially in primary deposits with low grades, where mining and utilization of titanium sands is more economically valuable. It is estimated that approximately 60% of global ilmenite production comes from titanium sands. Titanium ore sands are typically a mixture of various heavy minerals, including zircon, rutile, monazite, garnet, magnetite, and tourmaline, in addition to ilmenite. These minerals differ in density, magnetism, and surface properties, allowing for separation through various beneficiation methods.

[0004] In low-grade titanium ore sands, garnet often occurs in association with ilmenite, and the two are quite similar in density and magnetic properties, making it difficult to achieve effective separation using traditional gravity and magnetic separation methods. Although flotation can be used to separate garnet and ilmenite, due to their similar surface properties, it is still difficult to achieve good selective separation using a single flotation reagent.

[0005] Therefore, it is necessary to develop a new type of collector that can efficiently and selectively float garnet, thereby improving the beneficiation efficiency and resource utilization of low-grade titanium ore. Summary of the Invention

[0006] The purpose of this application is to overcome the shortcomings of the prior art and provide a collector composition for efficient flotation of garnet from low-grade titanium ore sand and its application. It breaks through the bottleneck of poor selectivity and low flotation recovery rate of existing collectors when flotating garnet in titanium ore sand, and at least achieves high-quality recovery of ilmenite from low-grade titanium ore sand.

[0007] The objective of this application is achieved through the following technical solution: On the one hand, this application provides a collector composition, which is obtained by compounding an amine agent, a fatty acid agent, and cyclohexanetetraacetic acid; The amine agents include C12-C18 amine agents; The fatty acid reagents include common fatty acid reagents such as sodium oleate, oxidized paraffin soap, naphthenic acid soap, oleic acid, and stearic acid.

[0008] In the above technical solution, the positively charged groups in the amine collector molecules can preferentially accumulate on the negatively charged active sites on the garnet surface through electrostatic adsorption, thereby achieving effective and selective collection of garnet; fatty acids, as auxiliary collectors, can significantly enhance the hydrophobicity of the garnet surface with their hydrophobic groups, and synergistically promote the flotation of garnet with the amine collectors; cyclohexanetetraacetic acid (CYDTA), as a chelating agent, can selectively complex with metal ions on the surface of gangue minerals, change their surface properties, enhance their hydrophilicity, and thus effectively inhibit the flotation of gangue minerals.

[0009] Furthermore, the weight ratio of the amine agent, the fatty agent, and the cyclohexanetetraacetic acid is 1:16:12.

[0010] Furthermore, the C12-C18 amine reagents include one of analytical grade dodecylamine and analytical grade octadecylamine.

[0011] On the other hand, this application provides a method for preparing the above-mentioned collector composition, comprising the following steps: The amine agent, the fatty acid agent, and the cyclohexanetetraacetic acid are added to oxalic acid and stirred for the first time to obtain a mixed solution; Water is added to the mixed solution for dilution and a second stirring to obtain the collector composition.

[0012] Furthermore, the concentration of the oxalic acid is 10% to 15%.

[0013] Furthermore, the total concentration of the collector composition obtained after dilution is 5% to 10%.

[0014] Furthermore, the water includes tap water.

[0015] Furthermore, the temperature of the first stirring is 40~60℃, and the stirring time is 10~15 min.

[0016] Furthermore, the temperature of the second stirring is 15~25℃, and the stirring time is 5~10 min.

[0017] Furthermore, this application provides the application of the above-mentioned collector composition or the collector composition prepared by the above method in the ilmenite beneficiation process of preferential flotation of garnet from titanium ore sand, including the following steps: S1. Stir the low-grade ilmenite in the flotation cell for 1 min, let it stand for 1-2 min, remove the supernatant, and adjust the pulp concentration to 50% to obtain a mixed pulp. S2. Add pH adjuster, inhibitor and collector composition to the mixed slurry in sequence, stir for 3 minutes for roughing and perform 3-4 minutes of skimming to obtain garnet concentrate and titanium rough concentrate; S3. Add the collector composition to the titanium rough concentrate again and perform one scavenging to obtain scavenged ore and titanium concentrate. The scavenged ore is returned to S2.

[0018] Furthermore, the titanium ore sand comprises a gravity-selected ore with a titanium content of 15% to 20%, a zircon content of 1% to 2%, a garnet content of 50% to 60%, and the remaining minerals such as quartz and feldspar having a content of less than 5%.

[0019] Furthermore, the pH adjuster includes sodium carbonate.

[0020] Furthermore, the inhibitor comprises water glass and sodium carboxymethyl cellulose in a weight ratio of 10:1.

[0021] Furthermore, based on low-grade ilmenite, the amount of pH adjuster used in S2 is 300~500 g / t.

[0022] Furthermore, based on low-grade ilmenite, the amount of the inhibitor used in S2 is 400~600 g / t.

[0023] Furthermore, based on low-grade ilmenite, the amount of the inhibitor used in S2 is 400~600 g / t.

[0024] Furthermore, based on low-grade ilmenite, the amount of the collector composition used in S2 is 1500~2000 g / t.

[0025] Furthermore, based on low-grade ilmenite, in S3, the amount of the collector composition used is 200~500 g / t.

[0026] The beneficial effects of this application are: 1. The collector composition provided in this application reduces the entrainment of gangue minerals by utilizing the synergistic effect of selective collection by amine agents, hydrophobic enhancement by fatty acid agents, and gangue inhibition by cyclohexanetetraacetic acid, thereby achieving efficient flotation separation of garnet and significantly improving the selectivity of garnet flotation from titanium ore sand and the recovery rate of ilmenite.

[0027] 2. In the roughing stage of flotation separation, this application uses less pH adjuster and inhibitor, which can save costs in titanium ore beneficiation.

[0028] 3. Using the collector composition provided in this application, garnet concentrate and titanium concentrate with ilmenite as the main component can be obtained by a flotation process of one roughing and one scavenging of titanium ore sand. The TiO2 grade in the titanium concentrate is above 41%, and the TiO2 recovery rate is above 95%. It is a collector composition with excellent mineral processing effect. Attached Figure Description

[0029] Figure 1 This is a process flow diagram of the flotation of titanium ore using a collector composition according to this application. Detailed Implementation

[0030] 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.

[0031] Example 1 The collector composition was prepared according to the following steps: Analytical grade dodecylamine, analytical grade sodium oleate, and analytical grade cyclohexanetetraacetic acid were added to 10% oxalic acid at a weight ratio of 1:16:12, and stirred at 40°C for 10 min to obtain a mixed solution. Tap water was added to the mixed solution to dilute it to a total concentration of 10%, and then stirred at 25°C for 5 min to obtain the collector composition.

[0032] Using the accumulated titanium middlings from the gravity separation tailings of a placer mine in Lianyungang as the low-grade titanium ore sand to be processed, a flotation process with garnet pre-separation was carried out using the aforementioned collector composition. The TiO2 content in the mineral was 15.84%. Combined with process mineralogical studies, it was found that the main mineral composition of this low-grade titanium ore sand was ilmenite, garnet, a small amount of quartz, zircon, and trace amounts of rutile. Among them, the total mineral content of ilmenite was 28.53%, the mineral content of garnet was 65.66%, the mineral content of rutile was 1.02%, and the content of other gangue minerals was 4.78%. The flotation process is as follows: S1. Stir 500 g of low-grade ilmenite in a hanging trough flotation cell of model XRF1.0L for 1 min, let stand for 1 min, remove the supernatant, and adjust the pulp concentration to 50% with tap water to obtain a mixed pulp. S2. Based on the weight of low-grade ilmenite, 500 g / t sodium carbonate, 600 g / t water glass and sodium carboxymethyl cellulose mixed in a weight ratio of 10:1 inhibitor, and 1600 g / t the collector composition prepared in this embodiment are added sequentially to the mixed slurry. The mixture is stirred for 3 minutes each time the reagent is added. After roughing, a 3-minute skimming operation is performed to obtain garnet concentrate and titanium rough concentrate. S3. Add 400 g / t of the collector composition to the titanium rough concentrate again, and perform one scavenging process for 3 min to obtain scavenged ore and titanium concentrate. The scavenged ore is returned to S2.

[0033] Example 2 The collector composition was prepared according to the following steps: Dodecylamine (analytical grade), sodium oleate (analytical grade), and cyclohexanetetraacetic acid (analytical grade) were added to 10% oxalic acid at a weight ratio of 1:16:12. The mixture was stirred at 30°C for 5 min to obtain a mixed solution. Tap water was added to the mixed solution to dilute it to a total concentration of 10%, and then the mixture was stirred at 15°C for 10 min to obtain the collector composition.

[0034] Using low-grade titanium ore concentrate from a coastal placer mine in Fujian as the target material, a flotation process with pre-separation of garnet was conducted using the aforementioned collector composition. The TiO2 content in the mineral was 16.7%. Combined with process mineralogical studies, it was found that the main mineral composition of this low-grade titanium ore concentrate was ilmenite, garnet, and small amounts of quartz and feldspar. Specifically, the total mineral content of ilmenite was 32.11%, the mineral content of garnet was 65.36%, and the total content of quartz and feldspar was 2.53%. The flotation process is as follows: S1. Stir 500 g of low-grade ilmenite in a hanging trough flotation cell of model XRF1.0L for 1 min, let stand for 1 min, remove the supernatant, and adjust the pulp concentration to 50% with tap water to obtain a mixed pulp. S2. Based on the weight of low-grade ilmenite, 500 g / t sodium carbonate, 600 g / t water glass and sodium carboxymethyl cellulose mixed in a weight ratio of 10:1 inhibitor, and 1500 g / t the collector composition prepared in this embodiment are added sequentially to the mixed slurry. The mixture is stirred for 3 minutes each time the reagent is added. After roughing is completed, a 3-minute skimming operation is performed to obtain garnet concentrate and titanium rough concentrate. S3. Add 300 g / t of the collector composition to the titanium rough concentrate again, and perform one scavenging process for 3 min to obtain scavenged ore and titanium concentrate. The scavenged ore is returned to S2.

[0035] Example 3 The collector composition was prepared according to the following steps: Analytical grade octadecylamine, oxidized paraffin soap, and analytical grade cyclohexanetetraacetic acid were added to 15% oxalic acid at a weight ratio of 1:16:12, and stirred at 25°C for 10 min to obtain a mixed solution. Tap water was added to the mixed solution to dilute it to a total concentration of 5%, and then stirred at 25°C for 10 min to obtain the collector composition.

[0036] Using sample No. 1 of accumulated titanium middlings from a foreign coastal placer mine, produced through combined gravity and magnetic pre-enrichment, as the low-grade titanium ore sand to be processed, a flotation process with garnet pre-separation was conducted using the aforementioned collector composition. The TiO2 content in the minerals was 21.2%. Combined with process mineralogical studies, it was found that the main mineral composition of this low-grade titanium ore sand was ilmenite, garnet, and small amounts of rutile, quartz, and zircon. Specifically, the total mineral content of ilmenite was 36.07%, garnet 59.66%, rutile 3.02%, and other gangue minerals 1.56%. The flotation process is as follows: S1. Stir 500 g of low-grade ilmenite in a hanging trough flotation cell of model XRF1.0L for 1 min, let stand for 2 min, remove the supernatant, and adjust the pulp concentration to 50% with tap water to obtain a mixed pulp. S2. Based on the weight of low-grade ilmenite, 400 g / t sodium carbonate, 500 g / t water glass and sodium carboxymethyl cellulose mixed in a weight ratio of 10:1 inhibitor, and 1500 g / t the collector composition prepared in this embodiment are added sequentially to the mixed slurry. The mixture is stirred for 3 minutes each time the reagents are added. After roughing, a 3-minute skimming operation is performed to obtain garnet concentrate and titanium rough concentrate. S3. Add 300 g / t of the collector composition to the titanium rough concentrate again, and perform one scavenging process for 3 min to obtain scavenged ore and titanium concentrate. The scavenged ore is returned to S2.

[0037] Example 4 The collector composition was prepared according to the following steps: Analytical grade octadecylamine, oxidized paraffin soap, and analytical grade cyclohexanetetraacetic acid were added to 15% oxalic acid at a weight ratio of 1:16:12, and stirred at 25°C for 10 min to obtain a mixed solution. Tap water was added to the mixed solution to dilute it to a total concentration of 5%, and then stirred at 25°C for 10 min to obtain the collector composition.

[0038] Using sample No. 2 of accumulated titanium middlings from a foreign coastal placer mine, produced through combined gravity and magnetic pre-enrichment, as the low-grade titanium ore sand to be processed, a flotation process with garnet pre-separation was conducted using the aforementioned collector composition. The TiO2 content in the minerals was 222.78%. Combined with process mineralogical studies, it was found that the main mineral composition of this low-grade titanium ore sand was ilmenite, garnet, and small amounts of rutile, quartz, and zircon. Specifically, the total mineral content of ilmenite was 39.96%, garnet 54.36%, rutile 2.78%, and other gangue minerals 2.89%. The flotation process is as follows: S1. Stir 500 g of low-grade ilmenite in a hanging trough flotation cell of model XRF1.0L for 1 min, let stand for 2 min, remove the supernatant, and adjust the pulp concentration to 50% with tap water to obtain a mixed pulp. S2. Based on the weight of low-grade ilmenite, 600 g / t sodium carbonate, 500 g / t water glass and sodium carboxymethyl cellulose mixed in a weight ratio of 10:1 inhibitor, and 1500 g / t the collector composition prepared in this embodiment are added sequentially to the mixed slurry. The mixture is stirred for 3 minutes each time the reagents are added. After roughing, a 3-minute skimming operation is performed to obtain garnet concentrate and titanium rough concentrate. S3. Add 200 g / t of the collector composition to the titanium rough concentrate again, and perform one scavenging process for 3 min to obtain scavenged ore and titanium concentrate. The scavenged ore is returned to S2.

[0039] Comparative Example 1 Prepare the collector according to the following steps: Analytical grade dodecylamine and analytical grade sodium oleate were added to 10% oxalic acid at a weight ratio of 1:16 and stirred at 40°C for 10 min to obtain a mixed solution. Add tap water to the mixed solution to dilute it to a total concentration of 10%, and then stir at 25°C for 5 min to obtain the collector composition.

[0040] Using the same minerals as in Example 1, and with the collector prepared in Comparative Example 1, the same flotation process as in Example 1 was performed to obtain garnet concentrate and titanium concentrate.

[0041] Comparative Example 2 Prepare the collector according to the following steps: Analytical grade sodium oleate was added to 10% oxalic acid and stirred at 40°C for 10 min to obtain a sodium oleate solution. The sodium oleate solution was diluted with tap water to a total concentration of 10%, and then stirred at 25°C for 5 minutes to obtain the collector composition.

[0042] Using the same minerals as in Example 1, and with the collector prepared in Comparative Example 2, the same flotation process as in Example 1 was performed to obtain garnet concentrate and titanium concentrate.

[0043] Comparative Example 3 Prepare the collector according to the following steps: Analytical grade octadecylamine and oxidized paraffin soap were added to 10% oxalic acid at a weight ratio of 1:16 and stirred at 40°C for 10 min to obtain a mixed solution. Add tap water to the mixed solution to dilute it to a total concentration of 10%, and then stir at 25°C for 5 min to obtain the collector composition.

[0044] Using the same minerals as in Example 3, and with the collector prepared in Comparative Example 3, the same flotation process as in Example 3 was performed to obtain garnet concentrate and titanium concentrate.

[0045] Comparative Example 4 Add oxidized paraffin soap to 10% oxalic acid and stir at 40°C for 10 min to obtain a mixed solution; Add tap water to the mixed solution to dilute it to a total concentration of 10%, and then stir at 25°C for 5 min to obtain the collector composition.

[0046] Using the same minerals as in Example 3, and with the collector prepared in Comparative Example 4, the same flotation process as in Example 3 was performed to obtain garnet concentrate and titanium concentrate.

[0047] Experimental Example Garnet concentrate and titanium concentrate obtained in Examples 1-4 and Comparative Examples 1-4 were characterized by chemical element analysis and mineral content determination. The TiO2 content was determined by chemical titration at a qualified testing center. The TiO2 recovery rate was calculated by the grade and yield formula. The specific test indicators are shown in Table 1.

[0048] Table 1. Indicators of garnet and titanium concentrates after flotation with different collectors The results show that through a simple closed-circuit flotation test of "one roughing and one scavenging", most of the garnet gangue minerals can be efficiently separated from low-grade titanium ore sand in Lianyungang, Fujian and foreign titanium ore sand, and iron concentrate with TiO2 grade of more than 41% and TiO2 recovery rate of more than 95% as the main component is ilmenite. Comparing the flotation effects of Example 1 and Comparative Example 1, it can be seen that, under the same conditions of other reagents, the collector composition of dodecylamine + sodium oleate has a strong overall collecting ability, but lacks selectivity, and some ilmenite is also selected when flotating garnet. Comparing the flotation effects of Example 1 and Comparative Example 2, it can be seen that, under the same conditions of other reagents, sodium oleate alone has a suitable collecting ability, but the selectivity is still poor, and it is easy to have substandard garnet purity and a lot of waste of titanium resources. Comparing the flotation effects of Example 3 and Comparative Example 3, it can be seen that, under the same conditions of other reagents, the collector composition of octadecylamine + oxidized paraffin soap has a strong overall collecting ability, but lacks selectivity, and some ilmenite is also selected when flotating garnet. Comparing the flotation effects of Example 3 and Comparative Example 4, it can be seen that, under the same conditions of other reagents, oxidized paraffin soap alone has a suitable collecting ability, but the selectivity is still poor, and it is easy to have substandard garnet purity and a lot of waste of titanium resources. In summary, the collector composition provided in this application possesses superior collecting and selective properties. The above description is merely a preferred embodiment of this application, and it should be understood that this application is not limited to the forms disclosed herein, nor should it 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 related technical or knowledge. 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. A collector composition, characterized in that, The collector composition is obtained by compounding amine agents, fatty acid agents, and cyclohexanetetraacetic acid; The amine agents include C12-C18 amine agents; The fatty acid reagents include common fatty acid reagents such as sodium oleate, oxidized paraffin soap, naphthenic acid soap, oleic acid, and stearic acid.

2. The collector composition according to claim 1, characterized in that, The weight ratio of the amine agent, the fatty agent, and the cyclohexanetetraacetic acid is 1:16:

12.

3. The collector composition according to claim 1, characterized in that, The C12-C18 amine reagents include one of analytical grade dodecylamine and analytical grade octadecylamine.

4. A method for preparing the collector composition according to any one of claims 1 to 3, characterized in that, Includes the following steps: The amine agent, the fatty acid agent, and the cyclohexanetetraacetic acid are added to oxalic acid and stirred for the first time to obtain a mixed solution; Water is added to the mixed solution for dilution and a second stirring to obtain the collector composition.

5. The method according to claim 4, characterized in that, The concentration of the oxalic acid is 10%~15%; And / or, the total concentration of the collector composition obtained after dilution is 5% to 10%.

6. The method according to claim 4, characterized in that, The water includes tap water.

7. The method according to claim 4, characterized in that, The temperature of the first stirring is 25~40℃, and the stirring time is 10~15 min; And / or, the temperature of the second stirring is 15~25℃, and the stirring time is 5~10 min.

8. The application of the collector composition according to any one of claims 1 to 3 or the collector composition prepared by the method according to any one of claims 4 to 7 in the ilmenite beneficiation process of preferential flotation of garnet from titanium ore sand, characterized in that, Includes the following steps: S1. Stir the low-grade ilmenite in the flotation cell for 1 min, let it stand for 1-2 min, remove the supernatant, and adjust the pulp concentration to 50% to obtain a mixed pulp. S2. Add pH adjuster, inhibitor and collector composition to the mixed slurry in sequence, stir for 3 min for roughing and perform 3-4 min for skimming to obtain garnet concentrate and titanium rough concentrate; S3. Add the collector composition to the titanium rough concentrate again and perform one scavenging to obtain scavenged ore and titanium concentrate. The scavenged ore is returned to S2.

9. The application according to claim 8, characterized in that, The titanium ore sand includes a gravity-selected ore with a titanium content of 15% to 20%, a zircon content of 1% to 2%, a garnet content of 50% to 60%, and the remaining minerals such as quartz and feldspar having a content of less than 5%. And / or, the pH adjuster includes sodium carbonate; And / or, the inhibitor comprises water glass and sodium carboxymethyl cellulose in a weight ratio of 10:

1.

10. The application according to claim 8, characterized in that, Based on low-grade ilmenite, the amount of pH adjuster used in S2 is 300~500 g / t; And / or, based on low-grade ilmenite, in S2, the amount of the inhibitor is 400~600 g / t; And / or, based on low-grade ilmenite, in S2, the amount of the inhibitor is 400~600 g / t; And / or, based on low-grade ilmenite, in S2, the amount of the collector composition used is 1500~2000 g / t; And / or, based on low-grade ilmenite, in S3, the amount of the collector composition used is 200~500 g / t.

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