Cycloalkane-based diphosphonic acid ilmenite collecting agent, preparation method and application

Abstract

The invention provides a naphthenyl diphosphonic acid ilmenite collecting agent, a preparation method and application. The general formula of the naphthenyl diphosphonic acid ilmenite collecting agent is C < n + 1 > H < 2n + 4 > O7P2. Wherein n is an integer from 3 to 18. The preparation method comprises the following steps: mixing cycloalkane carboxylic acid, phosphorous acid and phosphorus trichloride, and performing esterification reaction to obtain a phosphonate intermediate; then carrying out hydrolysis reaction and filtering to obtain cycloalkane diphosphonic acid filtrate; and at the low temperature, a non-polar solvent is adopted for purifying the naphthenyl diphosphonic acid filtrate, so that solids are separated out, the solids are separated, and the naphthenyl diphosphonic acid ilmenite collecting agent is obtained. And a good flotation effect can be achieved under the acidic and alkaline conditions. The preparation method is simple, convenient to operate and suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation and separation, and particularly to a cycloalkane-based bisphosphonate ilmenite collector, its preparation method, and its application. Background Technology

[0002] In the flotation process of oxidized minerals, developing novel and highly efficient collectors is key to improving separation performance. Common collectors for oxidized minerals mainly include carboxylic acids, bisphosphonates, arsenoic acids, and phosphonates. Although carboxylic acid collectors have strong collecting power, their selectivity is relatively poor. While arsenoic acid collectors can meet flotation requirements to some extent, their high toxicity poses potential hazards to the environment and human health, severely limiting their widespread application in industrial production. In contrast, bisphosphonate collectors, due to the presence of lone pairs of electrons in their oxygen and phosphorus atoms, can form stable chelates with metal ions, thus exhibiting high selectivity and collecting power. Commonly used bisphosphonate collectors include styrenephosphonic acid and alkylamine dimethylphosphonic acid. However, styrenephosphonic acid and alkylamine dimethylphosphonic acid cannot simultaneously achieve good flotation results for ilmenite under both acidic and alkaline conditions. Moreover, the high synthesis cost and low yield of existing bisphosphonate collectors limit their application in practical industrial flotation. Based on this, the present invention provides a cycloalkane-based bisphosphonic acid ilmenite collector, its preparation method and application, aiming to solve the technical problem that existing ilmenite collectors are unable to maintain high-efficiency collecting performance under both acidic and alkaline environments. Summary of the Invention

[0003] The main objective of this invention is to provide a cycloalkane-based bisphosphonic acid ilmenite collector, its preparation method, and its application, in order to solve the technical problem that existing ilmenite collectors are unable to maintain high-efficiency collecting performance under both acidic and alkaline environments.

[0004] To achieve the above objectives, the present invention provides a cycloalkane-based bisphosphonate ilmenite collector, wherein the general formula of the cycloalkane-based bisphosphonate ilmenite collector includes: C n+1 H 2n+4 O7P2.

[0005] Where n is an integer from 3 to 18.

[0006] According to embodiments of this application, under slurry conditions with a pH of 4 to 8, the cycloalkane-based bisphosphonate ilmenite collector exhibits collecting activity for ilmenite.

[0007] The cycloalkane-based bisphosphonate ilmenite collector contains cycloalkane groups and bisphosphonic acid groups in its molecular structure.

[0008] The TiO2 recovery rate is 75-85%, the TiO2 grade is 34-36%, and the yield of ilmenite is 40-50%.

[0009] This invention also provides a method for preparing the cycloalkane-based bisphosphonate ilmenite collector as described above, comprising the following steps: Cycloalkanes, carboxylic acids, phosphorous acid, and phosphorus trichloride are mixed and then subjected to esterification to obtain phosphonate intermediates.

[0010] The phosphonate intermediate was hydrolyzed and then filtered to obtain a cycloalkane-based bisphosphonic acid filtrate.

[0011] At low temperature, the cycloalkane-based bisphosphonic acid filtrate is purified using a non-polar solvent to precipitate the solid. The solid is then separated to obtain the cycloalkane-based bisphosphonic acid ilmenite collector.

[0012] According to embodiments of this application, the esterification reaction step includes: First, mix cycloalkanes, carboxylic acids, and phosphorous acid, and heat them at 70-85°C until they melt to obtain a molten mixture.

[0013] After phosphorus trichloride is added dropwise to the molten mixture until complete, the reaction is continued at 70-80°C for 3-5 hours to obtain the phosphonate intermediate.

[0014] The time for adding phosphorus trichloride is 25-35 minutes.

[0015] According to an embodiment of this application, the molar ratio of the cycloalkane carboxylic acid, the phosphorous acid, and the phosphorus trichloride is 1:(2.5~3.5):(2.5~3.5).

[0016] According to an embodiment of this application, in the hydrolysis reaction step, water is added to the phosphonate intermediate to carry out the hydrolysis reaction, and the volume ratio of the phosphonate intermediate to water is 1:(0.8~1.2).

[0017] According to an embodiment of this application, the temperature of the hydrolysis reaction is 90~110°C.

[0018] The hydrolysis reaction lasts for 1 to 2 hours.

[0019] According to embodiments of this application, the nonpolar solvent includes one or more of acetone, ethyl acetate, acetonitrile, and tetrahydrofuran.

[0020] The volume ratio of the nonpolar solvent to the cycloalkane-based bisphosphonic acid filtrate is 1:(3~8).

[0021] According to an embodiment of this application, the low temperature is 0~5°C.

[0022] The solid precipitation time is 2~24 h.

[0023] This invention also provides an application of the cycloalkane-based bisphosphonate ilmenite collector as described above or the cycloalkane-based bisphosphonate ilmenite collector prepared by the above preparation method, the steps of which include: Adding a cycloalkane-based bisphosphonic acid ilmenite collector to the flotation solution of ilmenite yields titanium concentrate.

[0024] The amount of the cycloalkane-based bisphosphonic acid ilmenite collector added is in a mass ratio of 3:(1500~3000) to ilmenite.

[0025] Compared with the prior art, the beneficial effects of the present invention are: The aforementioned cycloalkane-based bisphosphonic acid ilmenite collector contains specific cycloalkane and bisphosphonic acid groups in its molecular structure. These groups can specifically adsorb onto specific active sites on the ilmenite surface (such as hydroxyl groups on titanium oxide surfaces), preferentially adsorbing ilmenite while exhibiting relatively weaker adsorption capacity for other minerals (such as gangue minerals like quartz). This allows for effective enrichment of ilmenite during flotation, improving the separation efficiency between ilmenite and other minerals. The bisphosphonic acid groups possess strong coordination capabilities; each phosphonic acid group can provide two oxygen atoms as coordinating atoms, forming stable chemical bonds with metal ions (mainly titanium ions) on the ilmenite surface. These stable chemical bonds enable ilmenite particles to firmly adhere to the bubble surface, thus facilitating flotation. A suitable n value can balance the hydrophobicity and hydrophilicity of the collector molecule, further enhancing its collecting ability for ilmenite. In addition, because the coordination ability of the bisphosphonic acid group and the hydrophobic properties of the cycloalkane group can remain relatively stable, the cycloalkane-based bisphosphonic acid ilmenite collector described in this invention can achieve good flotation results under both acidic and alkaline conditions. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0027] Figure 1 This is the equation for the esterification reaction involved in the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 1 of this invention; Figure 2 This is the equation for the esterification reaction involved in the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 2 of this invention; Figure 3 This is the equation for the esterification reaction involved in the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 3 of the present invention; Figure 4 This is a flowchart of the preparation of the cycloalkane-based bisphosphonate ilmenite collector according to the present invention.

[0028] The realization of the objective, functional characteristics and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0031] To achieve the above objectives, the present invention provides a cycloalkane-based bisphosphonate ilmenite collector, wherein the general formula of the cycloalkane-based bisphosphonate ilmenite collector includes: C n+1 H 2n+4 O7P2.

[0032] Where n is an integer from 3 to 18.

[0033] In some embodiments, the general formula of the cycloalkane-based bisphosphonate ilmenite collector includes: C n+1 H 2n+4 O7P2.

[0034] Where n is an integer from 3 to 8.

[0035] In some embodiments, the general formula of the cycloalkane-based bisphosphonate ilmenite collector includes: C n+1 H 2n+4 O7P2.

[0036] Where n is an integer from 3 to 5.

[0037] In some embodiments, if the value of n is small, the carbon chain of the cycloalkane group is shorter, its hydrophobicity is relatively weaker, the hydrophobic film formed is not thick enough, and its adsorption capacity for ilmenite is limited. Although the bisphosphonic acid group can still chelate with metal ions on the surface of ilmenite, the overall collection capacity will be affected to some extent due to the insufficient hydrophobic support provided by the cycloalkane group, which may result in a lower recovery rate of ilmenite during the flotation process.

[0038] In some embodiments, if the value of n is large, the carbon chain of the cycloalkane group is longer. Although the hydrophobicity is enhanced, the corresponding molecular weight increases, and its solubility in water decreases. This will result in the collector not being dispersed evenly in the slurry, affecting production efficiency and increasing production costs.

[0039] In some embodiments, the cycloalkane-based bisphosphonate ilmenite collector contains cycloalkane groups and bisphosphonic acid groups in its molecular structure. The cycloalkane groups possess hydrophobicity, enabling the cycloalkane-based bisphosphonate ilmenite collector to form a hydrophobic film on the mineral surface, thereby enhancing its adsorption capacity for ilmenite. The bisphosphonic acid groups can chelate with metal ions (such as titanium ions, iron ions, etc.) on the ilmenite surface to form stable chemical bonds, further improving the collection efficiency of ilmenite and making it easier to separate from the aqueous phase during flotation, thus achieving efficient enrichment.

[0040] Moreover, due to its specific chemical structure, this collector exhibits good selectivity for ilmenite. In complex pulps containing multiple minerals, it preferentially adsorbs ilmenite, while its adsorption capacity for other minerals (such as gangue minerals like quartz and feldspar) is relatively weak. This facilitates the effective separation of ilmenite from other minerals during flotation, improves ilmenite recovery and concentrate grade, and reduces the contamination of impurity minerals. This is of great significance for improving the economic benefits and product quality of ilmenite beneficiation.

[0041] Furthermore, cycloalkane-based bisphosphonic acid ilmenite collectors have low toxicity. Their use during mineral processing does not cause serious environmental pollution and poses minimal health risks to operators, meeting modern environmental protection and safe production requirements.

[0042] The aforementioned cycloalkane-based bisphosphonic acid ilmenite collector contains specific cycloalkane and bisphosphonic acid groups in its molecular structure. These groups can specifically adsorb onto specific active sites on the ilmenite surface (such as hydroxyl groups on the surface of titanium oxides), preferentially adsorbing ilmenite while exhibiting relatively weaker adsorption capacity for other minerals (such as gangue minerals like quartz). This allows for the effective enrichment of ilmenite during flotation, improving the separation efficiency between ilmenite and other minerals. The bisphosphonic acid groups possess strong coordination capabilities. Each phosphonic acid group can provide two oxygen atoms as coordinating atoms, forming stable chemical bonds with metal ions (mainly titanium ions) on the ilmenite surface. These stable chemical bonds allow ilmenite particles to firmly adhere to the bubble surface, making them easier to float during flotation. A suitable n value can balance the hydrophobicity and hydrophilicity of the collector molecule, further enhancing its collecting ability for ilmenite. In addition, because the coordination ability of the bisphosphonic acid group and the hydrophobic properties of the cycloalkane group can remain relatively stable, the cycloalkane-based bisphosphonic acid ilmenite collector described in this invention can achieve good flotation results under both acidic and alkaline conditions.

[0043] In some embodiments, under slurry conditions with a pH of 4 to 8, the cycloalkane-based bisphosphonate ilmenite collector exhibits collecting activity for ilmenite.

[0044] The cycloalkane-based bisphosphonate ilmenite collector contains cycloalkane groups and bisphosphonic acid groups in its molecular structure.

[0045] The TiO2 recovery rate is 75-85%, the TiO2 grade is 34-36%, and the yield of ilmenite is 40-50%.

[0046] In some embodiments, the cycloalkane-based bisphosphonate ilmenite collector exhibits collecting activity for ilmenite under slurry conditions with a pH of 4.5 to 7.5.

[0047] In some embodiments, the cycloalkane-based bisphosphonate ilmenite collector contains a cycloalkane group and a bisphosphonic acid group in its molecular structure. The cycloalkane group is hydrophobic, which allows the collector to form a hydrophilic-hydrophobic amphoteric structure in aqueous solution. Therefore, it can maintain good stability in weakly acidic and weakly alkaline slurry environments.

[0048] In weakly acidic slurries, ilmenite exhibits a certain positive charge on its surface. The bisphosphonic acid groups in cycloalkane-based ilmenite collectors can partially dissociate, generating a negative charge. This negative charge exhibits electrostatic attraction with the positive charge on the ilmenite surface, facilitating the adsorption of collector molecules onto the ilmenite surface.

[0049] In weakly alkaline slurries, the coordination ability of bisphosphonic acid groups can still play a role. Moreover, the hydrophobic effect of cycloalkane groups can help the collector aggregate on the surface of ilmenite, thereby achieving collecting activity.

[0050] In some embodiments, TiO2 grade refers to the mass percentage of TiO2 in the ore. A higher TiO2 grade results in a more concentrated TiO2 content in the harvested ilmenite. This can reduce interference from impurities during subsequent processing, improve production efficiency, and reduce energy consumption.

[0051] This invention also provides a method for preparing the cycloalkane-based bisphosphonate ilmenite collector as described above, comprising the following steps: S1: Cycloalkanes, carboxylic acids, phosphorous acid, and phosphorus trichloride are mixed and then subjected to esterification to obtain phosphonate intermediates.

[0052] The steps of the esterification reaction include: First, mix cycloalkanes, carboxylic acids, and phosphorous acid, and heat them at 70-85°C until they melt to obtain a molten mixture.

[0053] After phosphorus trichloride is added dropwise to the molten mixture until complete, the reaction is continued at 70-80°C for 3-5 hours to obtain the phosphonate intermediate.

[0054] The time for adding phosphorus trichloride is 25-35 minutes.

[0055] In some embodiments, phosphorous acid and cycloalkane carboxylic acid are added sequentially to a three-necked flask and heated to a molten state at 75-85°C to obtain a molten mixture. Phosphorus trichloride is then slowly added dropwise to the molten mixture over 25-30 minutes until complete, and the reaction is continued at 72-78°C for 3-4 hours. If phosphorus trichloride is added to the cycloalkane carboxylic acid first, although the acyl chloride reaction occurs rapidly, it easily produces a large amount of hydrogen chloride gas, increasing side reactions, and ultimately resulting in a very small amount of phosphonate intermediate, which is almost negligible.

[0056] In some embodiments, a key step in the synthesis of bisphosphonates is the construction of the PCP backbone. This carbon atom comes from a carboxylic acid, but it must be "activated" to a sufficiently high energy state to react with phosphorous acid. Therefore, without phosphorus trichloride, the reaction hardly occurs.

[0057] In some embodiments, the molar ratio of the cycloalkane carboxylic acid, the phosphorous acid, and the phosphorus trichloride is 1:(2.5~3.5):(2.5~3.5).

[0058] In some embodiments, the molar ratio of the cycloalkane carboxylic acid, the phosphorous acid, and the phosphorus trichloride is 1:(2.8~3.2):(2.8~3.2).

[0059] S2: The phosphonate intermediate is hydrolyzed and then filtered to obtain a cycloalkane-based bisphosphonic acid filtrate.

[0060] The hydrolysis reaction is carried out at a temperature of 90~110℃.

[0061] The hydrolysis reaction lasts for 1 to 2 hours.

[0062] In some embodiments, water is slowly added to the phosphonate intermediate, the hydrolysis reaction is carried out at a temperature of 95~105°C for 1~2 hours, and after the hydrolysis reaction is completed, the mixture is filtered while hot to obtain a cycloalkane-based bisphosphonic acid filtrate.

[0063] In some embodiments, during the hydrolysis reaction step, water is added to the phosphonate intermediate to carry out the hydrolysis reaction, and the volume ratio of the phosphonate intermediate to water is 1:(0.8~1.2).

[0064] In some embodiments, the volume ratio of the phosphonate intermediate to water is 1:(0.9~1.1).

[0065] S3: At low temperature, the cycloalkane-based bisphosphonic acid filtrate is purified using a non-polar solvent to precipitate the solid. The solid is then separated to obtain the cycloalkane-based bisphosphonic acid ilmenite collector.

[0066] In some embodiments, at low temperature, a nonpolar solvent is added to the cycloalkane-based bisphosphonic acid filtrate for washing and purification, causing the solid to precipitate. The solid is then separated by filtration to obtain the cycloalkane-based bisphosphonic acid ilmenite collector. The low temperature is 0~5°C.

[0067] The solid precipitation time is 2~24 h.

[0068] In some embodiments, under low-temperature conditions (0-5°C in an ice-water bath), the cycloalkane-based bisphosphonic acid filtrate is transferred to a clean beaker, and acetone is slowly added dropwise to the filtrate while continuously stirring. With the addition of acetone, the system gradually becomes turbid, and then fine solid particles precipitate. After the addition is complete, stirring continues in the ice-water bath to ensure complete crystallization and promote crystal growth and purification. Finally, the solid is separated by filtration to obtain the cycloalkane-based bisphosphonic acid ilmenite collector.

[0069] In some embodiments, the low temperature is 0~2℃.

[0070] The solid precipitation time is 20~24 h.

[0071] In some embodiments, washing and purifying the cycloalkane-based bisphosphonic acid filtrate with a nonpolar solvent and precipitating the solid at low temperature can effectively improve the purity and yield of the product, improve product performance, reduce environmental impact, enhance operational safety, and reduce costs.

[0072] In some embodiments, the nonpolar solvent includes one or more of acetone, ethyl acetate, acetonitrile, and tetrahydrofuran.

[0073] The volume ratio of the nonpolar solvent to the cycloalkane-based bisphosphonic acid filtrate is 1:(3~8).

[0074] In some embodiments, the volume ratio of the nonpolar solvent to the cycloalkane-based bisphosphonic acid filtrate is 1:(4~6).

[0075] In some embodiments, the purity of the nonpolar solvent is analytical grade. The nonpolar solvent includes one of acetone, ethyl acetate, acetonitrile, and tetrahydrofuran.

[0076] In some embodiments, the nonpolar solvent includes acetone.

[0077] The preparation method of the aforementioned cycloalkane-based bisphosphonate ilmenite collector is simple and convenient, with good environmental friendliness and low toxicity of the raw materials and products, meeting the requirements of green mining. It is also cost-effective, with high efficiency and low dosage reducing overall costs. Therefore, the cycloalkane-based bisphosphonate ilmenite collector has broad application prospects in ilmenite flotation and is suitable for large-scale industrial production.

[0078] This invention also provides an application of the cycloalkane-based bisphosphonate ilmenite collector as described above or the cycloalkane-based bisphosphonate ilmenite collector prepared by the above preparation method, the steps of which include: Adding a cycloalkane-based bisphosphonic acid ilmenite collector to the flotation solution of ilmenite yields titanium concentrate.

[0079] The amount of the cycloalkane-based bisphosphonic acid ilmenite collector added is in a mass ratio of 3:(1500~3000) to ilmenite.

[0080] In some embodiments, the cycloalkane-based bisphosphonic acid ilmenite collector has a specific chemical structure, and its cycloalkane groups and bisphosphonic acid groups can generate a strong chemical adsorption effect with the surface of ilmenite, so that the collector forms a stable adsorption layer on the surface of the mineral particles, thereby effectively improving the floatability of ilmenite particles in the flotation process, allowing more ilmenite particles to be attached by bubbles and float to the surface of the pulp to form titanium concentrate, thereby significantly improving the flotation recovery rate of ilmenite.

[0081] To further illustrate the present invention, the following examples are provided: Example 1 A method for preparing a cycloalkane-based bisphosphonate ilmenite collector, the flowchart of which is shown below. Figure 4 As shown. The steps are: S1: In a three-necked flask, cyclobutane carboxylic acid (cycloalkane carboxylic acid) and phosphorous acid are first mixed and heated to a molten state at 80°C to obtain a molten mixture; then phosphorus trichloride is added dropwise to the molten mixture for 30 minutes until complete, and the reaction is continued at 75°C for 4 hours to obtain a phosphonate intermediate. The reaction equation is as follows. Figure 1 As shown, the molar ratio of cycloalkane carboxylic acid, phosphorous acid, and phosphorus trichloride is 1:3:3.

[0082] S2: Water was added to the phosphonate intermediate, and after hydrolysis, the mixture was filtered while hot to obtain a cycloalkane-based bisphosphonic acid filtrate. The hydrolysis reaction was carried out at 100°C for 2 hours. The volume ratio of the phosphonate intermediate to water was 1:1.

[0083] S3: At a low temperature of 0℃, the cycloalkane-based bisphosphonic acid filtrate was purified using acetone. The filtrate was transferred to a clean beaker, and acetone was slowly added dropwise while continuously stirring. With the addition of acetone, the system gradually became turbid, followed by the precipitation of fine solid particles. After the addition was complete, stirring continued to ensure complete crystallization and promote crystal growth and purification. Finally, the solid was separated by filtration to obtain the cycloalkane-based bisphosphonic acid ilmenite collector. The solid precipitation time was 24 hours. The volume ratio of acetone to cycloalkane-based bisphosphonic acid filtrate was 1:5.

[0084] The general formula of the cycloalkane-based bisphosphonic acid ilmenite collector prepared in Example 1 is: C5H 12 O7P2.

[0085] The cycloalkane-based bisphosphonic acid ilmenite collector prepared in Example 1 was added to the flotation solution of ilmenite, and flotation tests were conducted on the rough ore (raw ore) to obtain titanium concentrate. During the flotation process, the pH of the flotation solution was adjusted to 4.5. The mass ratio of the cycloalkane-based bisphosphonic acid ilmenite collector to ilmenite was 3:2000.

[0086] The flotation data of the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 1 are shown in Table 1.

[0087] Table 1. Flotation data of the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 1 As shown in Table 1, the TiO2 recovery rate in the obtained concentrate was 79.89%, the TiO2 grade was 35.73%, and the yield of ilmenite was 44.97%. This indicates good flotation performance.

[0088] Furthermore, during the flotation process, the pH of the flotation solution was adjusted to 7.0. The TiO2 recovery rate in the obtained concentrate was 78.43%, the TiO2 grade was 34.96%, and the yield of ilmenite was 43.59%. This indicates that the cycloalkane-based bisphosphonic acid ilmenite collector prepared in this invention has good flotation performance in both acidic and alkaline pulps.

[0089] Example 2 Compared to Example 1, the cycloalkane carboxylic acid was changed.

[0090] The cycloalkane carboxylic acid is cyclopentane carboxylic acid. The esterification reaction equation is as follows: Figure 2 As shown. The other steps are the same as in Example 1, and a cycloalkane-based bisphosphonate ilmenite collector is obtained.

[0091] The general formula of the cycloalkane-based bisphosphonic acid ilmenite collector prepared in Example 2 is: C6H 14 O7P2.

[0092] The flotation data of the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 2 are shown in Table 2.

[0093] Table 2. Flotation data of the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 2 As shown in Table 2, the TiO2 recovery rate in the obtained concentrate was 84.27%, the TiO2 grade was 35.55%, and the yield of ilmenite was 47.08%. This indicates good flotation performance.

[0094] Example 3 Compared to Example 1, the cycloalkane carboxylic acid was changed.

[0095] The cycloalkane carboxylic acid is cyclohexane carboxylic acid. The esterification reaction equation is as follows: Figure 3 As shown. The other steps are the same as in Example 1, and a cycloalkane-based bisphosphonate ilmenite collector is obtained.

[0096] The general formula of the cycloalkane-based bisphosphonic acid ilmenite collector prepared in Example 3 is: C7H 16 O7P2.

[0097] The flotation data of the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 3 are shown in Table 3.

[0098] Table 3. Flotation data of the cycloalkane-based bisphosphonate ilmenite collector prepared in Example 3 As shown in Table 3, the TiO2 recovery rate in the obtained concentrate was 82.73%, the TiO2 grade was 34.66%, and the yield of ilmenite was 46.76%. This indicates good flotation performance.

[0099] Based on the results of Examples 1 to 3, the cycloalkane-based bisphosphonic acid ilmenite collector prepared in this invention exhibits good collecting activity for ilmenite under slurry conditions with a pH of 4 to 8. Specifically, the TiO2 recovery rate is 75-85%, the TiO2 grade is 34-36%, and the ilmenite yield is 40-50%.

[0100] The cycloalkane-based bisphosphonic acid ilmenite collector prepared in this invention contains cycloalkane and bisphosphonic acid groups in its molecular structure. This allows for specific adsorption onto specific active sites on the ilmenite surface (such as hydroxyl groups on titanium oxide surfaces), preferentially adsorbing ilmenite while exhibiting relatively weaker adsorption on other minerals (such as gangue minerals like quartz). This enables effective enrichment of ilmenite during flotation, improving the separation efficiency between ilmenite and other minerals. The bisphosphonic acid groups possess strong coordination capabilities; each group can provide two oxygen atoms as coordinating atoms, forming stable chemical bonds with metal ions (mainly titanium ions) on the ilmenite surface. These stable bonds allow ilmenite particles to firmly adhere to the bubble surface, facilitating flotation. A suitable n value can balance the hydrophobicity and hydrophilicity of the collector molecule, further enhancing its collecting ability for ilmenite. In addition, because the coordination ability of the bisphosphonic acid group and the hydrophobic properties of the cycloalkane group can remain relatively stable, the cycloalkane-based bisphosphonic acid ilmenite collector described in this invention can achieve good flotation results under both acidic and alkaline conditions.

[0101] The preparation method of the aforementioned cycloalkane-based bisphosphonate ilmenite collector is simple and convenient, with good environmental friendliness and low toxicity of the raw materials and products, meeting the requirements of green mining. It is also cost-effective, with high efficiency and low dosage reducing overall costs. Therefore, the cycloalkane-based bisphosphonate ilmenite collector has broad application prospects in ilmenite flotation and is suitable for large-scale industrial production.

[0102] The above technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made under the technical concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included in the patent protection scope of the present invention.

Claims

1. A titanium ilmenite collector for naphthenic base bisphosphonates, characterized in that, The general formula of the naphthene-based titanomagnetite phosphonic acid collector includes: C n+1 H 2n+4 O7P2; Wherein, n is an integer of 3~18.

2. The titania ilmenite collector agent of claim 1, wherein, The cycloalkane-based titanomagnetite collector has a collecting activity on the titanomagnetite under the condition of a slurry with a pH value of 4~8. The cycloalkane-based titanomagnetite collector contains a cycloalkane group and a bisphosphonic acid group in the molecular structure. The recovery rate of TiO2 is 75~85%, the grade of TiO2 is 34~36%, and the yield of titanomagnetite is 40~50%.

3. A process for the preparation of a titanium ilmenite collector of cycloalkane-based bisphosphonate as claimed in any one of claims 1 to 2, characterized by the steps of Comprise: S1: mixing cycloalkane carboxylic acid, phosphorous acid and phosphorus trichloride, and then performing esterification reaction to obtain phosphonate intermediate; S2: performing hydrolysis reaction on the phosphonate intermediate, and then filtering to obtain cycloalkane-based bisphosphonic acid filtrate; S3: purifying the cycloalkane-based bisphosphonic acid filtrate at low temperature by using non-polar solvent, so that solid is precipitated, and the solid is separated, thereby obtaining the cycloalkane-based titanomagnetite collector.

4. The process for the preparation of a titanium ilmenite collector of cycloalkane-based bisphosphonates according to claim 3, characterized in that, The esterification reaction comprises: First, mix cycloalkane carboxylic acid and phosphorous acid, and heat to molten state at 70~85℃ to obtain molten mixed solution; Then, drop phosphorus trichloride into the molten mixed solution until the dropping is completed, and continue to react at 70~80℃ for 3~5h to obtain the phosphonate intermediate; The dropping time of phosphorus trichloride is 25~35min.

5. The process for the preparation of a titanium ilmenite collector of cycloalkane-based bisphosphonates according to claim 3, characterized in that, The molar ratio of the cycloalkane carboxylic acid, the phosphorous acid and the phosphorus trichloride is 1:(2.5~3.5):(2.5~3.5).

6. The process for the preparation of a titanium ilmenite collector of cycloalkane-based bisphosphonates according to claim 3, characterized in that, In the step of the hydrolysis reaction, water is added to the phosphonate intermediate for hydrolysis reaction, and the volume ratio of the phosphonate intermediate to water is 1:(0.8~1.2).

7. The process for the preparation of a titanium ilmenite collector of cycloparaffinic bisphosphonates according to claim 3, characterized in that, The temperature of the hydrolysis reaction is 90~110℃; The time length of the hydrolysis reaction is 1~2h.

8. The process for the preparation of a titanium ilmenite collector of cycloalkane-based bisphosphonates according to claim 3, characterized in that, The non-polar solvent comprises one or more of acetone, ethyl acetate, acetonitrile and tetrahydrofuran; The volume ratio of the non-polar solvent to the cycloalkane-based bisphosphonic acid filtrate is 1:(3~8).

9. The process for the preparation of a titanium ilmenite collector of cycloalkane-based bisphosphonates according to claim 3, characterized in that, The temperature of the low temperature is 0~5℃; The time length of the solid precipitation is 2~24h.

10. Use of a titanium ilmenite collector of cycloalkane-based bisphosphonic acids according to any one of claims 1 to 2 or a titanium ilmenite collector of cycloalkane-based bisphosphonic acids prepared according to the method of any one of claims 3 to 9, characterized in that the step Comprise: Adding cycloalkane-based titanomagnetite collector to the flotation slurry of titanomagnetite to obtain titanium concentrate; The mass ratio of the addition amount of the cycloalkane-based titanomagnetite collector to the titanomagnetite is 3:(1500~3000).

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