A mineral processing reagent, its preparation method and its application

Abstract

This invention belongs to the field of mineral flotation technology, specifically disclosing a mineral processing reagent, and also relating to its preparation method and application. The mineral processing reagent provided by this invention includes the structure shown in formula (I). This mineral processing reagent, used as a collector in mineral flotation operations, has the characteristics of low foaming and strong collecting power, which can improve the flotation separation effect of minerals.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation technology, specifically to a mineral processing reagent, as well as its preparation method and application. Background Technology

[0002] Amine collectors are cationic collectors commonly used in mineral flotation. They generally contain R-NH2 groups, which can hydrolyze in water to form -NH3. + These positively charged groups adsorb onto the mineral surface, and the hydrocarbon group is highly hydrophobic, making the mineral surface hydrophobic and thus improving its floatability. Currently, the R group in amine collectors used in mineral engineering is generally C. 12 -C 14 Aliphatic hydrocarbon groups.

[0003] Existing amine collectors have few polar groups, resulting in weak collecting power, but strong foaming properties and stable flotation foam, which easily leads to the entrainment of fine minerals, affecting concentrate grade and hindering mineral flotation separation. Furthermore, current aliphatic amine collectors are generally primary amines obtained from natural fatty acids through nitrification and hydrogenation reactions. The preparation methods suffer from long process routes and high reaction temperatures; in particular, the hydrogenation reaction utilizes materials such as hydrogen and Raney nickel, placing high demands on reaction equipment and safety management.

[0004] Therefore, improving existing amine collectors to address their shortcomings and developing new amine collectors to enhance their flotation performance for better application in mineral flotation remains a key focus in the field of flotation reagent research. Summary of the Invention

[0005] The main technical problem solved by this invention is to provide a mineral processing reagent, particularly an amine collector, which is used as a collector in mineral flotation operations and has the characteristics of low foaming and strong collecting power, thereby improving the flotation separation effect of minerals.

[0006] The present invention also provides a method for preparing mineral processing reagents, which can obtain amine collectors suitable for mineral flotation through a "one-pot method". The synthesis process is short, the reaction conditions are mild, and the post-processing is easy and the operation is simple.

[0007] The technical solution adopted in this invention is as follows: This invention provides a mineral processing reagent, the mineral processing reagent comprising the structure shown in formula (I):

[0008]

[0009] In formula (I),

[0010] R represents C5-C 10 Alkyl or cycloalkyl groups;

[0011] R1 is selected from H and C1-C5 alkyl groups;

[0012] R2 is selected from H, C2-C6 primary or secondary amino groups;

[0013] x represents 1 or 2.

[0014] As a preferred technical solution of the present invention, in formula (I), R represents C8-C 10 Alkyl groups; and / or,

[0015] The R1 is selected from H, methyl, ethyl, and propyl; and / or,

[0016] The R2 is selected from H, a -CH2-CH2NH2 group, or the H on the amino group of the -CH2-CH2NH2 group is further replaced by a -CH2-CH2NH2 group; and / or,

[0017] The x represents 1.

[0018] As a preferred technical solution of the present invention, in formula (I), R represents nonyl; and / or,

[0019] R1 is H; and / or,

[0020] The R2 is selected from H, -CH2-CH2NH2 group, or one H on the amino group of the -CH2-CH2NH2 group is further replaced by the -CH2-CH2NH2 group.

[0021] As a further preferred technical solution of the present invention, in formula (I), the R substitution position is at position 5, the -OH substitution position is at position 2, and the structural formula is:

[0022]

[0023] R, R1, and R2 are defined as described above.

[0024] Preferably, the mineral processing reagent provided by the present invention is selected from compounds with the following structures:

[0025]

[0026] The present invention also provides a method for preparing the aforementioned mineral processing reagent, wherein the reaction formula of the preparation method is as follows:

[0027]

[0028] in,

[0029] R1 is H; R2 is selected from H, -CH2-CH2NH2 group, or an H on the amino group of the -CH2-CH2NH2 group is further replaced by a -CH2-CH2NH2 group;

[0030] The amine is any one of ammonia, ethylenediamine, and diethylenetriamine; the solvent is methanol and / or ethanol.

[0031] The preparation method includes the following steps: mixing and stirring the nonylphenol (i.e., nonylphenol), formaldehyde, amine and the solvent, heating and reacting to obtain the mineral processing reagent shown in formula (I').

[0032] As a preferred embodiment of the present invention, the molar ratio of formaldehyde to nonylphenol is (1-1.2):1; and / or,

[0033] The molar ratio of the amine to the nonylphenol is (1-2):1; and / or,

[0034] The molar ratio of the solvent to the nonylphenol is (4-10):1, preferably (4-6):1.

[0035] As a preferred embodiment of the present invention, the heating temperature of the reaction is 70–100°C.

[0036] As a preferred technical solution of the present invention, the preparation method further includes a post-processing step, which includes: after the heating reaction is completed, adjusting the pH of the reaction system to neutral, then removing the reaction solvent, washing the residue with water and extracting it with an organic solvent to obtain an organic phase, and concentrating the organic phase to obtain the mineral processing reagent shown in formula (I').

[0037] This invention also provides the application of the mineral processing reagents described herein in mineral flotation.

[0038] Preferably, the mineral processing reagent of the present invention is used as a collector in mineral flotation.

[0039] When the mineral processing reagents described in this invention are used for mineral flotation, one mineral processing reagent can be used alone, or two or more mineral processing reagents can be used in combination.

[0040] More preferably, the mineral is a mica group mineral, and more preferably, it is lithium-bearing mica ore.

[0041] This invention provides a mineral processing reagent, a novel aromatic ring amine compound. This type of compound has hydrophobic groups consisting of benzene rings and straight-chain alkane structures, and polar groups consisting of multiple positively charged primary and / or secondary amine groups. Through modification of the hydrophobic chain structure and combination with multiple amine groups, the collector's own foaming properties are reduced, effectively solving the entrainment phenomenon in the flotation concentrate and reducing the loss of valuable metals in subsequent processes such as concentrate dewatering and transportation. Furthermore, the adsorption force between the collector and minerals is enhanced. Due to the unsaturated structure and the presence of multiple nitrogen sources, the polar groups of the collector have a stronger adsorption force on the target minerals, thus improving the recovery rate of valuable metals. Experiments have shown that the mineral processing reagent provided by this invention exhibits particularly strong collecting and flotation capabilities for mica group minerals, enabling efficient mineral recovery.

[0042] The method for preparing mineral processing reagents provided by this invention synthesizes aromatic cyclic amine compounds in a one-pot process. The synthesis process is short, simple to operate, and the reaction conditions are mild and safe. Attached Figure Description

[0043] Figure 1 This is the infrared spectrum of compound I-1 synthesized in Example 1 of this invention;

[0044] Figure 2 This is the mass spectrum of compound I-1 synthesized in Example 1 of this invention;

[0045] Figure 3 This is the infrared spectrum of compound I-2 synthesized in Example 2 of this invention;

[0046] Figure 4 This is the mass spectrum of compound I-2 synthesized in Example 2 of this invention;

[0047] Figure 5 This is the infrared spectrum of compound I-3 synthesized in Example 3 of this invention;

[0048] Figure 6 This is the mass spectrum of compound I-3 synthesized in Example 3 of this invention;

[0049] Figure 7 This is a flow chart of the flotation process used in the experimental examples of the effects of this invention. Detailed Implementation

[0050] The technical solution of the present invention will be described in detail below through specific embodiments.

[0051] Unless otherwise specified, all pharmaceutical agents used in the following examples or comparative examples are commercially available products.

[0052] Example 1

[0053] This embodiment provides a mineral processing reagent with the following structural formula:

[0054]

[0055] The preparation reaction formula for this mineral processing reagent is as follows:

[0056]

[0057] The specific preparation method is as follows: 50 mmol of nonylphenol, 100 mmol of ammonia, and 250 mmol of methanol solvent were added to a reactor and mixed thoroughly. 50 mmol of formaldehyde was added dropwise with stirring at 50°C. After the addition was complete, the reaction temperature was controlled at approximately 70°C, and the reaction was carried out for 6 hours. The pH of the reaction solution was then adjusted to 7, and the reaction solvent was removed. The residue was washed three times with water, and then extracted twice with ethyl acetate. The extracted organic phases were combined and rotary evaporated to obtain 9.8 g of the target product, 2-methylamino-4-nonylphenol (compound I-1), with a molar yield of 79%.

[0058] The infrared spectrum of 2-methylamino-4-nonylphenol is shown in [reference needed]. Figure 1 As shown, the mass spectrum is... Figure 2 As shown.

[0059] Example 2

[0060] This embodiment provides a mineral processing reagent with the following structural formula:

[0061]

[0062] The preparation reaction formula for this mineral processing reagent is as follows:

[0063]

[0064] The specific preparation method is as follows: 50 mmol of nonylphenol, 65 mmol of ethylenediamine, and 250 mmol of ethanol solvent were added to a reactor and mixed thoroughly. 50 mmol of formaldehyde was added dropwise while stirring at 50°C. The reaction temperature was then controlled at 80°C, and the reaction was carried out for 6 hours. The pH of the reaction solution was then adjusted to 7, and the reaction solvent was removed. The residue was washed three times with water, and then extracted twice with ethyl acetate. The extracted organic phases were combined and rotary evaporated to obtain 12.1 g of the target product 2-(((2-aminoethyl)amino)methyl)-4-nonylphenol (compound I-2), with a molar yield of 83%.

[0065] The infrared spectrum of 2-(((2-aminoethyl)amino)methyl)-4-nonylphenol is shown in [reference needed]. Figure 3 As shown, the mass spectrum is... Figure 4 As shown.

[0066] Example 3

[0067] This embodiment provides a mineral processing reagent with the following structural formula:

[0068]

[0069] The preparation reaction formula for this mineral processing reagent is as follows:

[0070]

[0071] The specific preparation method is as follows: 50 mmol of nonylphenol, 70 mmol of diethylenetriamine, and 250 mmol of methanol solvent were added to a reactor and mixed thoroughly. 60 mmol of formaldehyde was added dropwise with stirring at 50 °C. The reaction temperature was then controlled at 90 °C, and the reaction was carried out for 6 hours. The reaction was then terminated. The pH of the reaction solution was adjusted to 7, and the reaction solvent was removed. The residue was washed three times with water, and then extracted twice with ethyl acetate. The extracted organic phases were combined and rotary evaporated to obtain 13.4 g of the target product 2-(2-((((2-aminoethyl)amino)ethyl)amino)methyl)-4-nonylphenol (compound I-3), with a molar yield of 80%.

[0072] The infrared spectrum of 2-(2-((((2-aminoethyl)amino)ethyl)amino)methyl)-4-nonylphenol is shown in [reference needed]. Figure 5 As shown, the mass spectrum is... Figure 6 As shown.

[0073] Application Experiment Example

[0074] Mineral flotation experiments were conducted using the flotation reagents provided above, as detailed in Application Examples 1-3. The minerals treated in the following application examples were all lithium oxide ore from a certain region in Hunan Province. The main lithium mineral was lepidolite, followed by feldspar and quartz, with small amounts of chlorite, pyrolusite, and phosphogypsum.

[0075] Application Experiment Example 1

[0076] This application example uses compound I-1 (2-methylamino-4-nonylphenol) provided in Example 1 to perform flotation separation on the above-mentioned lithium oxide ore. The flotation process flow diagram is shown below. Figure 7 The specific processing procedure is as follows.

[0077] The raw ore is first ground and deslimed to obtain a material with a particle size of 0.025-0.15 mm and a mass fraction of 79.8%. The slurry is then prepared with a mass percentage concentration of 20%.

[0078] Sulfuric acid was then added to adjust the pH to 3, followed by the addition of collector compound I-1 and auxiliary methanol (the mass ratio of compound I-1 to auxiliary methanol was 6:1). The amount of collector compound I-1 added was 250g per ton of raw ore. One roughing, two scavenging, and two cleaning operations were performed. In the first and second scavenging operations, the amount of collector compound I-1 added was 50g per ton of raw ore. When adding collector compound I-1 in the first and second scavenging operations, auxiliary methanol was added according to the mass ratio (the mass ratio of compound I-1 to auxiliary methanol was 6:1). Finally, concentrate and tailings products were obtained.

[0079] Sulfuric acid is added during the primary selection, primary scavenging, and secondary scavenging processes to maintain the pH value of the slurry at 2-4.

[0080] Simply replace the collector in the above flotation process with compound I-1 (2-methylamino-4-nonylphenol) and replace it with dodecylamine collector, while keeping all other conditions unchanged, and you will still get concentrate and tailings products.

[0081] The flotation data for this experiment are shown in Table 1.

[0082] Table 1

[0083]

[0084] As can be seen from Table 1, compared with dodecylamine collector, the lithium concentrate obtained by flotation using the collector 2-methylamino-4-nonylphenol provided by this invention has a higher Li2O grade and a higher recovery rate.

[0085] Application Experiment Example 2

[0086] This application experiment uses compound I-2(2-(((2-aminoethyl)amino)methyl)-4-nonylphenol) provided in Example 2 to perform flotation separation on the above-mentioned lithium oxide ore. The flotation process flow diagram is shown below. Figure 7 The specific processing procedure is as follows.

[0087] The raw ore is first ground and deslimed to obtain a material with a particle size of 0.025-0.15 mm and a mass fraction of 70.9%, and the slurry concentration is adjusted to 30%.

[0088] Hydrochloric acid was then added to adjust the pH to 3. Collector compound I-2 and auxiliary methanol (mass ratio of compound I-2 to auxiliary methanol was 6:1) were then added. The amount of collector compound I-2 added was 250g per ton of raw ore. One roughing, two scavenging and two cleaning operations were carried out. In the first and second scavenging operations, the amount of collector compound I-2 added was 50g per ton of raw ore. When adding collector compound I-2 in the first and second scavenging operations, auxiliary methanol was added according to the mass ratio (mass ratio of compound I-2 to auxiliary methanol was 6:1). Finally, concentrate and tailings products were obtained.

[0089] Hydrochloric acid is added during the primary selection, primary scavenging, and secondary scavenging processes to maintain the pH value of the slurry at 2-4.

[0090] By simply replacing the collector in the above flotation process with compound I-2 and replacing it with dodecylamine collector, while keeping all other conditions unchanged, the same concentrate and tailings products can be obtained.

[0091] The flotation data for this experiment are shown in Table 2.

[0092] Table 2

[0093]

[0094] As shown in Table 2, compared with dodecylamine, the lithium concentrate obtained by flotation with collector I-2 has a higher Li2O grade and a significantly higher recovery rate.

[0095] Application Experiment Example 3

[0096] This application experiment uses compound I-3(2-(2-(2-((((2-aminoethyl)amino)ethyl)amino)methyl)-4-nonylphenol) provided in Example 3 to perform flotation separation on the above-mentioned lithium oxide ore. The flotation process flow diagram is shown below. Figure 7 The specific processing procedure is as follows.

[0097] The raw ore is first ground and deslimed to obtain a material with a particle size of 0.025-0.15 mm and a mass fraction of 74.2%, and the slurry concentration is adjusted to 35%.

[0098] Acetic acid was then added to adjust the pH to 3. Collector compound I-3 and auxiliary methanol (mass ratio of compound I-3 to auxiliary methanol was 6:1) were then added. The amount of collector compound I-3 added was 250g per ton of raw ore. One roughing, two scavenging and two cleaning operations were carried out. In the first and second scavenging operations, the amount of collector compound I-3 added was 50g per ton of raw ore. When adding collector compound I-3 in the first and second scavenging operations, auxiliary methanol was added according to the mass ratio (mass ratio of compound I-3 to auxiliary methanol was 6:1). Finally, concentrate and tailings products were obtained.

[0099] Acetic acid is added during the primary selection, primary scavenging, and secondary scavenging processes to maintain the pH value of the slurry at 2-4.

[0100] By simply replacing the collector in the above flotation process with compound I-3 and replacing it with dodecylamine collector, while keeping all other conditions unchanged, the same concentrate and tailings products can be obtained.

[0101] The flotation data for this experiment are shown in Table 3.

[0102] Table 3

[0103]

[0104] As shown in Table 3, compared with dodecylamine, the lithium concentrate obtained by flotation with collector I-3 has a higher Li2O grade and a significantly higher recovery rate.

[0105] In addition, the foaming properties of the aromatic amine compounds I-1 to I-3 provided in Examples 1 to 3 were tested.

[0106] The foaming performance test method is the tilting method. Taking the foaming performance test of compound I-1 as an example: acetic acid was used as a regulator to prepare a 0.01 mol / L amine aqueous solution of compound I-1; 500 mL of the sample to be tested was poured into a separatory funnel, and the solution was allowed to flow continuously from a height of 450 mm. After the liquid stopped flowing for 10 seconds, the volume of foam and the time it took for half of the foam volume to disappear were recorded.

[0107] The foaming performance test results of the dodecylamine collector and compounds I-1 to I-3 provided by the present invention are shown in Table 4.

[0108] Table 4

[0109] Foaming performance test results dodecylamine Compound I-1 Compound I-2 Compound I-3 Foam volume (mL) 100 30 68 75 Foam half-life (s) 65 14 22 34

[0110] As shown in Table 4, dodecylamine produces the largest foam volume and the longest half-life. The aromatic amine compounds provided in Examples 1-3 produce significantly smaller foam volumes and shorter half-lives than dodecylamine, suggesting that their foaming ability is weaker than that of traditional amine collectors. This will help reduce flotation entrainment and improve separation flotation efficiency in the cleaning process.

[0111] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. The application of a mineral processing reagent in mineral flotation, characterized in that, The mineral processing reagent is used as a collector in mineral flotation, and the mineral processing reagent comprises the structure shown in formula (I): （I） In formula (I), R represents C5-C 10 Alkyl or cycloalkyl groups; R1 is selected from H and C1-C5 alkyl groups; R2 is selected from H, C2-C6 primary or secondary amino groups; x represents 1 or 2.

2. The application according to claim 1, characterized in that, The R represents C8-C. 10 Alkyl groups; R1 is selected from H, methyl, ethyl, and propyl; The R2 is selected from H, -CH2-CH2NH2 group, or the H on the amino group of the -CH2-CH2NH2 group is further replaced by the -CH2-CH2NH2 group; The x represents 1.

3. The application according to claim 2, characterized in that, R represents nonyl; R1 is H; The R2 is selected from H, -CH2-CH2NH2 group, or one H on the amino group of the -CH2-CH2NH2 group is further replaced by the -CH2-CH2NH2 group.

4. The application according to claim 2 or 3, characterized in that, The R substitution position is at position 5, and the -OH substitution position is at position 2.

5. The application according to claim 1, characterized in that, The mineral processing reagent is selected from compounds with the following structures: I-1； I-2； I-3。 6. A method for preparing a mineral processing reagent, characterized in that, The reaction formula for the preparation method is: ； （I’） in, R1 is H; R2 is selected from H, -CH2-CH2NH2 group, or an H on the amino group of the -CH2-CH2NH2 group is further replaced by a -CH2-CH2NH2 group; The amine is any one of ammonia, ethylenediamine, and diethylenetriamine; the solvent is methanol and / or ethanol. The preparation method includes the following steps: mixing and stirring nonylphenol, formaldehyde, amine and the solvent, heating and reacting to obtain the mineral processing reagent shown in formula (I').

7. The preparation method according to claim 6, characterized in that, The molar ratio of formaldehyde to nonylphenol is (1~1.2):1; The molar ratio of the amine to the nonylphenol is (1~2):1; The molar ratio of the solvent to the nonylphenol is (4~10):

1.

8. The preparation method according to claim 6 or 7, characterized in that, The heating temperature for the reaction is 70~100℃; The preparation method further includes a post-processing step: after the heating reaction is completed, the pH of the reaction system is adjusted to neutral, then the reaction solvent is removed, and the residue is washed with water and extracted with an organic solvent to obtain an organic phase. The organic phase is then concentrated to obtain the mineral processing reagent shown in formula (I').

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