Collecting agent for reverse flotation of collophanite under acidic condition and preparation method of collecting agent

Abstract

The invention discloses a collecting agent for reverse flotation of collophanite under an acidic condition and a preparation method of the collecting agent, and belongs to the technical field of collophanite flotation. The collecting agent for reverse flotation of collophanite under the acidic condition is prepared from the following raw materials: 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid. The reverse flotation collecting agent containing two functional groups including carboxyl and a phosphonic acid group is prepared through reaction of 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid. The solubility of the reverse flotation collecting agent is 3-4 times that of oleic acid under acidity, the reverse flotation collecting agent has high collecting capacity for calcite and dolomite, meanwhile, the flotation capacity for apatite is poor, and efficient separation of apatite and other calcium carbonate can be achieved.

Description

Technical Field

[0001] The invention relates to a collector for reverse flotation of collophanite under acidic conditions and a preparation method thereof, belonging to the technical field of collophanite flotation. Background Art

[0002] The reverse flotation of collophanite is carried out in acidic pulp. Under acidic conditions, fatty acid collectors such as oleic acid have weak dissociation and low solubility, resulting in a large number of fatty acid molecules in the pulp. Some of these fatty acid molecules can be co-adsorbed with fatty acid ions on the dolomite surface, while the other part is mainly free in the pulp, resulting in a decrease in the flotation efficiency of the reagent. In addition, the solubility of fatty acids in acidic pulp is low, so that part of the reagent exists in the form of fatty acid droplets during the flotation process. These fatty acid droplets can only slowly dissociate into fatty acid ions as the reagent is consumed during the flotation process, which also leads to a decrease in flotation efficiency. Summary of the invention

[0003] In view of the problems existing in the prior art, the present invention provides a collector for reverse flotation of collophanite under acidic conditions, the structural formula of the collector is shown in Formula I:

[0004]

[0005] Wherein, R1 is a straight-chain alkyl group having 15 carbon atoms or a straight-chain alkyl group having 17 carbon atoms.

[0006] Preferably, the preparation method of the collector comprises the following steps:

[0007] (1) 3-Amino-5-phosphonobenzoic acid is added to carbon tetrachloride and stirred until completely dissolved, followed by adding stearic acid and palmitic acid to obtain a mixed fatty acid.

[0008] (2) Platinum plates are added to the mixed fatty acids for catalytic reaction, and carbon tetrachloride is removed by distillation after the reaction is completed to obtain a collector for reverse flotation of collophanite under acidic conditions.

[0009] Preferably, the mass percentages of 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid in step (1) are 20% to 40%, 10% to 60% and 20% to 50% respectively, wherein the total mass percentage of 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid is 100%.

[0010] Preferably, the mass ratio of the total mass of 3-amino-5-phosphonobenzoic acid, stearic acid and palmitic acid to the mass of the platinum plate is 10:(1-5).

[0011] Preferably, the temperature of the catalytic reaction in step (2) is 20 to 60° C., and the reaction time is 0.5 to 1 hour.

[0012] Preferably, the structural formula of the 3-amino-5-phosphonobenzoic acid is as shown in Formula II:

[0013]

[0014] Preferably, the collector for reverse flotation of collophanite under acidic conditions is used in an acidic slurry with a pH of 4 to 5.

[0015] The synthesis process of the collector for reverse flotation of collophanite under acidic conditions is as follows, wherein R1 is a 15-carbon straight-chain alkyl or a 17-carbon straight-chain alkyl:

[0016]

[0017] Compared with conventional agents, the bifunctional collector provided by the present invention has the characteristics of high solubility and strong hydrophilicity. Moreover, the agent contains one phosphonic acid group and one carboxyl group, both of which can bond with calcium ions and magnesium ions on the surface of dolomite and calcite to form multi-group adsorption, and has a strong ability to capture calcium carbonate.

[0018] Technical effects of the present invention:

[0019] (1) The collector prepared by the present invention contains two functional groups, namely, a carboxyl group and a phosphonic acid group. Its solubility in acidic conditions is 3 to 4 times that of oleic acid. It has a strong collecting ability for calcite and dolomite, but poor flotation ability for apatite. It can achieve efficient separation of apatite and other calcium carbonates.

[0020] (2) The collector of the present invention can be used in an acidic slurry with a pH of 4 to 5 to obtain a phosphate concentrate with a P2O5 grade of 29.2% to 29.4% and a recovery rate of 88% to 92%.

[0021] (3) The strong hydrophilicity of the reagent enables it to better contact with the mineral surface, enhancing the adsorption efficiency and thus improving the flotation effect.

[0022] (4) Compared with conventional reagents, the collector has a higher solubility in water and can be more evenly dispersed in the flotation system, thereby improving the reagent utilization rate, reducing the dosage, and reducing the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The P2O5 grades obtained with different dosages and types of collectors.

[0024] Figure 2 This is the closed-circuit flow chart of reverse flotation of “one roughing, one sweeping, and one fineness”. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with the accompanying drawings and specific examples, but the protection scope of the present invention is not limited to the above contents. Unless otherwise specified, the reagents used are conventional commercial reagents, and the 3-amino-5-phosphonobenzoic acid used is synthesized by a commissioned chemical plant.

[0026] Example 1

[0027] A preparation method for a collector for reverse flotation of collophanite under acidic conditions comprises the following steps:

[0028] (1) 4 g of 3-amino-5-phosphonobenzoic acid was added to 100 mL of carbon tetrachloride and stirred until dissolved, followed by the addition of 1 g of stearic acid and 5 g of palmitic acid to obtain a mixed fatty acid.

[0029] (2) 5 g of platinum plate was added to the mixed fatty acid, the reaction temperature was 40° C., the reaction time was 1 hour, and after the reaction was completed, carbon tetrachloride was removed by distillation at 77° C. to obtain a collector for reverse flotation of collophanite under acidic conditions.

[0030] Reverse flotation process: When the reverse flotation temperature is 15℃, the grinding fineness is -0.074mm, and the mass fraction is 85%, the following is adopted: Figure 2 The "one roughing, one scavenging, and one finishing" reverse flotation closed-circuit process is shown, wherein 15 kg / t of sulfuric acid is added to the roughing, stirred for 4 minutes, 800 g / t of a collector for reverse flotation of collophanite under acidic conditions is added, stirred for 3 minutes, 38 g / t of 2# oil is added, and stirred for 1 minute; 7.5 kg / t of sulfuric acid is added to the finishing, stirred for 4 minutes, 400 g / t of a collector for reverse flotation of collophanite under acidic conditions is added, stirred for 3 minutes, 19 g / t of 2# oil is added, and stirred for 1 minute, and finally phosphate concentrate and phosphate tailings are obtained, and the finished tailings and scavenged concentrate are returned to the roughing.

[0031] The results are shown in Table 1. The grade of P2O5 in the concentrate is 29.24%, and the recovery rate is 88.75%.

[0032] Example 2

[0033] A preparation method for a collector for reverse flotation of collophanite under acidic conditions comprises the following steps:

[0034] (1) 2 g of 3-amino-5-phosphonobenzoic acid was added to 100 mL of carbon tetrachloride and stirred until dissolved, and then 6 g of stearic acid and 2 g of palmitic acid were added to obtain a mixed fatty acid;

[0035] (2) Add 5 g of platinum plate to the mixed fatty acid, the reaction temperature is 20° C., the reaction time is 1 hour, and after the reaction is completed, the carbon tetrachloride is distilled off at 77° C. to obtain a collector for reverse flotation of collophanite under acidic conditions.

[0036] Reverse flotation process: When the reverse flotation temperature is 15℃, the grinding fineness is -0.074mm, and the mass fraction is 85%, the following is adopted: Figure 2 The "one roughing, one scavenging, and one finishing" reverse flotation closed-circuit process is shown, wherein 15 kg / t of sulfuric acid is added to the roughing, stirred for 4 minutes, 800 g / t of a collector for reverse flotation of collophanite under acidic conditions is added, stirred for 3 minutes, 38 g / t of 2# oil is added, and stirred for 1 minute; 7.5 kg / t of sulfuric acid is added to the finishing, stirred for 4 minutes, 400 g / t of a collector for reverse flotation of collophanite under acidic conditions is added, stirred for 3 minutes, 19 g / t of 2# oil is added, and stirred for 1 minute, and finally phosphate concentrate and phosphate tailings are obtained, and the finished tailings and scavenged concentrate are returned to the roughing.

[0037] The results are shown in Table 1. The grade of P2O5 in the concentrate is 29.34%, and the recovery rate is 90.92%.

[0038] Example 3

[0039] A preparation method for a collector for reverse flotation of collophanite under acidic conditions comprises the following steps:

[0040] (1) 3 g of 3-amino-5-phosphonobenzoic acid was added to 100 mL of carbon tetrachloride and stirred until dissolved, and then 3.5 g of stearic acid and 3.5 g of palmitic acid were added to obtain a mixed fatty acid;

[0041] (2) 3 g of platinum plate was added to the mixed fatty acid, the reaction temperature was 60° C., the reaction time was 0.5 hour, and after the reaction was completed, carbon tetrachloride was removed by distillation at 77° C. to obtain a collector for reverse flotation of collophanite under acidic conditions.

[0042] Reverse flotation process: When the reverse flotation temperature is 15℃, the grinding fineness is -0.074mm, and the mass fraction is 85%, the following is adopted: Figure 2 The "one roughing, one scavenging, and one finishing" reverse flotation closed-circuit process is shown, wherein 15 kg / t of sulfuric acid is added to the roughing, stirred for 4 minutes, 800 g / t of a collector for reverse flotation of collophanite under acidic conditions is added, stirred for 3 minutes, 38 g / t of 2# oil is added, and stirred for 1 minute; 7.5 kg / t of sulfuric acid is added to the finishing, stirred for 4 minutes, 400 g / t of a collector for reverse flotation of collophanite under acidic conditions is added, stirred for 3 minutes, 19 g / t of 2# oil is added, and stirred for 1 minute, and finally phosphate concentrate and phosphate tailings are obtained, and the finished tailings and scavenged concentrate are returned to the roughing.

[0043] The results are shown in Table 1. The grade of P2O5 in the concentrate is 29.38% and the recovery rate is 91.24%.

[0044] Comparative Example 1

[0045] The collector used in this embodiment is HEDP (hydroxyethylidene diphosphonic acid), and the flotation method is the same as that in Example 1, comprising the following steps:

[0046] A pure HEDP solution with a mass concentration of 60% was selected.

[0047] Reverse flotation process: When the reverse flotation temperature is 15℃, the grinding fineness is -0.074mm, and the mass fraction is 85%, the following is adopted: Figure 2 The reverse flotation closed-circuit process of "one roughing, one scavenging, and one finishing" is shown, wherein 15 kg / t of sulfuric acid is added to the roughing, stirred for 4 minutes, 800 g / t of HEDP collector is added, stirred for 3 minutes, 38 g / t of 2# oil is added, and stirred for 1 minute; 7.5 kg / t of sulfuric acid is added to the finishing, stirred for 4 minutes, 400 g / t of HEDP collector is added, stirred for 3 minutes, 19 g / t of 2# oil is added, and stirred for 1 minute, and finally phosphate concentrate and phosphate tailings are obtained, and the finished tailings and scavenged concentrate are returned to the roughing.

[0048] The results are shown in Table 1. The grade of P2O5 in the concentrate is 28.59% and the recovery rate is 78.16%.

[0049] Table 1 Results of closed-circuit processes with different collectors

[0050] Collector samples <![CDATA[Grade of P2O5 in Concentrate / %]]> <![CDATA[P2O5 recovery rate / %]]> Example 1 29.24 88.75 Example 2 29.34 90.92 Example 3 29.38 91.24 Comparative Example 1 28.59 78.16

[0051] The collector prepared in Example 3 and the collector in Comparative Example 1, the grades of P2O5 obtained by different dosages of the collector are as follows: Figure 1 As shown in the figure, it can be seen that the collector prepared in Example 3 has a higher P2O5 grade.

[0052] (1) The bifunctional collector is superior to ordinary phosphonic acid (HEDP) in terms of concentrate P2O5 grade and recovery rate, reflecting its high efficiency and superiority.

[0053] (2) The multi-group adsorption mechanism, high solubility and strong hydrophilicity of bifunctional collectors are the key reasons for their superior performance.

[0054] (3) In practical applications, bifunctional collectors can significantly improve the flotation efficiency of phosphate ore, reduce the amount of reagents used, and have higher economic benefits and environmental friendliness.

Claims

1. A collector for reverse flotation of collophanite under acidic conditions, characterized in that: The structural formula of the collector is shown in Formula I: Wherein, R1 is a straight-chain alkyl group having 15 carbon atoms or a straight-chain alkyl group having 17 carbon atoms.

2. The collector for reverse flotation of collophanite under acidic conditions according to claim 1, characterized in that: The collector for reverse flotation of collophanite under the acidic condition is used in an acidic ore pulp with a pH value of 4 to 5.

3. The method for preparing a collector for reverse flotation of collophanite under acidic conditions according to claim 1 or 2, characterized in that: The specific steps include: (1) adding 3-amino-5-phosphonobenzoic acid to carbon tetrachloride and stirring until dissolved, and then adding stearic acid and palmitic acid to obtain a mixed fatty acid; (2) Platinum plates are added to the mixed fatty acids for catalytic reaction, and carbon tetrachloride is removed by distillation after the reaction is completed to obtain a collector for reverse flotation of collophanite under acidic conditions.

4. The method for preparing a collector for reverse flotation of collophanite under acidic conditions as claimed in claim 3, characterized in that: In step (1), the mass percentages of 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid are 20% to 40%, 10% to 60% and 20% to 50% respectively, wherein the total mass percentage of 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid is 100%.

5. The method for preparing a collector for reverse flotation of collophanite under acidic conditions as claimed in claim 4, characterized in that: The structural formula of the 3-amino-5-phosphonobenzoic acid is shown in Formula II:

6. The method for preparing a collector for reverse flotation of collophanite under acidic conditions according to claim 3, characterized in that: The mass ratio of the total mass of 3-amino-5-phosphonobenzoic acid, stearic acid and palmitic acid to the mass of the platinum plate is 10:(1-5).

7. The method for preparing a collector for reverse flotation of collophanite under acidic conditions according to claim 3, characterized in that: The temperature of the catalytic reaction in step (2) is 20 to 60° C., and the reaction time is 0.5 to 1 hour.

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