A collector for reverse flotation of collophanite under acidic conditions and a preparation method thereof

Abstract

The application discloses a collector for reverse flotation of collophanite under acidic conditions and a preparation method thereof, and belongs to the technical field of collophanite flotation. The collector for reverse flotation of collophanite under acidic conditions is prepared from the following raw materials: 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid. The reverse flotation collector containing two functional groups of carboxyl and phosphonic acid groups is prepared through the reaction of 3-amino-5-phosphonobenzoic acid, palmitic acid and stearic acid. The reverse flotation collector has a solubility 3-4 times that of oleic acid under acidity, has a strong collecting capacity for calcite and dolomite, and has a poor flotation capacity for apatite, so that efficient separation of apatite and other calcareous carbonates can be realized.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of acidic conditions under reverse flotation collophanite collector and its preparation method, belong to collophanite flotation technical field. BACKGROUND

[0002] Collophanite reverse flotation is carried out in acidic slurry, under acidic conditions, weak dissociation of fatty acid collector such as oleic acid, low solubility, resulting in a large number of fatty acid molecules in the slurry, part of these fatty acid molecules can be co-adsorbed with fatty acid ions on the surface of dolomite, while the other part is mainly free in the slurry, resulting in the decline of the flotation efficiency of the reagent.In addition, the solubility of fatty acid in acidic slurry 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 fatty acid ions with the consumption of reagent during the flotation process, also leading to the decline of the flotation efficiency. SUMMARY

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

[0004]

[0005] Wherein, R1 is 15 carbon straight chain alkyl or 17 carbon straight chain alkyl.

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

[0007] (1) 3-amino-5 phosphine benzene acid is added to carbon tetrachloride and stirred until completely dissolved, then stearic acid and palmitic acid are added to obtain mixed fatty acid.

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

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

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

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

[0012] Preferably, the 3-amino-5 phosphonobenzoic acid has a structural formula as shown in formula II:

[0013]

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

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

[0016]

[0017] Compared with conventional reagents, the bifunctional collector provided by the present application has the characteristics of high solubility and strong hydrophilicity. Moreover, the reagent contains one phosphonic acid group and one carboxyl group, both of which can be bonded to calcium ions and magnesium ions on the surface of dolomite and calcite, thereby forming multi-group adsorption and having strong collecting ability for calcareous carbonates.

[0018] Technical effects of the present application:

[0019] (1) The collector prepared by the present application contains two functional groups of carboxyl and phosphonic acid group, has a solubility 3-4 times that of oleic acid under acidic conditions, and has strong collecting ability for calcite and dolomite, while having poor flotation ability for apatite, so that efficient separation of apatite and other calcareous carbonates can be achieved.

[0020] (2) The collector described in the present application can be used in an acidic ore slurry with pH = 4-5, and a phosphate concentrate with P2O5 grade of 29.2%-29.4% and recovery rate of 88%-92% is obtained.

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

[0022] (4) Compared with conventional reagents, the collector has higher solubility in water, can be more uniformly dispersed in the flotation system, improves the utilization rate of the reagent, reduces the dosage, and reduces the production cost. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 P2O5 grade obtained by different dosages and different types of collectors.

[0024] Figure 2 Reverse flotation closed-circuit flowchart of “one roughing, one scavenging, and one cleaning”. DETAILED DESCRIPTION

[0025] The application will be further described in detail below with reference to the accompanying drawings and specific examples, but the scope of protection of the application is not limited to the content described. Unless otherwise specified, the reagents used are conventional commercially available reagents, and the 3-amino-5-phosphonobenzoic acid is synthesized by a chemical factory.

[0026] Example 1

[0027] A preparation of a reverse flotation phosphate ore collector under acidic conditions includes the following steps:

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

[0029] (2) 5 g of platinum plates is added to the mixed fatty acid, the reaction temperature is 40℃, the reaction time is 1 hour, and after the reaction is completed, carbon tetrachloride is distilled off at 77℃ to obtain the reverse flotation phosphate ore collector under acidic conditions.

[0030] Reverse flotation process: at a reverse flotation temperature of 15℃, a grinding fineness of -0.074 mm, a mass fraction of 85%, and using the reverse flotation closed circuit process of "one roughing, one scavenging and one cleaning" as shown in Figure 2 , wherein 15 kg / t of sulfuric acid is added in roughing, stirring for 4 min, adding 800 g / t of the reverse flotation phosphate ore collector under acidic conditions, stirring for 3 min, adding 38 g / t of 2# oil, and stirring for 1 min; 7.5 kg / t of sulfuric acid is added in cleaning, stirring for 4 min, adding 400 g / t of the reverse flotation phosphate ore collector under acidic conditions, stirring for 3 min, adding 19 g / t of 2# oil, and stirring for 1 min, to finally obtain phosphate concentrate and phosphate tailings, and the tailings of cleaning and the concentrate of scavenging are returned to 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 of a reverse flotation phosphate ore collector under acidic conditions includes the following steps:

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

[0035] (2) 5 g of platinum plates is added to the mixed fatty acid, the reaction temperature is 20℃, the reaction time is 1 hour, and after the reaction is completed, carbon tetrachloride is distilled off at 77℃ to obtain the reverse flotation phosphate ore collector under acidic conditions.

[0036] Reverse flotation process: in the reverse flotation temperature is 15℃, grinding fineness is -0.074mm, mass fraction accounts for 85%, adopts the "one rough one scan one precision" reverse flotation closed loop process as shown in the figure Figure 2 , wherein the rough selection adds 15kg / t of sulfuric acid, stirs for 4min, adds 800g / t of the reverse flotation collophanite collector under acid condition, stirs for 3min, adds 38g / t of 2# oil, stirs for 1min; the selection adds 7.5kg / t of sulfuric acid, stirs for 4min, adds 400g / t of the reverse flotation collophanite collector under acid condition, stirs for 3min, adds 19g / t of 2# oil, stirs for 1min, finally obtains the phosphorus concentrate and the phosphorus tailings, and the tailings of the selection and the concentrate of the scan return to the rough selection.

[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 kind of preparation of reverse flotation collophanite collector under acid condition, comprising the following steps:

[0040] (1) 3g of 3-amino-5 phosphonic acid is added to 100mL of carbon tetrachloride and stirred to dissolve, then 3.5g of stearic acid and 3.5g of soft fat acid are added to obtain a mixed fatty acid;

[0041] (2) 3g of platinum plate is added to the mixed fatty acid, the reaction temperature is 60℃, the reaction time is 0.5 hours, after the reaction is completed, the carbon tetrachloride is distilled off at 77℃, to obtain the reverse flotation collophanite collector under acid condition.

[0042] Reverse flotation process: in the reverse flotation temperature is 15℃, grinding fineness is -0.074mm, mass fraction accounts for 85%, adopts the "one rough one scan one precision" reverse flotation closed loop process as shown in the figure Figure 2 , wherein the rough selection adds 15kg / t of sulfuric acid, stirs for 4min, adds 800g / t of the reverse flotation collophanite collector under acid condition, stirs for 3min, adds 38g / t of 2# oil, stirs for 1min; the selection adds 7.5kg / t of sulfuric acid, stirs for 4min, adds 400g / t of the reverse flotation collophanite collector under acid condition, stirs for 3min, adds 19g / t of 2# oil, stirs for 1min, finally obtains the phosphorus concentrate and the phosphorus tailings, and the tailings of the selection and the concentrate of the scan return to the rough selection.

[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 example is HEDP (hydroxyethylidene diphosphonic acid), and the flotation method is the same as that of Example 1, including the following steps:

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

[0047] Reverse flotation process: at a reverse flotation temperature of 15℃, a grinding fineness of -0.074mm, a mass fraction of 85%, and a reverse flotation closed circuit process of "one roughing, one scavenging and one cleaning" as shown in the table is used, wherein 15kg / t of sulfuric acid is added, stirred for 4min, 800g / t of HEDP collector is added, stirred for 3min, 38g / t of 2# oil is added, and stirred for 1min; 7.5kg / t of sulfuric acid is added in cleaning, stirred for 4min, 400g / t of HEDP collector is added, stirred for 3min, 19g / t of 2# oil is added, and stirred for 1min, finally obtaining phosphate concentrate and phosphate tailings, and the tailings of cleaning and the concentrate of scavenging are returned to roughing. Figure 2

[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 different collector closed circuit processes

[0050] Collector sample Concentrate P2O5 grade / % P2O5 recovery / % 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 P2O5 grade obtained by different doses of the collector prepared in Example 3 and the collector of Comparative Example 1 is shown in the table. Figure 1 From the figure, it can be seen that the collector prepared in Example 3 obtains a higher P2O5 grade.

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

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

[0054] (3) In practical application, the bifunctional collector can significantly improve the flotation efficiency of phosphate ore, reduce the dosage of reagents, and has higher economic benefits and environmental friendliness.​

Claims

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

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

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

4. The method for preparing a collector for reverse flotation of collophosphite under acidic conditions according to 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 collophane ore under acidic conditions according to 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 collophanate 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 collophanate 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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