Novel inhibitor for apatite in calcium (magnesium) collophanite and application thereof

Abstract

The invention discloses a novel inhibitor for apatite in calcium (magnesium) collophanite and application of the novel inhibitor, and belongs to the technical field of phosphorite beneficiation. According to the method, sodium ethylenediamine di-o-phenyl acetate is used as an inhibitor for separating and recycling apatite from calcium (magnesium) collophanite through reverse flotation, a high separation effect is achieved on the basis of low cost, environment friendliness and low reagent dosage, and reverse flotation can be conducted on complex low-grade phosphorite; and the contradictory relation between the high-grade phosphorite reserves and the consumption is effectively relieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of phosphate ore dressing, and particularly relates to a novel inhibitor for apatite in calcium (magnesium) collophanite and application thereof. BACKGROUND

[0002] Phosphate ore refers to a general term of economically usable phosphate minerals, and is an important chemical mineral raw material. The phosphate ore can be used for preparing phosphate fertilizer, yellow phosphorus, phosphoric acid, phosphide and other phosphate substances, and is used in the fields of medicine, food, dye and the like.

[0003] Apatite (phosphate part in the whole phosphate rock) as a component with high application value in the phosphate ore, recovery thereof is of great significance.

[0004] At present, the recovery of apatite in the phosphate ore is mainly carried out by using the reverse flotation process. However, on the one hand, the apatite in the phosphate ore is usually combined with carbonate and silicate gangue minerals, resulting in that it is difficult to separate and recover the apatite from the gangue minerals in the reverse flotation process, especially for the low-grade phosphate ore, it is more difficult to improve the grade of the recovered apatite. On the other hand, the existing reverse flotation process needs to be carried out under acidic conditions, and needs to use strong acids such as phosphoric acid and sulfuric acid to maintain the pH environment of the flotation slurry stable under acidic conditions. The acidic conditions have a negative impact on the collecting ability of the fatty acid collector, resulting in that the collecting ability of the collector is weakened, the consumption of the collector is increased, the froth is brittle, which is not conducive to the reverse flotation recovery of the apatite and the cost control of the reverse flotation. At the same time, the strong acid has strong corrosiveness, and has great safety risk in use, and causes great damage to the flotation equipment. In addition, the strong acid is easy to produce phosphorus-containing waste liquid in the flotation process, resulting in eutrophication of water body, low environmental friendliness, and easy to cause environmental pollution. In addition, with the development of industrial technology, the consumption of high-grade phosphate ore is increased, and its reserves are reduced quickly, so it is necessary to carry out dressing of low-grade phosphate ore to meet the industrial demand.

[0005] Therefore, it is necessary to provide a novel inhibitor for apatite in calcium (magnesium) collophanite and application thereof, so as to realize the purpose of environmentally friendly, high selectivity and low cost reverse flotation recovery of the phosphate ore, improve the flotation effect of the complex and refractory low-grade phosphate ore, and realize the reverse flotation recovery of high-grade apatite from the low-grade phosphate ore. SUMMARY

[0006] In order to overcome the problems in the background art, the present application promotes the settlement of apatite in the reverse flotation process by using ethylenediamine di-o-phenylacetic acid sodium (EDDHA-NA) as an inhibitor and utilizing the selective adsorption characteristics of EDDHA-NA at the calcium site of apatite in phosphate rock, and effectively reduces the negative impact on the collector in the reverse flotation process by using EDDHA-NA as an inhibitor, thereby effectively improving the reverse flotation recovery effect of apatite and reducing the amount of reagent used and the cost of reverse flotation. In addition, by using EDDHA-NA as an inhibitor, the amount of phosphorus-containing waste liquid generated in the flotation process can be reduced, the risk of water eutrophication can be alleviated, and the environmental friendliness is good; finally, the present application can complete the reverse flotation under neutral conditions to obtain apatite with high grade, the conditions are mild, the damage to the flotation equipment can be effectively alleviated, the amount of reagent can be further reduced, and the like, which is conducive to improving the cost and safety of the process of recovering apatite by reverse flotation.

[0007] In order to achieve the above-mentioned purpose, the present application is realized by the following technical solutions: The present application provides a new inhibitor for apatite in calcium (magnesium) collophanite, which is ethylenediamine di-o-phenylacetic acid sodium.

[0008] The present application provides the application of the above-mentioned new inhibitor in the reverse flotation recovery of apatite in calcium (magnesium) collophanite, and the specific process of the reverse flotation recovery of apatite in calcium (magnesium) collophanite includes the following steps: S1: grinding the calcium (magnesium) collophanite raw ore and preparing a slurry with water.

[0009] S2: adding ethylenediamine di-o-phenylacetic acid sodium and a collector to the slurry obtained in step S1 in sequence, performing reverse flotation roughing operation, and obtaining roughing concentrate and roughing tailings after one roughing.

[0010] S3: adding a collector to the roughing concentrate obtained in step S2, performing one reverse flotation cleaning operation, and obtaining concentrate and flotation froth, wherein the concentrate is apatite.

[0011] As a preferred embodiment, in step S1, the grinding fineness is 92% of the total mass of the raw ore with a particle size of 200 mesh, and the slurry concentration is 25%-35%.

[0012] As a preferred embodiment, in step S2, the amount of ethylenediamine di-o-phenylacetic acid sodium is 8 kg / t based on the total mass of the raw ore in the slurry.

[0013] Preferably, in the steps S2 and S3, the collector is a fatty acid collector, and the amount of the collector in the step S2 is 1.60 kg / t based on the total mass of the raw ore in the ore slurry, and the amount of the collector in the step S3 is 0.30 kg / t based on the total mass of the raw ore in the ore slurry.

[0014] Preferably, in the step S2, the reverse roughing operation time is 6 min.

[0015] Preferably, in the step S3, the reverse cleaning operation time is 6 min.

[0016] Preferably, the phosphorus-containing mineral in the calcium (magnesium) collophanite is fluorapatite.

[0017] Preferably, the gangue mineral in the calcium (magnesium) collophanite is dolomite or calcite.

[0018] The present application uses EDDHA-NA as a new type of inhibitor, and the inhibitor mainly interacts with the mineral surface through chemical adsorption.

[0019] EDDHA-NA selectively adsorbs on the calcium sites of apatite, and this adsorption forms a hydration film on the surface of apatite, making it hydrophilic, thereby promoting the settlement of apatite in the reverse flotation process. Since EDDHA-NA occupies the active calcium sites of apatite, it can hinder the adsorption of the collector to the surface of apatite, so that the apatite can be effectively inhibited. On the other hand, EDDHA-NA contains amide and carboxyl groups in the molecule, which has excellent chelating properties, can preferentially combine with difficult ions (Ca 2+ , Mg 2+ ) in the ore slurry in the reverse flotation process, effectively reducing the content of Ca 2+ , Mg 2+ ions, thereby reducing the consumption of the subsequently added collector. That is, the addition of EDDHA-NA increases the adsorption amount of the collector on the surface of carbonate, silicate and other gangue minerals, so that the collector can more fully play its effect, thereby effectively reducing the amount of the collector.

[0020] The present application has the following beneficial effects: 1. The present application uses EDDHA-NA as a new type of inhibitor to promote the settlement of apatite in the reverse flotation process, and at the same time reduces the influence of the collector on the settlement of apatite in the reverse flotation process, thereby strengthening the reverse flotation separation and recovery effect of apatite in the phosphate ore.

[0021] 2. The present application uses EDDHA-NA as a new type of inhibitor to reduce the content of Ca 2+ , Mg 2+The consumption of the collector is reduced, the consumption of the collector is effectively reduced, the consumption of the re-flotation process is reduced, the reagent is effectively saved, and the cost is reduced.

[0022] 3. The present application completes the reverse flotation process under neutral conditions, without using a large amount of strong acid reagent to maintain an acidic environment, the amount of reagent used is reduced, and it is beneficial to alleviate the damage to the flotation equipment and the eutrophication of the water body, and at the same time, the reverse flotation process basically does not produce waste liquid containing heavy metals, the required conditions for reverse flotation are relatively mild, the environmental friendliness is high, and the cost control is convenient.

[0023] 4. The present application can effectively separate the complex low-grade phosphate rock and obtain high-grade apatite, effectively alleviate the contradiction between high-grade phosphate rock and low reserves, and high consumption, and has high theoretical and economic value for improving the separation level of complex low-grade phosphate rock and the comprehensive utilization rate of resources, and provides a new idea for the sustainable development of phosphate rock resources.

[0024] 5. The reverse flotation process of the present application is simple, convenient to operate, has fewer types and amounts of reagents, has good process controllability, is environmentally friendly, and is suitable for industrialized application. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 Figure 1 is a reverse flotation process flow diagram of the present application; Figure 2 Figure 2 is a reverse flotation process flow diagram of the present application. DETAILED DESCRIPTION

[0026] The present application will be further described in detail below in combination with the drawings and specific examples, but the scope of protection of the present application is not limited to the content described.

[0027] In the examples and comparative examples of the present application, commercially available analytical pure chemicals are used for experiments unless otherwise specified.

[0028] Example 1 The raw ore in this example is a raw ore from a phosphate mine in Yunnan, which contains P2O5 of 23.46%, MgO of 5.05%, and the target mineral is mainly fluorapatite. The gangue mineral content in the raw ore is high, mainly being dolomite and calcite.

[0029] In this example, the raw ore is subjected to reverse flotation to separate and recover apatite by the following process: (1) The raw ore is ground to a grinding fineness of 92% of the total mass of the raw ore passing through a 200-mesh screen, and the ground raw ore is used to prepare a slurry with a concentration of 30% by mixing with water; (2) EDDHA-NA is added to the slurry, the amount of which is 8 kg / t based on the total mass of the raw ore, and then the collector FL is added 1-7, the collector is added in an amount of 1.60 kg / t based on the total mass of the raw ore, reverse flotation roughing is performed, and after 6 min of roughing (one roughing), a rough concentrate (mainly phosphate minerals, i.e., fluorapatite) and a rough tailing (mainly gangue minerals) are obtained.

[0030] (3) The obtained rough concentrate is added with a collector FL 1-7 in an amount of 0.30 kg / t based on the total mass of the raw ore, one reverse flotation cleaning is performed, and after 6 min of reverse flotation cleaning, a concentrate and flotation froth are obtained, the flotation froth is combined with the rough tailing in step (2) to discard the tailing, and finally a fluorapatite concentrate (i.e., a phosphate concentrate) is obtained.

[0031] The sorting yield, fluorapatite concentrate grade, and recovery rate of the present embodiment are tested, and the results are shown in Table 1.

[0032] Table 1 According to the results in Table 1, after sorting, the P2O5 grade of the fluorapatite concentrate reaches 31.27%, the recovery rate reaches 82.01%, the MgO grade is 0.61%, the recovery rate is 7.39%, and the enrichment ratio of P2O5 is 1.33, indicating that the use of EDDHA-NA as a new inhibitor in the present application can effectively separate phosphate from gangue minerals such as dolomite and calcite, achieving a good sorting effect. At the same time, the raw ore has a P2O5 grade of 23.46% and contains gangue minerals such as dolomite and calcite, which is a relatively complex low-grade phosphate rock, and the present application can sort the relatively complex low-grade phosphate rock to obtain fluorapatite with a high grade, and the fluorapatite yield and recovery rate are both at a high level.

[0033] Example 2 The same raw ore and method as in Example 1 are used for reverse flotation in the present embodiment, except that the pulp concentration is 25% in the present embodiment.

[0034] The reverse flotation results of the present embodiment are similar to those of Example 1.

[0035] Example 3 The same raw ore and method as in Example 1 are used for reverse flotation in the present embodiment, except that the pulp concentration is 35% in the present embodiment.

[0036] The reverse flotation results of the present embodiment are similar to those of Example 1.

[0037] Comparative Example In the present comparative example, the same raw ore and reverse flotation process as in the examples were used for raw ore separation, the difference being that in the present comparative example, EDDHA-NA was replaced by sulfuric acid and phosphoric acid, the amount of sulfuric acid used was 14 kg / t, and the amount of phosphoric acid used was 7 kg / t, and in the reverse flotation roughing process, FL 1-7 was added in an amount of 2.35 kg / t, and the order of addition of the reagents was sulfuric acid, phosphoric acid, and collector. In the reverse flotation cleaning process, FL 1-7 was added in an amount of 0.65 kg / t. And in the reverse flotation roughing process, the change in the pH value of the slurry was detected in real time, so that the pH value was kept within the acidic condition.

[0038] The separation yield, apatite concentrate grade, and recovery rate of the present comparative example were tested, and the results are shown in Table 2.

[0039] Table 2 According to the results in Table 2, the P2O5 grade in the concentrate of the present comparative example was 30.65%, which was 0.62% lower than the P2O5 grade in the concentrate of the example; the P2O5 recovery rate in the concentrate was 81.81%, which was 0.2% lower than the P2O5 recovery rate in the concentrate of the example. Although the flotation indicators of the present comparative example were basically the same as those of the example, the amounts of the inhibitors, sulfuric acid and phosphoric acid, in the present comparative example were 14 kg / t and 7 kg / t, respectively, and the total amount was 21 kg / t, which was 13 kg / t more than the amount of the inhibitors in the example; the amounts of the collectors in the present comparative example were 2.35 kg / t and 0.65 kg / t, respectively, and the total amount was 3 kg / t, which was 1.1 kg / t more than the total amount of the collectors in the example.

[0040] In summary, by using EDDHA-NA as a new type of inhibitor, the present application can effectively reduce the amount of reagents, and can make the reverse flotation process proceed under relatively mild conditions without the need to control the acidic condition, is environmentally friendly, has a lower cost, and has a better separation effect.

[0041] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present application and are not limiting, and although the present application has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to the form and details thereof without departing from the scope defined by the claims of the present application.

Claims

1. A novel inhibitor of apatite in calcium (magnesium) colophane, characterized in that: The new inhibitor is ethylenediamine sodium di-o-phenylacetate.

2. Application of the new inhibitor of apatite in calcium (magnesium) -bearing collophanite in reverse flotation of apatite in calcium (magnesium) -bearing collophanite in claim 1.

3. Use according to claim 2, characterized in that: The specific process of reverse flotation of apatite in calcium (magnesium) -bearing collophanite includes the following steps: S1: grinding the calcium (magnesium) -bearing collophanite raw ore and preparing a slurry with water; S2: adding ethylenediamine sodium di-o-phenylacetate and collector to the slurry obtained in step S1 in turn, performing reverse flotation roughing operation, and obtaining roughing concentrate and roughing tailings after one roughing; S3: adding collector to the roughing concentrate obtained in step S2, performing one reverse flotation cleaning operation, and obtaining concentrate and flotation froth, the concentrate being apatite.

4. Use according to claim 3, characterized in that: In step S1, the grinding fineness is that the amount of-200 mesh ore accounts for 92% of the total amount of raw ore, and the slurry concentration is 25%-35%.

5. Use according to claim 3, characterized in that: In step S2, the amount of ethylenediamine sodium di-o-phenylacetate is 8 kg / t based on the total amount of raw ore in the slurry.

6. Use according to claim 3, characterized in that: In steps S2 and S3, the collector is a fatty acid collector, in step S2, the amount of collector is 1.60 kg / t based on the total amount of raw ore in the slurry, and in step S3, the amount of collector is 0.30 kg / t based on the total amount of raw ore in the slurry.

7. Use according to claim 3, characterized in that: In step S2, the reverse flotation roughing operation time is 6 min.

8. Use according to claim 3, characterized in that: In step S3, the reverse flotation cleaning operation time is 6 min.

9. A novel inhibitor of apatite in calcium (magnesium) collophane according to claim 1, characterized by: The phosphorus-containing mineral in the calcium (magnesium) -bearing collophanite is fluorapatite.

10. A novel inhibitor of apatite in calcium (magnesium) collophane according to claim 1, characterized by: The gangue mineral in the calcium (magnesium) -bearing collophanite is dolomite and calcite.

Images