Gypsum flotation slow-release collecting agent and beneficiation recovery method of high-gypsum apatite

Abstract

The invention provides a gypsum flotation slow-release collecting agent and a beneficiation recovery method of high-gypsum apatite, the slow-release collecting agent comprises a collecting agent, a regulator, an emulsifier and an accelerant, the collecting agent and the regulator are packaged in capsules, after the collecting agent acts with gypsum, the regulator is slowly released and participates in the flotation process, and the high-gypsum apatite is separated from the collecting agent. And early consumption caused by advanced action of the regulator and the ore pulp is avoided. A step-by-step flotation method is adopted for apatite, a slow-release collecting agent is firstly added for flotation, gypsum is selected out, then an apatite collecting agent is added for apatite flotation, and apatite concentrate is obtained. According to the method, the gypsum is floated preferentially by adopting the gypsum slow-release collecting agent, so that the dissolution of the gypsum and the consumption of dissolved ions on the flotation reagent are reduced, the mutual conversion of mineral surfaces is reduced, the interference of the gypsum on apatite flotation is greatly reduced, and the reagent and the method have a very good application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of ore dressing, and particularly to a slow-release collector for gypsum flotation and a method for ore dressing and recovery of high-gypsum-type apatite. Background Art

[0002] Phosphorite is an important non-renewable and irreplaceable non-metallic mineral resource, which is widely used in multiple fields such as agriculture, medicine, food, national defense, sugar making, new energy, etc. Especially in agriculture, as one of the three important agricultural fertilizers, phosphate fertilizer has a significant effect on increasing the yield of the vast majority of crops, and many countries have included phosphorite in the list of strategic mineral resources. In recent years, with the continuous development of the phosphochemical industry, the consumption of high-quality phosphorite that can be directly used has been exhausted, and more and more medium and low-grade phosphorite needs to be beneficiated and concentrated before it can meet the needs of downstream wet-process phosphoric acid and high-concentration phosphate fertilizer production.

[0003] The separation methods of phosphorite in China mainly include flotation, scrubbing and desliming, heavy medium separation, magnetic separation, photoelectric sorting, roasting-digestion, chemical leaching, microbial treatment, and combined ore dressing processes. Flotation is the most effective and widely used method for phosphorite ore dressing, mainly including direct flotation, reverse flotation, direct-reverse flotation, reverse-direct flotation, and double reverse flotation, which correspondingly involve the inhibition of phosphate-containing minerals, the inhibition of silicate and carbonate minerals.

[0004] Among them, the flotation of low-grade phosphorite mainly adopts direct flotation. By adding sodium carbonate or sodium hydroxide to adjust the pH, adding inhibitors of silicate minerals and carbonate minerals to inhibit gangue minerals, and then adding fatty acid collectors such as oxidized paraffin soap and oleic acid for flotation. However, low-grade phosphorite is usually associated with calcite, dolomite, anhydrite and other calcium-containing minerals. These calcium-containing minerals are slightly soluble, especially gypsum, which hydrolyzes a large amount of Ca 2+ and SO4 2- in water, causing mutual conversion on the mineral surface, increasing the similarity of the surface chemical properties of apatite and gypsum, and further exacerbating the difficulty of mineral separation.

[0005] At present, the main problems in the separation and recovery of high-gypsum-type apatite ore dressing are as follows: (1) The solubility of gypsum is large, and a large amount of Ca 2+ and SO4 2- are hydrolyzed in water. A large amount of dissolved Ca 2+ in the pulp is easily reacted with fatty acid reagents, which will consume a large amount of regulators and collectors, resulting in an increase in ore dressing costs. (2) Both apatite and gypsum are calcium-containing minerals, and it is difficult to separate them. The dissolution of minerals and the migration of ions in the pulp will cause mutual conversion on the surfaces of gypsum and apatite minerals, increasing the similarity of the surface chemical properties of apatite and gypsum, and further exacerbating the difficulty of mineral separation.

[0006] The flotation of high-gypsum ore has always been a difficult problem in ore dressing. By using conventional flotation methods, the recovery rate of apatite is only about 50%, and qualified apatite concentrate products cannot be obtained. At present, there are mainly two solutions for this type of resource. One is to add a large amount of sodium carbonate to consume the excessive calcium ions in the solution and reduce the impact on flotation. However, this method is only applicable to the case of low gypsum content. When the gypsum content is high, the amount of sodium carbonate added increases exponentially, and the ore dressing cost is relatively high. The other is to wash the ore by adding a large amount of water to completely dissolve the gypsum, thereby eliminating the influence of gypsum. However, the treatment of the recycled water after washing is a problem and it is difficult to achieve in industry. Summary of the Invention

[0007] The present invention provides a slow-release collector for gypsum flotation and a method for beneficiation and recovery of high-gypsum apatite, which solves the problems of large dosage of flotation reagents and poor separation effect for apatite containing gypsum.

[0008] The technical solution of the present invention is realized as follows: A slow-release collector for gypsum flotation comprises the following components in mass percentage: 30-50% of collector reagent, 20-40% of regulator, 5-15% of emulsifier, and 5-15% of promoter.

[0009] Further, the collector reagent comprises at least one of fatty amine, ether amine, quaternary ammonium salt, and amino acid collector.

[0010] Further, the regulator comprises at least one of sodium carbonate, water glass, and sodium hexametaphosphate.

[0011] Further, the emulsifier comprises at least one of fatty alcohol polyoxyethylene ether, sodium dodecylbenzenesulfonate, alkylamide betaine, and Span-60

[0012] Further, the promoter comprises at least one of diesel, kerosene, liquid paraffin, and fuel oil.

[0013] The preparation method of the slow-release collector for gypsum flotation comprises the following steps:

[0014] (1) Add 1 / 2 of the dosage of the emulsifier to the collector reagent and stir for 10-20 min to obtain a mixed solution;

[0015] (2) Add the remaining emulsifier to the regulator and stir for 10-20 min to obtain an emulsified regulator;

[0016] (3) Mix the mixed solution and the emulsified regulator, then add the promoter and stir for 20-40 min to obtain the slow-release collector for gypsum flotation.

[0017] A method for beneficiation and recovery of high-gypsum apatite comprises the following steps:

[0018] Put the high-gypsum-type apatite into a flotation machine for pulp conditioning, add the slow-release collector for gypsum flotation. After floating out the gypsum, add an apatite collector in the flotation cell for apatite flotation to obtain apatite concentrate. The fineness of the high-gypsum-type apatite is that the proportion of particles with a particle size of -0.074 mm accounts for 40%-80%.

[0019] Further, the gypsum flotation includes one-stage roughing and one-stage scavenging. The dosage of the slow-release collector in one-stage roughing is 200-600 g / t, and the dosage of the slow-release collector in one-stage scavenging is 100-300 g / t.

[0020] Further, the apatite flotation includes one roughing, one scavenging and three cleanings. The apatite collector is at least one of oleic acid, oxidized paraffin soap, sodium petroleum sulfonate, and sodium dodecyl sulfonate, and the dosage of the collector in roughing is 300-600 g / t.

[0021] The beneficial effects of the present invention:

[0022] The slow-release collector for gypsum and the step-by-step flotation process of the present invention jointly solve the problem of separation and recovery of high-gypsum-type apatite. The slow-release collector is formulated into a water-in-oil microcapsule structure by assembling, encapsulating the regulator and the collector into the capsule to avoid the premature action and consumption of the regulator with the pulp. When the collector acts on the gypsum, the regulator is slowly released and participates in the flotation process; the slow release of the regulator greatly reduces the consumption of the reagent.

[0023] The high-gypsum-type apatite of the present invention adopts step-by-step flotation to preferentially float out gypsum, reducing the surface mutual conversion between gypsum and apatite, as well as the consumption and interference of the dissolved ions of gypsum on the apatite flotation collector, improving the apatite beneficiation index, and solving the problem of separation and recovery of high-gypsum-type apatite. Description of the Drawings

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0025] Figure 1 It is the process flow diagram of the beneficiation and recovery method for high-gypsum-type apatite. Detailed Embodiments

[0026] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0027] Embodiment 1

[0028] A slow-release collector for gypsum flotation, calculated by mass percentage, consists of the following components: 50% of collector reagent, 30% of regulator, 10% of emulsifier, and 10% of promoter. Among them, the collector reagent is ether amine; the regulator includes: 15% of sodium carbonate and 15% of water glass; the emulsifier is fatty alcohol polyoxyethylene ether; the promoter is kerosene.

[0029] The preparation method of the above slow-release collector for gypsum flotation includes the following steps:

[0030] (1) Weigh each component by mass percentage: weigh 50% of ether amine, 15% of sodium carbonate, 15% of water glass, 10% of fatty alcohol polyoxyethylene ether, and 10% of kerosene.

[0031] (2) Add 1 / 2 of the amount of fatty alcohol polyoxyethylene ether weighed in step (1) to the weighed ether amine and stir for 20 min to obtain a mixed solution;

[0032] (3) Add 1 / 2 of the amount of fatty alcohol polyoxyethylene ether in step (1) to the weighed sodium carbonate and water glass and stir for 20 min to obtain an emulsified regulator;

[0033] (4) Mix the mixed solution obtained in step (2) and the emulsified regulator obtained in step (3), and add the kerosene weighed in step (1), and stir for 30 min to obtain the slow-release collector for gypsum flotation.

[0034] Application of a slow-release collector for gypsum flotation in the beneficiation recovery of high-gypsum apatite. As Figure 1 shown, it includes the following steps:

[0035] Put high-gypsum apatite (gypsum content > 10 wt.%) with a fineness of 55% of particle size -0.074 mm into a flotation machine for pulp conditioning, add the above slow-release collector for gypsum flotation for flotation, and preferentially select gypsum. The gypsum flotation process is one roughing and one scavenging. The dosage of the slow-release collector for roughing is 300 g / t, and the slow-release collector for scavenging is 200 g / t.

[0036] Then, add oleic acid, a collector for apatite, into the flotation cell for apatite flotation. The flotation process is one roughing, one scavenging, and three cleanings. The dosage of the collector in roughing is 400 g / t, and the dosage of the collector in scavenging is 200 g / t. The obtained apatite concentrate has a P2O5 grade of 30.08% and a recovery rate of 70.86%.

[0037] Example 2

[0038] A slow-release collector for gypsum flotation, by mass percentage, consists of the following components: 40% of collector reagent, 40% of regulator, 15% of emulsifier, and 5% of promoter. Among them, the collector reagent is dodecylamine; the regulator includes: 30% of sodium carbonate and 10% of sodium hexametaphosphate; the emulsifier is Span-60; the promoter is diesel oil.

[0039] The preparation method of the above slow-release collector for gypsum flotation includes the following steps:

[0040] (1) Weigh each component by mass percentage: weigh 40% of dodecylamine, 30% of sodium carbonate, 10% of sodium hexametaphosphate, 15% of Span-60, and 5% of diesel oil.

[0041] (2) Add 1 / 2 of the dosage of Span-60 weighed in step (1) to the weighed dodecylamine and stir for 15 min to obtain a mixed solution;

[0042] (3) Add 1 / 2 of the dosage of Span-60 in step (1) to the weighed sodium carbonate and sodium hexametaphosphate and stir for 15 min to obtain an emulsified regulator;

[0043] (4) Mix the mixed solution obtained in step (2) and the emulsified regulator obtained in step (3), and add the diesel oil weighed in step (1), and stir for 40 min to obtain the slow-release collector for gypsum flotation.

[0044] Application of a slow-release collector for gypsum flotation in the ore dressing and recovery of high-gypsum-type apatite. As Figure 1 shown, it includes the following steps:

[0045] Put high-gypsum-type apatite (gypsum content > 10%) with a fineness of -0.074 mm particle size accounting for 60% into a flotation machine for pulp conditioning, add the above slow-release collector for gypsum flotation for flotation, and preferentially select gypsum. The gypsum flotation process is one roughing and one scavenging. The dosage of the slow-release collector in roughing is 600 g / t, and the slow-release collector in scavenging is 300 g / t.

[0046] Then, add oxidized paraffin soap, a collector for apatite, into the flotation cell for apatite flotation. The flotation process is one roughing, one scavenging, and three cleanings. The dosage of the collector in roughing is 600 g / t, and the dosage of the collector in scavenging is 200 g / t. The obtained apatite concentrate has a P2O5 grade of 32.16% and a recovery rate of 68.63%.

[0047] Example 3

[0048] A slow-release collector for gypsum flotation, the components of which are composed of the following components by mass percentage: 30% of collector agent, 40% of regulator, 15% of emulsifier, and 15% of promoter. Among them, the collector agent is sodium dodecyl aminopropionate; the regulator includes: 20% of sodium carbonate, 15% of water glass, and 5% of sodium hexametaphosphate; the emulsifier is dodecyl dimethyl betaine; the promoter is kerosene.

[0049] The preparation method of the above slow-release collector for gypsum flotation includes the following steps:

[0050] (1) Weigh each component by mass percentage: weigh 30% of sodium dodecyl aminopropionate, 20% of sodium carbonate, 15% of water glass, 5% of sodium hexametaphosphate, 15% of dodecyl dimethyl betaine, and 15% of kerosene.

[0051] (2) Add 1 / 2 of the amount of dodecyl dimethyl betaine weighed in step (1) to the weighed sodium dodecyl aminopropionate, and stir for 10 min to obtain a mixed solution;

[0052] (3) Add 1 / 2 of the amount of dodecyl dimethyl betaine in step (1) to the weighed sodium carbonate, water glass, and sodium hexametaphosphate, and stir for 10 min to obtain an emulsified regulator;

[0053] (4) Mix the mixed solution obtained in step (2) and the emulsified regulator obtained in step (3), and add the kerosene weighed in step (1), and stir for 40 min to obtain the slow-release collector for gypsum flotation.

[0054] Application of a slow-release collector for gypsum flotation in the beneficiation and recovery of high-gypsum apatite. As Figure 1 shown, it includes the following steps:

[0055] Put the high-gypsum apatite (gypsum content > 10 wt.%) with a fineness of 50% of the particle size -0.074 mm into the flotation machine for pulp conditioning, add the above slow-release collector for gypsum flotation for flotation, and preferentially select gypsum. The gypsum flotation process is one roughing and one scavenging. The dosage of the slow-release collector for roughing is 500 g / t, and the slow-release collector for scavenging is 250 g / t. Then add the collector for apatite, oxidized paraffin soap and petroleum sulfonate (1:1), in the flotation cell for apatite flotation. The flotation process is one roughing, one scavenging and three cleaning. The dosage of the collector for roughing is 400 g / t, and the dosage of the collector for scavenging is 200 g / t. The obtained apatite concentrate has a P2O5 grade of 29.27% and a recovery rate of 72.53%.

[0056] Comparative Example 1

[0057] The raw materials processed in Comparative Example 1 and Example 1 are the same. The differences are as follows: In the comparative example, a conventional apatite flotation reagent system is adopted, and a one-roughing, one-scavenging, and three-cleaning flotation process is used. The dosage of sodium carbonate in roughing is 3000 g / t, the dosage of water glass is 1000 g / t, the dosage of the collector oxidized paraffin soap is 1000 g / t, and the dosage of oxidized paraffin soap in scavenging is 500 g / t. The grade of P2O5 in the apatite concentrate obtained is 20.47%, and the recovery rate is 41.77%.

[0058] In this comparative example, both the grade and recovery rate of apatite are lower than those in Example 1. The main reason is that the content of gypsum in the ore is relatively large, and a large amount of Ca 2+ and SO4 2- are hydrolyzed in the pulp, which will consume a large amount of regulators and collectors. At the same time, it will cause the surface conversion between gypsum and apatite minerals, increasing the similarity of the surface chemical properties of apatite and gypsum, and further exacerbating the difficulty of mineral separation.

[0059] Comparative Example 2

[0060] The raw materials processed in Comparative Example 2 and Comparative Example 1 are the same, and the processing steps are similar. The difference is only that: the dosage of sodium carbonate in roughing is increased to 20000 g / t, and the grade of P2O5 in the apatite concentrate obtained is 25.65%, and the recovery rate is 61.62%.

[0061] In this comparative example, by increasing the dosage of sodium carbonate, the Ca 2+ in the pulp is consumed, reducing the surface conversion of minerals and the consumption of collectors, and improving the flotation index of apatite. However, if the dosage of sodium carbonate is too large, the economy of the ore will be reduced.

[0062] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A gypsum flotation slow-release collector, characterized in that: The invention comprises the following components in percentage by mass: 30-50% of a collecting agent, 20-40% of a regulating agent, 5-15% of an emulsifier and 5-15% of a accelerator.

2. A gypsum flotation slow-release collector according to claim 1, characterized in that: The collecting agent includes at least one of aliphatic amines, ether amines, quaternary ammonium salts and amino acid collectors.

3. A gypsum flotation slow-release collector according to claim 1, characterized in that: The adjusting agent includes at least one of sodium carbonate, water glass and sodium hexametaphosphate.

4. The gypsum flotation slow-release collector according to claim 1, characterized in that: The emulsifier includes at least one of fatty alcohol polyoxyethylene ether, sodium dodecylbenzene sulfonate, alkylamide betaine and Span-60.

5. The gypsum flotation slow-release collector according to claim 1, characterized in that: The accelerator includes at least one of diesel, kerosene, liquid paraffin and fuel oil.

6. The method for preparing the gypsum flotation slow-release collector according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Add 1 / 2 amount of emulsifier to the collecting agent and stir for 10-20 minutes to obtain a mixed solution; (2) adding the remaining emulsifier to the adjusting agent and stirring for 10-20 minutes to obtain an emulsified adjusting agent; (3) The mixed liquid and the emulsifier are mixed, and then the accelerator is added and stirred for 20-40 minutes to obtain a gypsum flotation slow-release collector.

7. A method for recovering high-gypsum apatite by mineral processing, characterized in that: The following steps are involved: The high-gypsum apatite is put into a flotation machine for slurry preparation, and the slow-release collector described in any one of claims 1 to 5 is added to carry out gypsum flotation. After the gypsum is floated out, the apatite collector is added into the flotation tank to carry out apatite flotation to obtain an apatite concentrate.

8. The ore dressing and recovery method according to claim 7, characterized in that: Gypsum flotation includes a roughing stage and a scavenging stage. The dosage of slow-release collector in the roughing stage is 200-600g / t, and the dosage of slow-release collector in the scavenging stage is 100-300g / t.

9. The ore dressing and recovery method according to claim 7, characterized in that: Apatite flotation includes one roughing, one sweeping and three refining. The apatite collector is at least one of oleic acid, oxidized paraffin soap, sodium petroleum sulfonate and sodium dodecyl sulfonate. The amount of roughing collector is 300-600g / t.

Images