CN113060752A - Recycling method of fluorite flotation tailings - Google Patents
Recycling method of fluorite flotation tailings Download PDFInfo
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- CN113060752A CN113060752A CN202110305148.6A CN202110305148A CN113060752A CN 113060752 A CN113060752 A CN 113060752A CN 202110305148 A CN202110305148 A CN 202110305148A CN 113060752 A CN113060752 A CN 113060752A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/32—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for recycling fluorite flotation tailings, which comprises the following steps: a. adding a hydrochloric acid solution into the tailings, performing acid leaching on the tailings, and dissolving calcium carbonate in the tailings; b. carrying out solid-liquid separation on the ore pulp obtained after acid leaching to obtain solid-phase mineral powder and leachate; c. further floating the solid-phase mineral powder to obtain high-quality fluorite powder; d. adding a pH regulator into the leachate, controlling the pH value of the solution, carrying out impurity removal reaction to convert magnesium, manganese, iron and the like in the solution into precipitates, and carrying out solid-liquid separation to obtain a pure calcium chloride solution; e. adding the calcium chloride solution and sulfuric acid into a stirring reaction tank in proportion for reaction; f. carrying out solid-liquid separation on the reaction liquid after the reaction to obtain a hydrochloric acid solution and a gypsum filter cake; g. returning the obtained hydrochloric acid solution to the acid leaching process of the tailings again; h. and washing and drying the gypsum filter cake to obtain a gypsum product. The method has high product recovery rate and low cost.
Description
Technical Field
The invention relates to a beneficiation method, in particular to a method for recycling fluorite flotation tailings.
Background
Flotation is generally used for sorting fluorite ores. Fluorite ore produces a large amount of tailings during the flotation process. A large amount of valuable metals and fluorite still remain in the fluorite flotation tailings, the content of the fluorite in the tailings is 10-50%, and the recycling value exists.
At present, because no proper recycling method is found, most of fluorite flotation tailings are treated in a tailing pond for stockpiling. The treatment mode not only needs to occupy a large amount of land and wastes resources, but also causes solid waste pollution in the stacking process.
How to overcome the defects in the prior art and find a feasible method for recycling fluorite flotation tailings is a technical problem which is urgently solved by technical personnel in the field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for recycling fluorite flotation tailings.
In order to solve the technical problem, the method for recycling fluorite flotation tailings comprises the following steps:
a. adding a hydrochloric acid solution into the tailings, stirring, controlling the addition of the hydrochloric acid by detecting the pH value of a leaching solution, carrying out acid leaching on the tailings, and dissolving calcium carbonate in the tailings;
b. carrying out solid-liquid separation on the ore pulp obtained after acid leaching to obtain solid-phase mineral powder and leachate;
c. further floating the solid-phase mineral powder to obtain high-quality fluorite powder;
d. adding a pH regulator into the leachate, controlling the pH value of the solution, carrying out impurity removal reaction to convert magnesium, manganese, iron and the like in the solution into precipitates, and carrying out solid-liquid separation to obtain a pure calcium chloride solution;
e. adding the calcium chloride solution and sulfuric acid into a stirring reaction tank in proportion for reaction;
f. carrying out solid-liquid separation on the reaction liquid after the reaction to obtain a hydrochloric acid solution and a gypsum filter cake;
g. returning the obtained hydrochloric acid solution to the acid leaching process of the tailings again;
h. and washing and drying the gypsum filter cake to obtain a gypsum product.
The content of fluorite in the tailings is 10-50%.
Preferably, in the step a, the pH value of the leaching solution is 1-6.
Preferably, in the step d, the pH regulator is one of limestone, lime, carbide slag or sodium hydroxide or materials containing the substances, and the pH value of the solution is 8-10.
Preferably, the molar ratio of calcium chloride to sulfuric acid is 0.98-1.02: 1.
Preferably, the solid-liquid separation is one of filter pressing, vacuum filtration and centrifugal separation.
By adopting the method, the fluorite content in the processed tailings is generally about 10-50%, the soluble impurity content is generally about 30-60%, and after acid leaching of hydrochloric acid, the soluble impurities such as calcium carbonate and the like in the tailings can be completely removed, so that the fluorite grade in the tailings is greatly improved and is changed into high-grade concentrated fluorite ore, the fluorite grade is not less than 70%, the fluorite grade of the concentrated fluorite ore can be further improved to more than 97% by a flotation method and is changed into fluorite concentrate, the aim of recycling the fluorite in the tailings is fulfilled, the problems of difficult treatment and high treatment cost of the tailings are solved, and a certain economic benefit can be created by recycling the fluorite.
The gypsum obtained by the reaction of the calcium chloride solution and the sulfuric acid in the method can be further prepared into high-strength gypsum and gypsum whiskers. The high-strength gypsum and the gypsum whisker have better application prospects in the aspects of composite materials, water treatment, road modified asphalt, coatings, paints, flame-retardant and fireproof materials and papermaking.
The method has short process flow and simple operation, the whole production process is operated in a material balance controllable circulation state, and the zero emission of waste acid, waste water and waste residue (mainly silicon slag which is sent to a cement plant) is basically achieved; the hydrochloric acid for leaching can be recycled; the produced gypsum is synthesized in the whole liquid phase; the additional value of the by-product of the subsequent deep processing is high, and the economic benefit of the output value is not lower than that of the main product.
Detailed Description
Example one
100Kg of fluorite tailings are put into a stirring barrel, wherein the fluorite tailings contain 35 percent of fluorite, 30 percent of calcium carbonate and other soluble impurities. Adding 20% hydrochloric acid into a stirring barrel for stirring and acid leaching. And controlling the pH value of the solution after acid leaching to be 1, and stopping adding the hydrochloric acid. And (3) carrying out solid-liquid separation on the solution after acid leaching by a filter press to obtain concentrated fluorite ore (the fluorite grade is more than or equal to 70 percent) and leachate. The concentrated fluorite ore can be floated to obtain high-quality fluorite concentrate (the grade of the fluorite is more than or equal to 97 percent).
Adding quicklime into the leachate obtained by solid-liquid separation for impurity removal, and adjusting the pH value of the leachate to 8.5. And carrying out solid-liquid separation by a filter press to obtain a pure calcium chloride solution.
Adding the obtained pure calcium chloride solution and sulfuric acid into a reactor according to the molar ratio of 0.98:1 for reaction, and performing solid-liquid separation by a filter press after the reaction is completed to obtain a liquid-phase hydrochloric acid solution (the hydrochloric acid concentration is 18%) and solid-phase gypsum. Recycling the obtained hydrochloric acid solution to the acid leaching process; the obtained gypsum is washed and dried (the drying temperature is 80 ℃) to obtain a gypsum product.
Example two
200Kg of fluorite tailings are put into a stirring barrel, wherein the fluorite content in the fluorite tailings is 60 percent, and the soluble impurities such as calcium carbonate and the like are 28 percent. Adding 15% hydrochloric acid into a stirring barrel, stirring, carrying out acid leaching, controlling the pH value of the solution after acid leaching to 3, and stopping adding hydrochloric acid. And (3) carrying out solid-liquid separation on the solution after acid leaching by a filter press to obtain concentrated ore containing fluorite (the grade is more than or equal to 80%) and leachate. Further floating the fluorite concentrate to obtain fluorite products (the grade is more than or equal to 97 percent).
Adding quicklime into the leachate obtained by solid-liquid separation for impurity removal, and adjusting the pH value of the leachate to 10. And carrying out solid-liquid separation by a filter press to obtain a pure calcium chloride solution.
Adding the obtained pure calcium chloride solution and sulfuric acid into a reactor according to the molar ratio of 1.02:1 for reaction, and performing solid-liquid separation by a filter press after the reaction is completed to obtain a liquid-phase hydrochloric acid solution (the hydrochloric acid concentration is 13%) and solid-phase gypsum. Recycling the obtained hydrochloric acid solution to the acid leaching process; the obtained gypsum is washed and dried (the drying temperature is 120 ℃) to obtain a gypsum product.
Claims (6)
1. A method for recycling fluorite flotation tailings is characterized by comprising the following steps:
a. adding a hydrochloric acid solution into the tailings, stirring, controlling the addition of the hydrochloric acid by detecting the pH value of a leaching solution, carrying out acid leaching on the tailings, and dissolving calcium carbonate in the tailings;
b. carrying out solid-liquid separation on the ore pulp obtained after acid leaching to obtain solid-phase mineral powder and leachate;
c. further floating the solid-phase mineral powder to obtain high-quality fluorite powder;
d. adding a pH regulator into the leachate, controlling the pH value of the solution, carrying out impurity removal reaction to convert magnesium, manganese, iron and the like in the solution into precipitates, and carrying out solid-liquid separation to obtain a pure calcium chloride solution;
e. adding the calcium chloride solution and sulfuric acid into a stirring reaction tank in proportion for reaction;
f. carrying out solid-liquid separation on the reaction liquid after the reaction to obtain a hydrochloric acid solution and a gypsum filter cake;
g. returning the obtained hydrochloric acid solution to the acid leaching process of the tailings again;
h. and washing and drying the gypsum filter cake to obtain a gypsum product.
2. The method of claim 1, further comprising: the content of fluorite in the tailings is 10-50%.
3. The method of claim 1, further comprising: and a, controlling the pH value of the leaching solution to be 1-6.
4. The method of claim 1, further comprising: and d, the PH regulator is one of limestone, lime, carbide slag or sodium hydroxide or materials containing the substances, and the PH value of the solution is 8-10.
5. The method of claim 1, further comprising: the molar ratio of the calcium chloride to the sulfuric acid is 0.98-1.02: 1.
6. The method of claim 1, further comprising: the solid-liquid separation adopts one of filter pressing, vacuum filtration and centrifugal separation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110305148.6A CN113060752A (en) | 2021-03-23 | 2021-03-23 | Recycling method of fluorite flotation tailings |
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| CN202110305148.6A CN113060752A (en) | 2021-03-23 | 2021-03-23 | Recycling method of fluorite flotation tailings |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100841A (en) * | 2021-11-02 | 2022-03-01 | 湖南有色郴州氟化学有限公司 | Metallurgical-grade low-grade fluorite quality improving method |
| CN114988484A (en) * | 2022-05-16 | 2022-09-02 | 安徽大学绿色产业创新研究院 | Gypsum tailing treatment method of solid lithium ore neutralization process |
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| CN105709940A (en) * | 2016-01-29 | 2016-06-29 | 长沙矿冶研究院有限责任公司 | Method for recovering fluorite from polymetallic ore floatation tailings |
| CN110292991A (en) * | 2019-07-03 | 2019-10-01 | 南华大学 | A kind of fluorite method for concentrating |
| CN111170350A (en) * | 2018-11-13 | 2020-05-19 | 中蓝连海设计研究院有限公司 | Beneficiation method for quartz-calcite type fluorite ore |
| CN111170349A (en) * | 2018-11-12 | 2020-05-19 | 中蓝连海设计研究院有限公司 | Acid leaching purification method suitable for fluorite ore |
| CN111960456A (en) * | 2020-08-06 | 2020-11-20 | 六盘水师范学院 | Recycling and treating process for calcium-containing waste acid after acid leaching of fluorite |
| CN112237986A (en) * | 2020-11-12 | 2021-01-19 | 力上资源科技开发有限公司 | Mineral flotation process |
-
2021
- 2021-03-23 CN CN202110305148.6A patent/CN113060752A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709940A (en) * | 2016-01-29 | 2016-06-29 | 长沙矿冶研究院有限责任公司 | Method for recovering fluorite from polymetallic ore floatation tailings |
| CN111170349A (en) * | 2018-11-12 | 2020-05-19 | 中蓝连海设计研究院有限公司 | Acid leaching purification method suitable for fluorite ore |
| CN111170350A (en) * | 2018-11-13 | 2020-05-19 | 中蓝连海设计研究院有限公司 | Beneficiation method for quartz-calcite type fluorite ore |
| CN110292991A (en) * | 2019-07-03 | 2019-10-01 | 南华大学 | A kind of fluorite method for concentrating |
| CN111960456A (en) * | 2020-08-06 | 2020-11-20 | 六盘水师范学院 | Recycling and treating process for calcium-containing waste acid after acid leaching of fluorite |
| CN112237986A (en) * | 2020-11-12 | 2021-01-19 | 力上资源科技开发有限公司 | Mineral flotation process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100841A (en) * | 2021-11-02 | 2022-03-01 | 湖南有色郴州氟化学有限公司 | Metallurgical-grade low-grade fluorite quality improving method |
| CN114988484A (en) * | 2022-05-16 | 2022-09-02 | 安徽大学绿色产业创新研究院 | Gypsum tailing treatment method of solid lithium ore neutralization process |
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