Use of a phosphono carboxylic acid copolymer as an inhibitor in a fluorite ore

Abstract

The application discloses a new use of phosphono carboxylic acid copolymer, which is a fluorite ore flotation inhibitor, especially in the flotation of fluorite ore containing calcite or barite; the phosphono carboxylic acid copolymer is added as a gangue inhibitor in roughing and cleaning, so that the calcite and the barite can be effectively inhibited, and the grade and the recovery rate of fluorite concentrate are improved. The phosphono carboxylic acid copolymer has the advantages of good inhibition effect, low dosage, wide source and environmental friendliness as the fluorite ore inhibitor.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing reagents and relates to a new use of phosphonocarboxylic acid copolymers, specifically the application of phosphonocarboxylic acid copolymers as inhibitors in the flotation of fluorite ore. Background Technology

[0002] Currently, fluorite is the main source of fluorine in various fluorine products. As an important non-metallic mineral, it is closely related to the development of the national economy. With the rapid development of fluorine-containing compounds globally, fluorite's status as a basic industrial raw material is becoming increasingly important, and it has become a crucial resource. my country has abundant fluorite resources, but they are mostly composed of impurities and associated minerals. Impurity removal is the primary objective of fluorite enrichment. Currently, flotation is the most commonly used method for obtaining high-grade fluorite concentrate, and selecting appropriate beneficiation reagents is key to fluorite impurity removal.

[0003] For quartz-type fluorite deposits with a single gangue, sodium carbonate as a modifier, water glass as a depressant, and fatty acids as a collector can easily achieve effective enrichment of fluorite through roughing and multiple cleaning processes. However, for fluorite deposits containing a significant amount of calcite or barite, to obtain high-grade fluorite concentrate, impurities such as quartz and barite in the calcite need to be removed during beneficiation. Since calcite, barite, and fluorite have similar mineral properties, including similar surface physical and chemical properties, it is difficult to obtain good flotation performance using only water glass or acidified water glass as a depressant.

[0004] Phosphonocarboxylic acid copolymers are compounds in which phosphonic acid groups are introduced onto the original carboxylic acid groups. They exhibit excellent dispersing properties for calcium carbonate and calcium phosphate scale in circulating cooling water, and effectively inhibit the deposition of barium sulfate, strontium sulfate, and silica scale. Phosphonocarboxylic acid copolymers are mainly used for scale inhibition and corrosion inhibition in industrial circulating cooling water systems and oilfield reinjection water systems, featuring a wide range of applicable water qualities, good chemical stability, and strong resistance to chlorine oxidation. To date, there are no reports of phosphonocarboxylic acid copolymers being used as mineral processing inhibitors. Summary of the Invention

[0005] The present invention aims to provide a novel application of phosphonocarboxylic acid copolymers as inhibitors in fluorite ore. Addressing the problem of low beneficiation efficiency and difficulty in obtaining high-grade fluorite concentrate in fluorite ores containing calcite and barite, the phosphonocarboxylic acid copolymers of the present invention, used as inhibitors in fluorite ore, can effectively remove impurities such as calcite and barite, significantly improving the grade and recovery rate of fluorite concentrate.

[0006] The objective of this invention is achieved through the following means.

[0007] The application of a phosphonocarboxylic acid copolymer as an inhibitor in fluorite ore, which is used as a calcite or barite inhibitor in fluorite ore flotation.

[0008] A method for using a phosphonocarboxylic acid copolymer as an inhibitor in fluorite ore involves first adjusting the pH of the slurry with hydrochloric acid, sodium hydroxide, or sodium carbonate, then adding the inhibitor water glass (or acidified water glass) and the phosphonocarboxylic acid copolymer of the present invention for slurry conditioning, and finally adding a collector for slurry conditioning before flotation.

[0009] The fluorite flotation process consists of roughing, roughing and cleaning operations, or roughing, cleaning and scavenging operations.

[0010] Phosphonocarboxylic acid copolymers are used as inhibitors in the roughing and cleaning of fluorite.

[0011] The crude selection amount of phosphonocarboxylic acid copolymer is 50-500 g / t, and the refined selection amount is 10-200 g / t.

[0012] The phosphonocarboxylic acid copolymer of the present invention is a common scale inhibitor and dispersant. It contains multiple carboxyl and phosphonic acid groups in its molecule, has a strong inhibitory effect on calcium carbonate and barium sulfate, and can selectively adsorb on the surface of calcium carbonate and barium sulfate, thereby enhancing the hydrophilicity of gangue mineral surfaces.

[0013] The phosphonocarboxylic acid copolymer of the present invention, as a fluorite mineral inhibitor, has the following beneficial effects:

[0014] In the flotation of fluorite ore, phosphonocarboxylic acid copolymers can effectively suppress the flotation of calcite or barite, improve the grade and recovery rate of fluorite concentrate, and are of great significance for the development of low-grade fluorite ore.

[0015] Phosphonocarboxylic acid copolymers are common compounds that are widely available, inexpensive, and easy to use. These compounds are also biodegradable and environmentally friendly. Detailed Implementation

[0016] The present invention is further illustrated by the following embodiments, but is not limited to these embodiments.

[0017] Example 1

[0018] In the laboratory, flotation tests were conducted on pure minerals such as fluorite, calcite, and barite using an XFG hanging-tank pure mineral flotation machine. After adding 10g of pure mineral to the flotation tank and adjusting the slurry with water, the pH of the slurry was adjusted to about 11 with sodium carbonate. After adding 50mg / L of water glass and adjusting the slurry for 2 minutes, 60mg / L of collector oleic acid was added. After stirring for 2 minutes, the foam was manually skimmed off, and the recovery rate was calculated based on the weight of the foam product.

[0019] Comparative Example 1

[0020] When adding water glass in the single mineral flotation test, 20 mg / L of phosphonocarboxylic acid copolymer was added simultaneously. The rest was the same as in Example 1. The recovery rate was calculated based on the weight of the foam product.

[0021] Table 1. Data from single-mineral comparative tests

[0022]

[0023] Example 2

[0024] This embodiment uses a fluorite mine in Zhejiang Province. The fluorite ore contains 36.20% CaF2, 5.62% CaCO3, and 52.35% SiO2, with -200 mesh accounting for -65% of the ore. Water was first added to adjust the slurry concentration to 30%. Then, 1500 g / t sodium carbonate, 800 g / t water glass, and 800 g / t oleic acid (collector) were added to adjust the slurry. Flotation tests were conducted at approximately 30°C. 200 g / t of 1-3 water glass was used for fine selection, and 100 g / t of 4-6 water glass was used for fine selection. After one roughing and six fine selections, a fluorite concentrate with a grade of 92.35% and a recovery rate of 56.67% was obtained.

[0025] Comparative Example 2

[0026] Using the fluorite ore from Example 2, the flotation process is the same. The inhibitor phosphonocarboxylic acid copolymer is used for roughing at 100 g / t, for cleaning 1-3 at 50 g / t, and for cleaning 4-6 at 30 g / t. The dosage of other reagents is the same as in Example 2. After one roughing and six cleaning processes, a fluorite concentrate with a grade of 94.31% and a recovery rate of 65.36% can be obtained.

[0027] Example 3

[0028] This embodiment uses a fluorite mine in Inner Mongolia. This fluorite mine is a rare earth flotation tailings. The fluorite ore fed into the flotation contains 49.56% CaF2, 5.21% CaCO3, 2.56% BaSO4, and 30.23% SiO2, with -200 mesh accounting for -95% of the ore. Water is first added to adjust the slurry concentration to 40%. 1200 g / t of acidified water glass and 1100 g / t of collector oleic acid are added to adjust the slurry separately. Flotation tests are conducted at a room temperature of about 30°C. 200 g / t of 1-3 water glass is used for fine selection, and 100 g / t of 4-7 water glass is used for fine selection. After one roughing and seven fine selections, a fluorite concentrate with a grade of 82.35% and a recovery rate of 30.35% can be obtained.

[0029] Comparative Example 3

[0030] Using the fluorite ore from Example 3, the flotation process is the same. The phosphonocarboxylic acid copolymer inhibitor is used for roughing at 150 g / t, for cleaning 1-3 at 60 g / t, and for cleaning 4-7 at 20 g / t. The dosage of other reagents is the same as in Example 3. After one roughing and seven cleaning processes, a fluorite concentrate with a grade of 88.65% and a recovery rate of 33.23% can be obtained.

Claims

1. The application of a phosphonocarboxylic acid copolymer as an inhibitor in fluorite ore, characterized in that: Phosphonocarboxylic acid copolymers are used as calcite or barite inhibitors in the flotation separation of fluorite and gangue minerals.

2. The application of the phosphonocarboxylic acid copolymer according to claim 1 as an inhibitor in fluorite ore, characterized in that: Phosphonocarboxylic acid copolymers are used as gangue mineral inhibitors in the roughing and cleaning processes of fluorite flotation.

3. The application of the phosphonocarboxylic acid copolymer according to claim 1 as an inhibitor in fluorite ore, characterized in that: First, the pH of the pulp is adjusted with hydrochloric acid, sodium hydroxide or sodium carbonate, then water glass and phosphonocarboxylic acid copolymer are added as inhibitors to condition the pulp, and finally collectors are added to condition the pulp before flotation.

4. The application of the phosphonocarboxylic acid copolymer according to claim 3 as an inhibitor in fluorite ore, characterized in that: The fluorite flotation process consists of roughing and cleaning operations, or roughing, cleaning and scavenging operations.

5. The application of the phosphonocarboxylic acid copolymer according to claim 3 as an inhibitor in fluorite ore, characterized in that: The crude selection amount of phosphonocarboxylic acid copolymer is 50-500 g / t, and the refined selection amount is 10-200 g / t.

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