阅读说明：本技术 一种硅酸盐、碳酸盐类型萤石矿的选矿方法 (Beneficiation method for silicate and carbonate type fluorite ore ) 是由 刘守信 师伟红 王奕斐 周涛 余江鸿 黄国贤 李飞 路军兵 高彦萍 梁友乾 肖胤 于 2020-04-28 设计创作，主要内容包括：本发明公开了一种硅酸盐、碳酸盐类型萤石矿的选矿方法,属于非金属矿选矿技术领域,解决了现有选矿方法存在的回收率偏低、精矿产品杂质含量高的问题。本发明包括以下步骤：磨矿；粗选作业,脉石抑制剂采用T20和酸性水玻璃组合,捕收剂采用Y-8,脉石抑制剂T20包括聚天冬氨酸、硫酸铝和羟基乙叉二膦酸,质量比为3～6︰4︰0.5～1,捕收剂Y-8包括油酸钠、4-氧桥十四酸和聚乙二醇单辛基苯基醚,质量比为6～7︰2～3︰1；扫选作业,加入捕收剂Y-8；粗精矿再磨；精选作业,采用抑制剂T20和酸性水玻璃,捕收剂采用Y-8。本发明在较低温度条件下,可有效降低精矿产品中的杂质含量,提高萤石精矿品级。(The invention discloses a beneficiation method of silicate and carbonate type fluorite ores, belongs to the technical field of beneficiation of nonmetallic ores, and solves the problems of low recovery rate and high impurity content of concentrate products in the existing beneficiation method. The invention comprises the following steps: grinding ore; roughing, combining a gangue inhibitor with T20 and acidic water glass, using a collecting agent Y-8, wherein the gangue inhibitor T20 comprises polyaspartic acid, aluminum sulfate and hydroxyethylidene diphosphonic acid at a mass ratio of 3-6: 4: 0.5-1, and the collecting agent Y-8 comprises sodium oleate, 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether at a mass ratio of 6-7: 2-3: 1; carrying out scavenging operation, and adding a collecting agent Y-8; regrinding the rough concentrate; the concentration operation adopts inhibitor T20 and acid water glass, and the collector adopts Y-8. The invention can effectively reduce the impurity content in the concentrate product and improve the grade of the fluorite concentrate under the condition of lower temperature.)

1. A mineral separation method for silicate and carbonate fluorite ores is characterized by comprising the following steps:

step one, grinding ore: grinding the ore until the granularity is below 74 mu m and accounts for 60-70 percent;

step two, roughing operation: sulfuric acid is used as a pH regulator, a gangue mineral inhibitor is a combination of a gangue inhibitor T20 and acidic water glass, a collecting agent Y-8 is used as a collecting agent, the flotation pH value is controlled to be 5-7, the temperature is 20-25 ℃, the rough flotation operation of fluorite ore is carried out, the flotation time is 8-10 minutes, and fluorite rough concentrate is obtained; the gangue inhibitor T20 comprises polyaspartic acid, aluminum sulfate and hydroxyethylidene diphosphonic acid, and the mass ratio of the polyaspartic acid to the aluminum sulfate to the hydroxyethylidene diphosphonic acid is 3-6: 4: 0.5-1; the collecting agent Y-8 comprises sodium oleate, 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether, and the mass ratio of the sodium oleate to the 4-oxo-tetradecanoic acid to the polyethylene glycol mono-octyl phenyl ether is 6-7: 2-3: 1;

step three, scavenging operation: adding a collecting agent Y-8 into the tailings obtained in the second step to carry out scavenging operation;

step four, regrinding the rough concentrate: grinding the fluorite rough concentrate obtained in the step two until the granularity is below 43 mu m and accounts for 75% -80%, and obtaining reground fluorite rough concentrate;

step five, selection operation: and (4) carrying out concentration operation on the reground fluorite rough concentrate obtained in the fourth step under the condition that the pH value of ore pulp is 6-7, wherein T20 and acidic water glass are adopted as gangue mineral inhibitors, and Y-8 is adopted as a collecting agent.

2. The method for beneficiation of silicate, carbonate type fluorite ore according to claim 1, characterized in that: in the third step, the scavenging operation adopts twice scavenging, and collecting agent Y-8 is added in both the twice scavenging.

3. The method for beneficiation of silicate and carbonate type fluorite ore according to claim 2, characterized in that: in the fifth step, the concentration operation adopts six times of concentration, the temperature is 10-20 ℃, and gangue inhibitor T20, acidic water glass and collecting agent Y-8 are added in the first time of concentration; adding acid water glass and a collecting agent Y-8 into the second and third concentration; only adding the acid water glass from the fourth concentration to the sixth concentration, and obtaining fluorite concentrate after the six concentrations.

4. The method for beneficiation of silicate, carbonate type fluorite ore according to claim 3, characterized in that: and step five, returning the middlings in the first concentration operation to the second scavenging, and returning the middlings in other concentration operations to the previous operation in sequence.

5. A method for beneficiation of silicate-type, carbonate-type fluorite ore according to any one of claims 1 to 4, wherein: the acidic water glass is prepared by diluting industrial water glass and then adding sulfuric acid for acidification, wherein the modulus of the industrial water glass is 2.0-3.0, the weight ratio of the industrial water glass to the sulfuric acid is 1: 0.5, and the total mass concentration of the acidified water glass is 5-10%.

6. A method for beneficiation of silicate-type, carbonate-type fluorite ore according to any one of claims 1 to 4, wherein: the preparation method of the collecting agent Y-8 comprises the following steps: and (3) adding sodium oleate, 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether into a stirring kettle in proportion at normal temperature and normal pressure, and stirring at room temperature for 2.5-3 hours to obtain the collecting agent Y-8.

7. A method for beneficiation of silicate-type, carbonate-type fluorite ore according to any one of claims 1 to 4, wherein: the gangue inhibitor T20 is prepared by compounding polyaspartic acid, aluminum sulfate and hydroxyethylidene diphosphonic acid in proportion.

Technical Field

The invention belongs to the technical field of nonmetallic ore dressing, and particularly relates to a method for dressing silicate and carbonate fluorite ore.

Background

Fluorite is the most important industrial raw material containing fluorine, is widely applied to industrial departments of chemical industry, metallurgy, building materials, machinery, aviation and the like, and is also used as an important high-energy material of new industries. The fluorite resources in China are rich, but the single-type fluorite deposit reserves are small, the associated (or symbiotic) fluorite deposit reserves are rich, the low-grade refractory fluorite ores are more, the high-grade easily selected ores are less, especially when the ores contain gangue minerals such as silicate and carbonate, the symbiotic relationship is complex, the floatability of the ores is similar, and the separation difficulty of the fluorite is increased.

Flotation is the most common method for enriching fluorite, and a large number of flotation practices show that the conventional flotation method generally adopts substitutes of oleic acid and oleic acid as collecting agents and adopts water glass, sodium hexametaphosphate, tannins and the like as regulating agents, but the fluorite concentrate has low quality and is difficult to obtain satisfactory effects. In the aspect of the mineral processing process flow, in the current fluorite mineral processing practice, most fluorite processing plants adopt modes of regrinding rough concentrates, sequentially returning middlings, directly throwing tails after scavenging the refined middlings and the like, so that the field is difficult to control, when slime circulates, the yield is high, the impurities of concentrate products exceed the standard, the yield is low, the recovery rate of useful minerals is low, and the technical indexes cannot achieve the satisfactory flotation effect.

With the development of modern technology, the requirements on the grade and the impurity content of fluorite concentrate are higher and higher. Therefore, in order to adapt to the increasingly complex ore properties and the increasingly high environmental requirements and obtain high-quality fluorite concentrate, the selection of a reasonable separation process and the development of an efficient and environmental-friendly medicament system are inevitable trends for realizing the enrichment of the fluorite ore.

Disclosure of Invention

The invention aims to provide a beneficiation method for silicate and carbonate fluorite ores, which aims to solve the problems of low recovery rate and high impurity content of concentrate products in the existing beneficiation method.

The technical scheme of the invention is as follows: a mineral separation method for silicate and carbonate fluorite ores comprises the following steps:

step one, grinding ore: grinding the ore until the granularity is below 74 mu m and accounts for 60-70 percent;

step two, roughing operation: sulfuric acid is used as a pH regulator, a gangue mineral inhibitor is a combination of a gangue inhibitor T20 and acidic water glass, a collecting agent Y-8 is used as a collecting agent, the flotation pH value is controlled to be 5-7, the temperature is 20-25 ℃, the rough flotation operation of fluorite ore is carried out, the flotation time is 8-10 minutes, and fluorite rough concentrate is obtained; the gangue inhibitor T20 comprises Polyaspartic Acid (PASP), aluminum sulfate and hydroxyethylidene diphosphonic acid, and the mass ratio of the polyaspartic acid to the aluminum sulfate to the hydroxyethylidene diphosphonic acid is 3-6: 4: 0.5-1; the collecting agent Y-8 comprises sodium oleate, 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether, and the mass ratio of the sodium oleate to the 4-oxo-tetradecanoic acid to the polyethylene glycol mono-octyl phenyl ether is 6-7: 2-3: 1;

step three, scavenging operation: adding a collecting agent Y-8 into the tailings obtained in the second step to carry out scavenging operation;

step four, regrinding the rough concentrate: grinding the fluorite rough concentrate obtained in the step two until the granularity is below 43 mu m and accounts for 75% -80%, and obtaining reground fluorite rough concentrate;

step five, selection operation: and (4) carrying out concentration operation on the reground fluorite rough concentrate obtained in the fourth step under the condition that the pH value of ore pulp is 6-7, wherein T20 and acidic water glass are adopted as gangue mineral inhibitors, and Y-8 is adopted as a collecting agent.

As a further improvement of the invention, in the third step, the scavenging operation adopts twice scavenging, and collecting agent Y-8 is added in both the twice scavenging.

As a further improvement of the invention, in the fifth step, the concentration operation adopts six times of concentration, the temperature is 10-20 ℃, and gangue inhibitor T20, acidic water glass and collecting agent Y-8 are added in the first time of concentration; adding acid water glass and a collecting agent Y-8 into the second and third concentration; only adding the acid water glass from the fourth concentration to the sixth concentration, and obtaining fluorite concentrate after the six concentrations.

As a further improvement of the invention, in step five, the middlings in the first concentration operation are returned to the second scavenging, and the middlings in the other concentration operations are returned to the previous operation in sequence.

As a further improvement of the invention, the acidic water glass is prepared by diluting industrial water glass and then adding sulfuric acid for acidification, wherein the modulus of the industrial water glass is 2.0-3.0, the weight ratio of the industrial water glass to the sulfuric acid is 1: 0.5, and the total mass concentration of the acidified water glass is 5-10%.

As a further improvement of the invention, the preparation method of the collector Y-8 comprises the following steps: and (3) adding sodium oleate, 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether into a stirring kettle in proportion at normal temperature and normal pressure, and stirring at room temperature for 2.5-3 hours to obtain the collecting agent Y-8.

As a further improvement of the invention, the gangue inhibitor T20 is compounded by polyaspartic acid, aluminum sulfate and hydroxyethylidene diphosphonic acid according to a certain proportion.

The invention has the beneficial effects that:

1. the method has a good effect on treating silicate and carbonate fluorite ores, adopts a reasonable process flow, adds sulfuric acid to adjust the pH value of ore pulp to 5-7, and adds the combination of gangue inhibitor T20 and acidic water glass and collecting agent Y-8 under the condition that the temperature is 10-25 ℃ to perform fluorite ore flotation, so that the impurity content in concentrate products can be effectively reduced, and the grade of fluorite concentrate is improved.

2. The rough concentration operation of the invention carries out fluorite ore flotation under the condition of lower temperature (20-25 ℃), and compared with the conventional fluorite ore heating flotation (about 35 ℃), the invention can obviously reduce the energy consumption generated by heating and reduce the ore dressing cost.

3. The invention optimizes the process flow, adopts the process flow of one-coarse two-scavenging six-fine, and adopts the process flow of the direct return-back two-operation of the fine-medium ore after the regrinding of the coarse ore concentrate, thereby reducing the circulating load of the medium ore, being easy to implement and control on site, achieving the purpose of fine scavenging on the other hand, and avoiding the problems that the impurity content of the ore concentrate product is high, the technical index of the target mineral cannot achieve the satisfactory flotation effect and the like caused by the circulation of a large amount of slime.

4. According to the invention, the combination of the gangue inhibitor T20 and the acidic water glass is added in the flotation operation, and the organic inhibitor and the inorganic inhibitor are used in combination, so that the synergistic effect among different agents is exerted, and the contents of silicon dioxide and calcium carbonate in the concentrate product are effectively reduced. The main components of the gangue inhibitor T20 are PASP, aluminum sulfate and hydroxyethylidene diphosphonic acid, firstly, PASP in the components, namely polyaspartic acid, is a gangue mineral inhibitor, the molecular structure of the gangue mineral inhibitor contains a large number of carboxyl groups and other groups, the hydrophilicity of the surface of gangue minerals can be enhanced, the gangue mineral inhibitor has stronger selective adsorption effect on the surface of gangue minerals such as quartz, calcite and the like, and the gangue inhibitor is non-toxic, soluble in water, completely biodegradable and especially suitable for flotation separation of high-calcium fluorite ores; secondly, the aluminum sulfate in the components has the inhibiting effect on the gangue minerals, plays a role in dispersing slime, and can enhance the inhibition on the gangue minerals by being matched with an organic inhibitor; thirdly, under the weak acidic condition, the hydroxyethylidene diphosphonic acid in the components can assist the polyaspartic acid and the aluminum sulfate to strengthen the selective inhibition effect on calcite and quartz.

5. Compared with the conventional collecting agent, the collecting agent Y-8 has the advantages of small medicament dosage, good water solubility and good selective collecting effect on fluorite. The main components of the collecting agent Y-8 are oleic acid, 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether, firstly, the 4-oxo-tetradecanoic acid in the components is one of ether acids, and the collecting agent is characterized by strong collecting force, good selectivity, hard water and low temperature resistance, and capability of improving the collecting property and selectivity of the collecting agent; secondly, the polyethylene glycol mono-octyl phenyl ether in the components has the characteristics of good emulsifying and dispersing performance, and the dispersity and the collecting performance of the collecting agent can be improved; thirdly, the sodium oleate in the components is a conventional collecting agent for fluorite ore flotation, has stronger collecting capability, and can effectively solve the problems of poor selectivity, poor water solubility, low dispersivity, large using amount and the like of common oleic acid after being matched with 4-oxo-tetradecanoic acid and polyethylene glycol mono-octyl phenyl ether for use.

Drawings

FIG. 1 is a flow chart of a method for beneficiation of silicate and carbonate type fluorite ore according to the present invention.

Detailed Description

The following examples further illustrate the invention but are not intended to limit the invention in any way.

FIG. 1 shows the process scheme of the present invention, wherein a represents sulfuric acid, b represents gangue depressant T20, c represents acidic water glass, and d represents collector Y-8.