CN105331836B - A kind of method of outfield intensifying without ammonia leached ions type Rare Earth Mine - Google Patents

Abstract

The invention relates to a method for external field enhanced ammonia-free leaching of ionic rare earth ores, and belongs to the technical field of hydrometallurgy. Add the ionic rare earth ore to the ammonia-free salt leaching agent solution with a concentration of 1wt%~10wt% according to the liquid-solid ratio of 1:1~20:1ml/g, stir and leaching under the action of ultrasonic waves at room temperature for 10~180min, after the leaching is completed The leaching solution is obtained through liquid-solid separation, wherein the ammonia-free salt leaching agent is calcium chloride or a mixture of calcium chloride and magnesium sulfate in any ratio. The invention reduces the generation of ammonia nitrogen wastewater while ensuring a high rare earth leaching rate, and is a green and economical new process.

Description

A method for external field enhanced ammonia-free leaching of ionic rare earth ores

technical field

The invention relates to a method for external field enhanced ammonia-free leaching of ionic rare earth ores, and belongs to the technical field of hydrometallurgy.

Background technique

Rare earths are recognized worldwide as an indispensable strategic resource for the development of high-tech, cutting-edge defense technologies, and transformation of traditional industries. Ionic rare earth ores have a complete distribution of light, medium and heavy rare earths, and are rich in medium and heavy rare earth elements that are closely related to high-tech, high-tech, and new material industries. The development and utilization of ionic rare earth ores occupies an important strategy in my country's economic development status.

Sodium chloride and ammonium sulfate are successively used as leaching agents in the leaching process of ionic rare earth ores. The leaching selectivity of ammonium sulfate is obviously better than that of sodium chloride, which is beneficial to the extraction of rare earth ions in the leach solution, and is currently the main method for rare earth leaching. Leaching agent. However, the ammonium sulfate leaching agent will bring a large amount of ammonia nitrogen wastewater. With an annual output of 3,000 tons of rare earth (REO), the amount of wastewater generated is about 1.8 million tons/year, and the discharge of ammonia nitrogen is about 6,000 tons/year. High; in addition, when ammonium sulfate leaches rare earths, the consumption of leaching agent is large, resulting in waste of resources. Therefore, the development of a green and efficient leaching process to reduce the pollution of ammonia nitrogen wastewater and realize economical and environmentally friendly rare earth extraction has far-reaching significance for the sustainable development of my country's rare earth industry.

In recent years, the external field enhanced leaching technology (ultrasonic wave) has been more and more used in the metallurgical industry, such as the enhanced leaching of gold, silver, and copper ores. Jet erosion makes the chemical reaction under the ultrasonic field easy to carry out, and achieves the enhanced leaching process, which has certain development prospects.

Contents of the invention

Aiming at the problems and deficiencies in the above-mentioned prior art, the present invention provides a method for intensified ammonia-free leaching of ion-type rare earth ores in an external field. The present invention reduces the generation of ammonia nitrogen wastewater while ensuring a high rare earth leaching rate, and is a green and economical new process. The present invention is realized through the following technical solutions.

A method for intensified ammonia-free leaching of ion-type rare earth ore in an external field, the specific steps are as follows: add ammonia-free salt with a concentration of 1wt% to 10wt% to the ion-type rare earth ore at a liquid-solid ratio of 1:1 to 20:1ml/g The leaching agent solution is stirred and leached under the action of ultrasonic waves at room temperature for 10 to 180 minutes. After the leaching is completed, the leaching solution is obtained through liquid-solid separation. The ammonium-free leaching agent is calcium chloride or a mixture of calcium chloride and magnesium sulfate in any ratio.

The ionic rare earth ores refer to southern ionic rare earth ores in which rare earths are adsorbed on clay minerals with hydrated ions or hydroxyl hydrated ions.

The power of the ultrasonic wave is above 100W.

The beneficial effects of the present invention are: (1) The present invention uses an ammonia-free leaching agent as a raw material, fundamentally solves the technical problem of ammonia nitrogen pollution, and conforms to the national industrial policy of developing the rare earth industry. (2) The present invention uses ultrasonic waves to strengthen the leaching of rare earths. This technology not only greatly improves the leaching rate, but also has the advantages of simple operation and no pollution. (3) The rare earth leaching rate can reach up to 99.62% through the method of the present invention, while the rare earth leaching rate is 72.55% during ammonium sulfate leaching, an increase of 37.31%.

detailed description

The present invention will be further described below in combination with specific embodiments.

Example 1

The method for the field-enhanced ammonia-free leaching of ionic rare earth ores, the specific steps are as follows: 1 kg of ionic rare earth ores (ionic rare earth ores refer to southern ionic rare earth ores in which rare earths are adsorbed on clay minerals with hydrated ions or hydroxyl hydrated ions) , the mass percentage components are shown in Table 1) According to the liquid-solid ratio of 1:1ml/g, add the ammonia-free salt leaching agent solution with a concentration of 1wt%, stir and leaching under the action of ultrasonic waves at room temperature for 10min, after the leaching is completed, the liquid-solid The leaching solution is separated and obtained, wherein the ammonium-free leaching agent is calcium chloride, and the ultrasonic power is 1500W.

Table 1

The leaching rate of the rare earth was measured by EDTA titration method for the leachate prepared in this example, and the leaching rate under this condition was 92.34%.

Example 2

The method for the field-enhanced ammonia-free leaching of ionic rare earth ores, the specific steps are as follows: 1 kg of ionic rare earth ores (ionic rare earth ores refer to southern ionic rare earth ores in which rare earths are adsorbed on clay minerals with hydrated ions or hydroxyl hydrated ions) , the mass percentage components are shown in Table 2) According to the liquid-solid ratio of 20:1ml/g, add the ammonia-free salt leaching agent solution with a concentration of 10wt%, and stir and leaching under the action of ultrasonic waves at room temperature for 180min. After the leaching is completed, the liquid-solid The leaching solution is separated and obtained, wherein the ammonium-free leaching agent is a mixture of calcium chloride and magnesium sulfate with a mass ratio of 1:1, and the ultrasonic power is 100W.

Table 2

The leaching rate of the rare earth was measured by EDTA titration method for the leachate prepared in this example, and the leaching rate under this condition was 99.62%.

Example 3

The method for the field-enhanced ammonia-free leaching of ionic rare earth ores, the specific steps are as follows: 1 kg of ionic rare earth ores (ionic rare earth ores refer to southern ionic rare earth ores in which rare earths are adsorbed on clay minerals with hydrated ions or hydroxyl hydrated ions) , the mass percentage components are shown in Table 3) According to the liquid-solid ratio of 10:1ml/g, add the ammonia-free salt leaching agent solution with a concentration of 8wt%, and stir and leaching under the action of ultrasonic waves at room temperature for 120min. After the leaching is completed, the liquid-solid The leaching solution is separated and obtained, wherein the ammonium-free leaching agent is a mixture of calcium chloride and magnesium sulfate with a mass ratio of 2:1, and the ultrasonic power is 1500W.

table 3

The leaching rate of the rare earth was measured by the EDTA titration method for the leachate prepared in this example, and the leaching rate under this condition was 93.68%.

The specific embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the gist of the present invention within the scope of knowledge possessed by those of ordinary skill in the art .

Claims (1)

1. method of a kind of outfield intensifying without ammonia leached ions type Rare Earth Mine, it is characterised in that comprise the following steps that：By ionic Rare Earth Mine, ion type rareearth ore refer to that rare earth adsorbs the southern ion on clay mineral with hydrated ion or hydroxyl hydrated ion Type Rare Earth Mine, it is 1 according to liquid-solid ratio:1ml/g adds concentration and leaches agent solution without ammonia salt for 1wt%, in the work of room temperature ultrasonic With lower leaching 10min, leach and obtain leachate through solid-liquor separation after completing, wherein being calcium chloride without ammonia salt leaching agent, surpass The power of sound wave is 1500W.