阅读说明：本技术 一种用工业级铍制备氟化铍的方法 (Method for preparing beryllium fluoride from industrial-grade beryllium ) 是由 行卫东 陈小浪 朱刘 于 2019-10-08 设计创作，主要内容包括：本发明提供了一种用工业级铍制备氟化铍的方法,包括以下步骤：(1)将工业级铍用酸溶液浸出；(2)浸出液采用有机萃取剂萃取,得到负载有机相；(3)使用酸溶液洗涤负载有机相；(4)使用氟化氢铵水溶液萃取步骤(3)得到的负载有机相,萃取完毕后收集水相；(5)使用氨水调节步骤(4)得到的水相的pH值为5～8,除去沉淀获得滤液；(6)将步骤(5)得到的滤液在70～130℃度下浓缩结晶得到氟铍酸铵；(7)将氟铍酸铵在850～1000℃煅烧得到氟化铍。本发明方法依次将酸浸提、萃取、酸洗、氟化氢铵水溶液萃取、氨水除杂、浓缩结晶和煅烧结合起来制备氟化铍,得到的氟化铍的纯度高于99.95％。(The invention provides a method for preparing beryllium fluoride from industrial-grade beryllium, which comprises the following steps: (1) leaching industrial grade beryllium with an acid solution; (2) extracting the leachate by using an organic extractant to obtain a loaded organic phase; (3) washing the loaded organic phase with an acid solution; (4) extracting the loaded organic phase obtained in the step (3) by using an ammonium bifluoride aqueous solution, and collecting a water phase after extraction is finished; (5) adjusting the pH value of the water phase obtained in the step (4) to 5-8 by using ammonia water, and removing precipitates to obtain a filtrate; (6) concentrating and crystallizing the filtrate obtained in the step (5) at 70-130 ℃ to obtain ammonium fluoberyllate; (7) and calcining ammonium fluoberyllate at 850-1000 ℃ to obtain beryllium fluoride. The method combines acid leaching, extraction, acid washing, ammonium bifluoride aqueous solution extraction, ammonia water impurity removal, concentration crystallization and calcination in sequence to prepare the beryllium fluoride, and the purity of the obtained beryllium fluoride is higher than 99.95%.)

1. A method for preparing beryllium fluoride from industrial-grade beryllium, comprising the steps of:

(1) leaching industrial-grade beryllium with an acid solution, and performing solid-liquid separation to obtain a leaching solution;

(2) adding an organic extracting agent into the leachate obtained in the step (1) for extraction, wherein the organic extracting agent takes one or two of methyl isobutyl ketone, tributyl phosphate, sec-octanol, di (2-ethylhexyl) phosphate and 2-ethylhexyl phosphate mono-2-ethylhexyl as solutes and sulfonated kerosene as a solvent, and collecting a loaded organic phase after extraction;

(3) washing the loaded organic phase obtained in the step (2) by using an acid solution, and collecting the loaded organic phase after washing;

(4) extracting the loaded organic phase obtained in the step (3) by using an ammonium bifluoride aqueous solution, and collecting a water phase after extraction is finished;

(5) adjusting the pH value of the water phase obtained in the step (4) to 5-8 by using ammonia water, and removing solid precipitates to obtain a filtrate;

(6) concentrating and crystallizing the filtrate obtained in the step (5) at 70-130 ℃ to obtain ammonium fluoberyllate;

(7) and calcining ammonium fluoberyllate at 850-1000 ℃ to obtain beryllium fluoride.

2. The method according to claim 1, wherein in the step (2), the volume ratio of the leachate to the organic extractant is 1: (1-10), wherein the volume ratio of solute in the organic extractant is 15-55%.

3. The method according to claim 1, wherein in the step (4), the concentration of the ammonium bifluoride in the aqueous ammonium bifluoride solution is 10-250 g/L, and the volume ratio of the aqueous ammonium bifluoride solution to the loaded organic phase obtained in the step (3) in the extraction process is 1: (1-10).

4. The method according to claim 1, wherein in the step (1), the acid solution is a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution or a hydrofluoric acid solution, the concentration of the sulfuric acid solution is 49-98 g/L, the concentration of the nitric acid solution is 32.5-65 g/L, the concentration of the hydrochloric acid solution is 17.5-35 g/L, and the concentration of the hydrofluoric acid solution is 17.5-35 g/L.

5. The method as claimed in claim 4, wherein the ratio of the technical beryllium to the acid solution used in step (1) is 1:5 by weight.

6. The method according to claim 1, wherein in the step (1), stirring is carried out during leaching, the stirring speed is 0-200 rpm, the leaching temperature is 25-80 ℃, and the leaching time is 1-4 h.

7. The method according to claim 1, wherein in the step (3), the acid solution is a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution or a hydrofluoric acid solution, the concentration of the sulfuric acid solution is 9.8-49 g/L, the concentration of the nitric acid solution is 6.5-32.5 g/L, the concentration of the hydrochloric acid solution is 3.5-17.5 g/L, and the concentration of the hydrofluoric acid solution is 3.5-17.5 g/L.

8. The method of claim 1, wherein in the step (7), the calcination time is 1-3 h.

9. The method according to claim 1, wherein in the step (3), the loaded organic phase obtained in the step (2) is washed with an acid solution 2 to 3 times.

10. The method according to claim 2, wherein the industrial-grade beryllium is industrial crude beryllium beads, and in the step (2), the volume ratio of the leaching solution to the organic extractant is 1: (3-10).

Technical Field

The invention belongs to the field of preparation of metallurgical materials, and particularly relates to a method for preparing beryllium fluoride from industrial-grade beryllium.

Background

The prior preparation process of industrial-grade beryllium metal mainly comprises the following methods: melting electrolysis, pyrolysis of beryllium hydride, vacuum distillation, alkali metal reduction and other process methods. Then, industrial-grade beryllium metal is prepared into beryllium chloride, beryllium oxide or beryllium fluoride and the like for application.

Application No. 201310371862.0 discloses a method for recovering beryllium from a chrysophyte-type beryllium concentrate with a low beneficiation enrichment ratio.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a method for preparing beryllium fluoride from industrial-grade beryllium.

In order to achieve the purpose, the invention adopts the technical scheme that: a method for making beryllium fluoride from technical grade beryllium, comprising the steps of:

(1) leaching industrial-grade beryllium with an acid solution, and performing solid-liquid separation to obtain a leaching solution;

(2) adding an organic extracting agent into the leachate obtained in the step (1) for extraction, wherein the organic extracting agent takes one or two of methyl isobutyl ketone (MIBK), tributyl phosphate (TBP), sec-octanol, di (2-ethylhexyl) phosphate (P207) and 2-ethylhexyl mono 2-ethylhexyl phosphate (P507) as solutes and sulfonated kerosene as a solvent, and collecting a loaded organic phase after extraction is finished;

(3) washing the loaded organic phase obtained in the step (2) by using an acid solution, and collecting the loaded organic phase after washing;

(4) extracting the loaded organic phase obtained in the step (3) by using an ammonium bifluoride aqueous solution, and collecting a water phase after extraction is finished;

(5) adjusting the pH value of the water phase obtained in the step (4) to 5-8 by using ammonia water, and removing solid precipitates to obtain a filtrate;

(6) concentrating and crystallizing the filtrate obtained in the step (5) at 70-130 ℃ to obtain ammonium fluoberyllate;

(7) and calcining ammonium fluoberyllate at 850-1000 ℃ to obtain beryllium fluoride.

The method combines acid leaching, extraction, acid pickling, extraction with an ammonium bifluoride aqueous solution, impurity removal with ammonia water, concentration and crystallization and calcination in sequence to prepare the beryllium fluoride, and the purity of the obtained beryllium fluoride is higher than 99.9%. In the step (1), the main metal beryllium and a small amount of impurity metals in the industrial beryllium are leached out through an acid solution, and the leaching residues can be continuously recycled as the industrial beryllium; after the treatment of the step (4), the concentration of aluminum ions in the collected water phase is less than 10mg/L, and the concentration of other metal ions is less than 1mg/L, so that the purity of the final product is greatly improved; in the method, ammonium fluoberyllate is crystallized in the step (6) and the step (7) is calcined to obtain the beryllium fluoride, so that the purity of the beryllium fluoride product is improved, and the flue gas generated by calcination can be recycled to prepare corresponding fluoride salt for reuse.

Preferably, in the step (2), the volume ratio of the leachate to the organic extractant is 1: (1-10), wherein the volume ratio of solute in the organic extractant is 15-55%.

More preferably, in the step (2), the volume ratio of the leachate to the organic extractant is 1: (3-10).

The extraction efficiency is higher under the condition of the volume ratio, and the dosage of the extractant is less.

Preferably, in the step (4), the concentration of ammonium bifluoride in the aqueous solution of ammonium bifluoride is 10-250 g/L, and the volume ratio of the aqueous solution of ammonium bifluoride to the loaded organic phase obtained in the step (3) in the extraction process is 1: (1-10).

Under the concentration and the dosage of the ammonium bifluoride aqueous solution, the extraction effect is better, the impurity ions are effectively reduced from entering the aqueous phase, and the purity of beryllium in the aqueous phase is improved.

Preferably, the organic phase remaining after collecting the aqueous phase in step (4) is used as the organic extractant in step (2).

The recycling of the organic phase collected in the step (4) can save organic solvent and reduce environmental pollution.

Preferably, in the step (1), the acid solution is a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution or a hydrofluoric acid solution, the concentration of the sulfuric acid solution is 49-98 g/L, the concentration of the nitric acid solution is 32.5-65 g/L, the concentration of the hydrochloric acid solution is 17.5-35 g/L, and the concentration of the hydrofluoric acid solution is 17.5-35 g/L.

Preferably, in the step (1), the weight ratio of the industrial-grade beryllium to the acid solution is 1: 5.

Under the acid solution concentration and the dosage, the leaching efficiency is higher, and the leaching rate of impurity metals is low.

Preferably, in the step (1), stirring is performed in the leaching process, the stirring speed is 0-200 rpm, the leaching temperature is 25-80 ℃, and the leaching time is 1-4 hours.

Preferably, in the step (3), the acid solution is a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution or a hydrofluoric acid solution, the concentration of the sulfuric acid solution is 9.8-49 g/L, the concentration of the nitric acid solution is 6.5-32.5 g/L, the concentration of the hydrochloric acid solution is 3.5-17.5 g/L, and the concentration of the hydrofluoric acid solution is 3.5-17.5 g/L.

Preferably, in the step (6), the filtrate obtained in the step (5) is concentrated and crystallized at 70-130 ℃ to obtain ammonium fluoberyllate, and then the ammonium fluoberyllate is re-dissolved, concentrated and crystallized, and repeated for 3-4 times.

The ammonium fluoberyllate can be further purified by re-dissolving, concentrating and crystallizing.

Preferably, in the step (7), the calcination time is 1-3 h.

Preferably, in the step (3), the loaded organic phase obtained in the step (2) is washed with an acid solution 2-3 times.

In the step (3), the washing is carried out for 2-3 times by using the acid solution, so that the using amount of the washing liquid can be saved, and the washing effect is improved.

Preferably, the industrial-grade beryllium is industrial coarse beryllium beads.

In the step (2), the extraction time is 5-15 min, and the extraction mode is mixing and shaking.

In the step (4), the extraction time is 5-15 min, and the extraction mode is mixing and shaking.

The invention has the beneficial effects that: the invention provides a method for preparing beryllium fluoride from industrial-grade beryllium, which combines acid leaching, extraction, acid washing, ammonium bifluoride aqueous solution extraction, ammonia water impurity removal, concentration crystallization and calcination to prepare the beryllium fluoride, wherein the purity of the obtained beryllium fluoride is higher than 99.9%. The method of the invention has the following advantages: (1) industrial crude beryllium beads are adopted as raw materials, a small amount of impurity metals are mixed in the pickle liquor, part of beryllium metals are leached at the same time, the leaching residues can be continuously used as the industrial crude beryllium, and the beryllium metals are fully utilized without loss; (2) the acid leaching solution can be directly used for extracting and separating beryllium, and the loaded organic phase is subjected to acid washing and purification and then extracted by high-purity ammonium bifluoride to obtain a high-purity ammonium fluoberyllate solution, wherein the concentration of aluminum is less than 10mg/L, and the concentration of other impurity metal ions is less than 1 mg/L; (3) the method has simple operation, low equipment investment and no waste gas and waste water discharge; (4) the flue gas generated by calcination in the method can be recycled to prepare corresponding fluoride salt for reuse, so that the effective circulation of valuable metals and resources is realized; (4) the pickling solution remained after the organic phase is collected in the step (3) can be used for leaching in the step (1), so that the pickling solution is saved.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.