阅读说明：本技术 一种低度apt渣中富集钨的方法 (Method for enriching tungsten in low-grade APT slag ) 是由 杨剑 廖云秀 杨乐能 朱国平 张仲军 于 2019-10-16 设计创作，主要内容包括：本发明涉及资源综合回收利用技术领域,公开了一种低度APT渣中富集钨的方法,包括三次连续富集工艺；第一次富集工艺完成后,APT渣中的钨元素含量可提升到1.3-1.5倍,含量达到1.01％-2.70％；第二次富集工艺完成后,APT渣中的钨元素含量再提升到1.2-1.3倍,含量达到1.32％-3.51％；第三次富集工艺完成后,APT渣中的钨元素含量再提升到2-3.5倍,含量达到4.62％-12.28％；经过三次富集综合折算,钨元素总的回收率为86.6％-92.2％。对于本发明,通过三次连续的富集工艺,有效地对钨元素进行富集,工艺简单,可操作性强,生产成本低,使生产企业取得可观经济效益,且清洗渣料后的废水可以循环使用,对环境友好,易于实现工业规模化生产,实现了对环境保护、社会效益和企业经济效益的多赢。(The invention relates to the technical field of comprehensive recycling of resources, and discloses a method for enriching tungsten in low-grade APT slag, which comprises a three-time continuous enrichment process, wherein after the -time enrichment process is completed, the content of tungsten in the APT slag can be increased to 1.3-1.5 times and the content reaches 1.01-2.70%, after the second-time enrichment process is completed, the content of tungsten in the APT slag is increased to 1.2-1.3 times and the content reaches 1.32-3.51%, after the third-time enrichment process is completed, the content of tungsten in the APT slag is increased to 2-3.5 times and the content reaches 4.62-12.28%, and after the three-time comprehensive conversion of enrichment, the total recovery rate of tungsten is 86.6-92.2%.)

The method for enriching tungsten in low-grade APT slag is characterized by comprising three continuous enrichment processes;

the th enrichment process comprises the following steps:

s1, adding the APT slag into the liquid for ball milling, wherein the ball milling fineness is 300 meshes, and placing the mixture into a stirring tank for stirring;

s2, adding dilute hydrochloric acid in the stirring process of the step S1 to adjust the pH value, stirring, and performing pressure filtration to realize residue-liquid separation to obtain a th pressure filtrate and a th pressure filtration residue;

s3, enabling the th press filtrate obtained in the step S2 to enter other metal recovery procedures, and cleaning the th press filter residue obtained in the step S2 with clean water to obtain th cleaning residue and th cleaning liquid;

the second enrichment process comprises the following steps:

s4, adding dilute hydrochloric acid into part of the th cleaning slag obtained in the step S3 to adjust the pH value, stirring and then performing pressure filtration to realize slag-liquid separation, and obtaining a second pressure filtration liquid and a second pressure filtration slag;

s5, enabling the second press-filtered liquid obtained in the step S4 to enter other metal recovery procedures, and cleaning the second press-filtered residues obtained in the step S4 with clear water to obtain second cleaning residues and second cleaning liquid;

the third enrichment process comprises the following steps:

s6, adding concentrated sulfuric acid into the second cleaning slag obtained in the step S5, stirring, and performing pressure filtration to realize slag-liquid separation to obtain a third pressure filtrate and a third pressure filtration slag;

s7, performing other metal recovery procedures on the third filter-pressing residue obtained in the step S6, and performing pH value adjustment twice on the third filter-pressing liquid obtained in the step S6, wherein after the pH value is adjusted times, filter pressing is performed to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue, and the fourth filter-pressing liquid is subjected to the pH value adjustment for the second time, and filter pressing is performed to obtain a fifth filter-pressing liquid and a fifth filter-pressing residue;

and S8, feeding the fifth pressure filtrate obtained in the step S7 into other metal recovery procedures, wherein the fifth pressure filtration residue obtained in the step S7 is an enriched tungsten residue product.

2. The method of claim 1, wherein the liquid is clean water, the cleaning solution or the second cleaning solution, and the ratio of the APT slag to the liquid is 1 (1.5-2.5) in step S1.

3. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein: in step S2, the concentration of the added dilute hydrochloric acid is 4% -6%, and the pH value of the adjusted solution is 6-8.

4. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein in step S3, the th filter-pressing slag is cleaned with clean water for times, the solid-liquid mass ratio during cleaning is 1 (1-3), the stirring time is 20-40 minutes, and filter pressing is carried out to obtain th cleaning slag and th cleaning liquid, and the th cleaning liquid can be recycled in the process of adjusting the pH value in step S2.

5. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein: in step S4, the concentration of the added dilute hydrochloric acid is 6% -8%, and the pH value of the adjusted solution is 0.8-1.2.

6. The method for enriching tungsten in low-APT slag according to claim 1, wherein in step S5, the second filter-pressing slag is washed times with clear water, the solid-liquid mass ratio during washing is 1 (1-3), the stirring time is 20-40 minutes, and the filter pressing is carried out to obtain the second washing slag and the second washing liquid, and the second washing liquid can be recycled in the process of adjusting the pH value in step S4.

7. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein: in step S6, the concentration of the added concentrated sulfuric acid is 90%, and the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1 (0.5-1.5).

8. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein: in step S6, the temperature is controlled to 50 to 60 ℃ while stirring after the concentrated sulfuric acid is added.

9. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein: in step S7, the PH of the third press filtrate is adjusted as follows:

1) adding part of cleaning slag obtained in the step S3 into the third pressure filtrate, adjusting the pH value to 0.4-0.6, and performing pressure filtration to realize slag-liquid separation to obtain a fourth pressure filtrate and fourth pressure filter slag;

2) and (2) feeding the fourth filter-pressing residue obtained in the step (1) into the step (S6), adding iron powder into the fourth filter-pressing residue obtained in the step (1), adjusting the pH value to 2.5-3.0, wherein the tungsten element becomes heteropoly acid and precipitates, performing filter pressing, and realizing residue-liquid separation to obtain the fifth filter-pressing residue and the fifth filter-pressing residue.

10. The method for enriching tungsten in low-grade APT slag according to claim 1, wherein: in step S2, the stirring speed is 80-120r/min, and the stirring time is 50-70 minutes; in step S4, the stirring speed is 80-120r/min, and the stirring time is 50-70 minutes; in step S6, the stirring speed is 80-120r/min, and the stirring time is 80-100 minutes.

Technical Field

The invention relates to the technical field of comprehensive resource recycling, in particular to a method for enriching tungsten in low-grade APT (ammonium paratungstate) slag.

Background

China has listed the comprehensive utilization industry of resources into a strategic emerging industry. At present, about 70 ten thousand tons of waste APT (ammonium paratungstate) production slag exist in China, and about 15 ten thousand tons of newly added slag are added every year. With the increasingly mature technology of APT manufacturers, the content of the residual tungsten in the produced production slag is reduced to 0.7-1.8% from the previous 3-5%. For waste recycling enterprises, the traditional simple production method for recycling tungsten cannot achieve economic benefits, and how to discuss a new process to enable enterprises to have power and benefit for recycling becomes a development direction of waste disposal.

Therefore, it is urgently needed to develop low-cost production processes to realize better 'enrichment' of tungsten element in low-grade APT slag, so that production enterprises can obtain considerable economic benefits, and further realize multiple benefits of environmental protection, social benefits and enterprise economic benefits.

Disclosure of Invention

In order to overcome the technical problems in the prior art, the invention aims to provide a method for enriching tungsten in low-grade APT slag, which effectively enriches tungsten elements by three continuous enrichment processes, has simple process, strong operability and low production cost, and realizes multiple benefits of environmental protection, social benefit and enterprise economic benefit.

In order to solve the problems, the invention is realized according to the following technical scheme:

method for enriching tungsten in low-grade APT slag, which comprises three times of continuous enrichment process;

the th enrichment process comprises the following steps:

s1, adding the APT slag into the liquid for ball milling, wherein the ball milling fineness is 300 meshes, and placing the mixture into a stirring tank for stirring;

s2, adding dilute hydrochloric acid in the stirring process of the step S1 to adjust the pH value, stirring, and performing pressure filtration to realize residue-liquid separation to obtain a th pressure filtrate and a th pressure filtration residue;

s3, enabling the th press filtrate obtained in the step S2 to enter other metal recovery processes (iron, copper and silver recovery processes), and cleaning the th press filter residue obtained in the step S2 with clean water to obtain th cleaning residue and th cleaning liquid;

the second enrichment process comprises the following steps:

s4, adding dilute hydrochloric acid into part of the th cleaning slag obtained in the step S3 to adjust the pH value, stirring and then performing pressure filtration to realize slag-liquid separation, and obtaining a second pressure filtration liquid and a second pressure filtration slag;

s5, enabling the second press-filtered liquid obtained in the step S4 to enter other metal recovery procedures (iron, copper and silver recovery procedures), and cleaning the second press-filtered residue obtained in the step S4 with clear water to obtain second cleaning residue and second cleaning liquid;

the third enrichment process comprises the following steps:

s6, adding concentrated sulfuric acid into the second cleaning slag obtained in the step S5, stirring, and performing pressure filtration to realize slag-liquid separation to obtain a third pressure filtrate and a third pressure filtration slag;

s7, performing other metal recovery procedures (tin recovery procedures) on the third filter-pressing residue obtained in the step S6, and performing pH value adjustment twice on the third filter-pressing liquid obtained in the step S6, wherein after the pH value is adjusted times, filter pressing is performed to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue, and the fourth filter-pressing liquid is subjected to the pH value adjustment for the second time, and filter pressing is performed to obtain a fifth filter-pressing liquid and a fifth filter-pressing residue;

s8, the fifth pressure filtration liquid obtained in the step S7 enters other metal recovery procedures (tin recovery procedures), and the fifth pressure filtration residue obtained in the step S7 is the enriched tungsten residue product.

, in step S1, the liquid is clear water, the th cleaning liquid or the second cleaning liquid, and the ratio of the APT slag to the liquid is 1 (1.5-2.5), so that the APT slag can be ground more fully.

, in step S2, the concentration of the added dilute hydrochloric acid is 4% -6%, the pH value of the adjusted solution is 6-8, preferably, the concentration of the dilute hydrochloric acid is 5%, the pH value of the adjusted solution is 7, when the concentration is more than 7%, tungsten can be leached out, the pH value is adjusted to 7, and mainly, substances dissolved in liquid in a neutral state, such as iron, copper, silver, calcium and the like, are removed.

, in the step S3, the th filter pressing residue is washed times with clean water, the solid-liquid mass ratio during washing is 1 (1-3), the stirring time is 20-40 minutes, filter pressing is conducted, the th washing residue and the th washing liquid are obtained, and the th washing liquid can be recycled in the PH value adjusting process in the step S2, so that waste water can be recycled, the cost is saved, and the environment is protected.

, in step S4, the concentration of the added dilute hydrochloric acid is 6% -8%, the pH value of the adjusted solution is 0.8-1.2, preferably, the concentration of the dilute hydrochloric acid is 7%, the pH value of the adjusted solution is 1.0, and , impurities such as iron, copper, silver, calcium, small amount of silicon and the like are removed.

, in the step S5, the second filter-pressing residues are washed with clean water for times, the solid-liquid mass ratio during washing is 1 (1-3), the stirring time is 20-40 minutes, filter pressing is conducted, the second washing residues and the second washing liquid are obtained, and the second washing liquid can be recycled in the process of adjusting the PH value in the step S4, so that the waste water can be recycled, the cost is saved, and the environment is protected.

, in step S6, the concentration of the added concentrated sulfuric acid is 90%, the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1 (0.5-1.5), preferably, the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1: 1, and when the ratio of the th cleaning slag to the concentrated sulfuric acid is 1: 1, the leaching effect is the best for leaching tungsten.

, in step S6, the temperature is controlled to 50-60 ℃ when stirring after adding the concentrated sulfuric acid, because the concentrated sulfuric acid releases heat energy after adding, and the reaction of the second cleaning slag and the concentrated sulfuric acid is affected by too high temperature.

, in step S7, the pH of the third press filtrate is adjusted as follows:

1) adding part of cleaning slag obtained in the step S3 into the third pressure filtrate, adjusting the pH value to 0.4-0.6, and performing pressure filtration to realize slag-liquid separation to obtain a fourth pressure filtrate and fourth pressure filter slag;

2) and (2) feeding the fourth filter-pressing residue obtained in the step (1) into the step (S6), adding iron powder into the fourth filter-pressing residue obtained in the step (1), adjusting the pH value to 2.5-3.0, wherein the tungsten element becomes heteropoly acid and precipitates, performing filter pressing, and realizing residue-liquid separation to obtain the fifth filter-pressing residue and the fifth filter-pressing residue.

When the pH value of the iron element is 0.4-0.6, precipitates are easy to form, so that the iron removal effect is achieved; tungsten tends to form heteropoly acid precipitates at pH 2.5-3.0.

, stirring at 80-120r/min for 50-70 min in S2, at 80-120r/min for 50-70 min in S4, at 80-120r/min for 80-100 min in S6, and setting the stirring speed and stirring time to make the slag and acid solution combine and react fully, remove other substances and enrich tungsten element better.

Compared with the prior art, the invention has the beneficial effects that:

according to the method for enriching tungsten in low-grade APT slag, slag with the tungsten element content of 0.72-1.80% is subjected to a three-time continuous enrichment process, after times of enrichment process is completed, the tungsten element content in the APT slag can be increased to 1.3-1.5 times and 1.01-2.70% and the recovery rate of the tungsten element is 96-98%, after the second time of enrichment process is completed, the tungsten element content in the APT slag is increased to 1.2-1.3 times and 1.32-3.51% and the recovery rate of the tungsten element is 96-98%, after the third time of enrichment process is completed, the tungsten element content in the APT slag is increased to 2-3.5 times and 4.62-12.28% and the recovery rate of the tungsten element is 94-96%, and after three times of enrichment process is completed, the total recovery rate of the tungsten element is 86.6-92.2%, the three-time of tungsten element is effectively enriched by the three-time of continuous process, the tungsten element is effectively subjected to the recovery rate of tungsten elements, the industrial production is simple, the economic benefit of enterprises is achieved, the environmental benefits of industrial production is achieved, the environmental protection, and the environmental benefits of enterprises are achieved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a process flow diagram of the method for enriching tungsten in low-grade APT slags.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only partial embodiments of the present invention, rather than all embodiments.

The APT slag selected by the invention is Ganzhou tungsten slag charge, Chenzhou tungsten slag charge and Fujian tungsten slag charge; the reagents and equipment used in the invention are all commercial products.