阅读说明：本技术 一种低度apt渣中富集锡的方法 (Method for enriching tin in low-grade APT slag ) 是由 朱国平 张仲军 杨剑 杨乐能 廖云秀 于 2019-10-17 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渣中富集锡的方法,包括四次连续富集工艺；第一次富集工艺完成后,APT渣中的锡元素含量可提升到1.2-1.5倍,含量达到0.72％-1.20％；第二次富集工艺完成后,APT渣中的锡元素含量再提升到1.2-1.5倍,含量达到0.86％-1.80％；第三次富集工艺完成后,APT渣中的锡元素含量再提升到1.5-2.0倍,含量达到1.29％-3.60％；第四次富集工艺完成后,APT渣中的锡元素含量再提升到8.0-12.0倍,含量达到15.0％-30.2％；经过四次富集综合折算,锡元素总的回收率为73.9％-80.5％。对于本发明,通过四次连续的富集工艺,有效地对锡元素进行富集,工艺简单,可操作性强,生产成本低,对环境友好,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 tin in low-grade APT slag, which comprises four times of continuous enrichment processes, wherein after times of enrichment processes are completed, the content of tin in the APT slag can be increased to 1.2-1.5 times and the content reaches 0.72% -1.20%, after the second time of enrichment processes are completed, the content of tin in the APT slag is increased to 1.2-1.5 times and the content reaches 0.86% -1.80%, after the third time of enrichment processes are completed, the content of tin in the APT slag is increased to 1.5-2.0 times and the content reaches 1.29% -3.60%, after the fourth time of enrichment processes are completed, the content of tin in the APT slag is increased to 8.0-12.0 times and the content reaches 15.0% -30.2%, and after four times of enrichment processes are comprehensively converted, the total recovery rate of tin is 73.9% -80.5%.)

1, method for enriching tin in low-grade APT slag, which is characterized by comprising four 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 the th cleaning residue obtained in the step S3 to adjust the pH value, stirring, and performing pressure filtration to realize residue-liquid separation to obtain a second pressure filtration liquid and a second pressure filtration residue;

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, feeding the third press filtrate obtained in the step S6 into other metal recovery process;

the fourth enrichment process comprises the following steps:

s8, performing ball milling on the third filter-pressing residue obtained in the step S6, wherein the ball milling fineness is 300 meshes, and obtaining ore pulp;

s9, performing table roughing on the ore pulp obtained in the step S8 to obtain a rough concentrate from a concentrate end;

and S10, carrying out table concentration on the rough concentrate obtained in the step S9, wherein the material discharged from the concentrate end is the enriched tin concentrate.

2. The method of claim 1, wherein in step S1, 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).

3. The method for enriching tin in low-grade APT slag according to claim 1, characterized in that: 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; the stirring speed is 80-120r/min, and the stirring time is 50-70 minutes.

4. The method for enriching tin 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, filter pressing is carried out, the th cleaning slag and the th cleaning liquid are obtained, and the th cleaning liquid can be recycled in the process of adjusting the pH value in step S2.

5. The method for enriching tin in low-grade APT slag according to claim 1, characterized in that: 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; the stirring speed is 80-120r/min, and the stirring time is 50-70 minutes.

6. The method for enriching tin in low-APT slag according to claim 1, wherein in step S5, the second press filtration 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 press filtration 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 tin in low-grade APT slag according to claim 1, characterized in that: 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); and (3) adding the concentrated sulfuric acid, and stirring for 80-100 minutes at the temperature of 50-60 ℃ and the stirring speed of 80-120 r/min.

8. The method for enriching tin in low-grade APT slag according to claim 1, characterized in that: in step S8, the solid-liquid mass ratio during ball milling is 1 (2.3-3.0), so that the concentration of the ore pulp is controlled to be 25% -30%.

9. The method for enriching tin in low-grade APT slag according to claim 1, characterized in that: in step S9, the roughing gradient is 5 degrees, and the vibration frequency is 60 times/min; and step S10, the selected gradient is 3.5 degrees, and the vibration frequency is 80 times/min.

10. The method for enriching tin in low-grade APT slag according to claim 1, characterized in that: in step S9 and step S10, the shaking table water can be collected and precipitated and then continuously used for the shaking table process, and the tailings except the slag discharged from the concentrate end can be sold to a cement plant or a brick factory.

Technical Field

The invention relates to the technical field of comprehensive resource recycling, in particular to a method for enriching tin 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 tin cannot achieve economic benefits, and how to discuss a new process to enable the 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 tin 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 tin in kinds of low-grade APT slag, effectively enriches tin elements by four times of 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 tin in low-grade APT slag, which comprises four 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, the th press filtrate obtained in the step S2 is subjected to other metal recovery processes (metal recovery processes such as iron, copper, silver and the like), and the th press residue obtained in the step S2 is washed by clean water to obtain th washing residue and th washing liquid;

the second enrichment process comprises the following steps:

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

s5, enabling the second press-filtered liquid obtained in the step S4 to enter other metal recovery procedures (metal recovery procedures such as iron, copper, silver and the like), and cleaning the second press-filtered residue obtained in the step S4 with clean water to obtain second cleaning slag 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, introducing the third press filtrate obtained in the step S6 into a step of recovering other metals (tungsten and iron recovery step);

the fourth enrichment process comprises the following steps:

s8, performing ball milling on the third filter-pressing residue obtained in the step S6, wherein the ball milling fineness is 300 meshes, and obtaining ore pulp;

s9, performing table roughing on the ore pulp obtained in the step S8 to obtain a rough concentrate from a concentrate end;

and S10, carrying out table concentration on the rough concentrate obtained in the step S9, wherein the material discharged from the concentrate end is the enriched tin concentrate.

, 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, the stirring speed is 80-120r/min, the stirring time is 50-70 minutes, preferably, the concentration of the dilute hydrochloric acid is 5%, the pH value of the adjusted solution is 7, the stirring speed is 60 minutes, and copper, silver, calcium, small amount of silicon and the like are removed under a neutral condition.

The stirring speed and the stirring time are set so as to ensure that the slag and the acid solution are fully combined and reacted, remove other substances and better enrich the tin element.

, 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, the stirring speed is 80-120r/min, and the stirring time is 50-70 minutes, preferably, the concentration of the dilute hydrochloric acid is 7%, the pH value of the adjusted solution is 1.0, and the stirring speed is 60 minutes, so as to better remove impurities.

The stirring speed and the stirring time are set so as to ensure that the slag and the acid solution are fully combined and reacted, remove other substances and better enrich the tin element.

, 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), when the concentrated sulfuric acid is added and stirred, the temperature is controlled to be 50-60 ℃, the stirring speed is 80-120r/min, and the stirring time is 80-100 minutes.

The stirring speed and the stirring time are set so as to ensure that the slag and the acid solution are fully combined and reacted, remove other substances and better enrich the tin element. The temperature is controlled to be about 55 ℃ because the concentrated sulfuric acid releases heat energy after being added, and the reaction of the second cleaning slag and the concentrated sulfuric acid is influenced by overhigh temperature.

, in step S8, the solid-liquid mass ratio is 1 (2.3-3.0) during ball milling, so that the concentration of the ore pulp is controlled to be 25% -30% during discharging, and the separation effect is better in the shaking table process.

, in step S9, the rough gradient is 5 degrees and the vibration frequency is 60 times/min, and in step S10, the fine gradient is 3.5 degrees and the vibration frequency is 80 times/min.

, in step S9 and step S10, the water used by the shaking table can be collected and precipitated and then continuously used for the shaking table process, and the tailings except the slag discharged from the concentrate end can be sold to a cement plant or a brick plant, so that the waste water and the tailings can be recycled, the cost is saved, and the environment is protected.

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

the method for enriching tin in low-grade APT slag disclosed by the invention has the advantages that four continuous enrichment processes are carried out on slag materials with the tin element content of 0.6-0.8%, after times of enrichment processes are completed, the tin element content in the APT slag can be increased to 1.2-1.5 times and the tin element content reaches 0.72-1.20%, the recovery rate of the tin element is 96-98%, after the second time of enrichment processes are completed, the tin element content in the APT slag is increased to 1.2-1.5 times and the tin element content reaches 0.86-1.80%, the recovery rate of the tin element is 94-96%, after the third time of enrichment processes are completed, the tin element content in the APT slag is increased to 1.5-2.0 times and the tin element content reaches 1.29-3.60%, the recovery rate of the tin element is 92-94%, after the fourth time of enrichment processes are completed, the tin element content in the APT slag is increased to 8.0-12.0%, the tin element content reaches 15.0-3.60%, the tin element recovery rate is 92-94%, the recovery rate of the tin element is 92-94%, the tin element recovery rate is easily obtained by a large-scale production process, the industrial production process, the recovery rate of tin element is effectively increased, the recovery rate of tin element recovery of enterprises, the industrial production is increased, the industrial production cost of the industrial production is increased, the industrial production cost of the.

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 tin 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 Chenzhou tungsten slag material, Ganxianzhou tungsten slag material and Fujian tungsten slag material; the reagents and equipment used in the invention are all commercial products.