CN110760677A - Method for enriching iron, copper and silver coprecipitation material and calcium sulfate in low-grade APT slag - Google Patents
Method for enriching iron, copper and silver coprecipitation material and calcium sulfate in low-grade APT slag Download PDFInfo
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Abstract
The invention relates to the technical field of comprehensive recycling of resources, and discloses a method for enriching iron, copper and silver coprecipitation materials and calcium sulfate in low-grade APT slag, which comprises four continuous enrichment processes, wherein the iron, copper, silver and calcium elements in the original APT slag are enriched through the four enrichment processes, and the comprehensive conversion can be known as follows: the iron content is enriched from 18.83-20.15% to about 40.55-41.72%; the copper content is enriched from 0.28 to 0.33 percent to about 11.22 to 16.34 percent; the silver content is enriched from 66 g/t-78 g/t to 5910 g/t-7855 g/t; the original calcium content is 18.08-19.10%, and the calcium sulfate content in the product obtained by enrichment treatment reaches 88.37-90.45%. Therefore, the four-step continuous enrichment process effectively enriches the elements of iron, copper, silver and calcium, has simple process, strong operability and low production cost, and simultaneously, the cleaning solution and the filter pressing solution generated in the whole enrichment process are recycled, thereby not only reducing the waste of resources, but also reducing the pollution to the environment, and further realizing the win-win of environmental protection, social benefit and enterprise economic benefit.
Description
Technical Field
The invention relates to the technical field of comprehensive resource recycling, in particular to a method for enriching iron, copper and silver coprecipitation materials and calcium sulfate in low-grade APT slag.
Background
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. Although the content of tungsten in the produced production slag is reduced along with the gradual maturity of the technology of APT manufacturers, the waste of tungsten resources is reduced to a certain extent, the production slag contains many other valuable elements (such as copper, silver and the like) besides tungsten, and has a great recovery value. For waste recovery enterprises, the economic benefit cannot be obtained by only recovering tungsten from low-grade APT slag by adopting a traditional mode, so that a new method is urgently needed to be researched to enrich and recover valuable elements such as iron, copper, silver, calcium and the like except for tungsten from the low-grade APT slag, so that the production enterprises can obtain considerable economic benefit, and further multiple benefits of environmental protection, social benefit and enterprise economic benefit are realized.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention aims to provide a method for enriching iron, copper and silver coprecipitations and calcium sulfate in low-grade APT slag, which effectively enriches iron, copper, silver and calcium elements by four continuous enrichment processes, and has the advantages of simple process, strong operability and low production cost; meanwhile, the cleaning liquid and the filter pressing liquid generated in the whole enrichment process are recycled, so that the waste of resources is reduced, the pollution to the environment is reduced, and further, the win-win effect on environmental protection, social benefit and enterprise economic benefit is realized.
In order to solve the problems, the invention is realized according to the following technical scheme:
a method for enriching iron, copper and silver coprecipitation materials and calcium sulfate in low-grade APT slag comprises four continuous enrichment processes:
the first enrichment process comprises the following steps:
s1, adding clear water into the APT slag for ball milling, wherein the ball milling fineness is 300 meshes;
s2, under the condition of mechanical stirring, adding dilute hydrochloric acid into the APT slag obtained in the step S1 to adjust the pH value, continuing stirring when the pH value is adjusted to 6-8, and then performing pressure filtration to realize slag-liquid separation to obtain a first pressure filtrate and a first pressure filtration residue;
s3, storing the first press filtrate obtained in the step S2 for subsequent processes; cleaning the first filter-pressing residue obtained in the step S2 with clear water once, and performing filter-pressing separation to obtain first cleaning residue and first cleaning liquid;
the second enrichment process comprises the following steps:
s4, under the condition of mechanical stirring, adding dilute hydrochloric acid into the first cleaning slag obtained in the step S3 to adjust the pH value, continuing stirring when the pH value is adjusted to 1, and then performing pressure filtration to realize slag-liquid separation to obtain a second pressure filtration liquid and a second pressure filtration slag;
s5, storing the second press filtrate obtained in the step S4 for subsequent processes; cleaning the first filter-pressing residue obtained in the step S4 with clear water once, and performing filter-pressing separation 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 under the condition of mechanical stirring, and performing pressure filtration after stirring to realize slag-liquid separation to obtain a third pressure filtrate and a third pressure filter slag;
s7, feeding the third filter-pressing residue obtained in the step S6 into a tin recovery process, adjusting the pH value of the third filter-pressing liquid obtained in the step S6 by using the first filter-pressing residue obtained in the step S2, and performing filter-pressing separation when the pH value is adjusted to 0.5 to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue; wherein the fourth filter-press residue is recycled to the step of step S6;
the fourth enrichment process comprises the following steps:
s8, under the condition of mechanical stirring, mixing the first pressure filtrate obtained in the step S3, the second pressure filtrate obtained in the step S5 and the fourth pressure filtrate obtained in the step S7, stirring, press-filtering, and realizing residue-liquid separation to obtain a fifth pressure filtrate and fifth pressure-filtered residue; the fifth filter pressing residue is an enriched calcium sulfate product;
s9, adding iron powder into the fifth pressure filtrate obtained in the step S8 under the condition of mechanical stirring, adjusting the pH value through the reaction of iron and acid, continuing stirring when the pH value is adjusted to 2-2.5, and then performing pressure filtration to realize residue-liquid separation to obtain a sixth pressure filtrate and sixth pressure filter residue;
s10, enabling the sixth filter-pressing residue obtained in the step S9 to enter a tungsten recovery process; adding the pH value of calcium hydroxide into the sixth pressure filtrate obtained in the step S9 under the condition of mechanical stirring, continuously stirring and precipitating the sixth pressure filtrate when the pH value is 2.5-3.5, and performing pressure filtration after precipitation to realize residue-liquid separation to obtain seventh pressure filtrate and seventh pressure filter residue; and the seventh filter pressing residue is the enriched iron, copper and silver coprecipitation material.
Furthermore, in step S1, the liquid is clear water, and the solid-liquid mass ratio of the APT slag to the liquid is 1 (1.5-2.5), so that the APT slag can be sufficiently ground.
Further, in step S2 and step S4, the concentration of the added dilute hydrochloric acid is 4% to 8%, wherein, in step S2, the preferred concentration of the added dilute hydrochloric acid is 5%, and the pH of the adjusted solution is 7. When the concentration of the dilute hydrochloric acid is more than 7%, tungsten is easily decomposed by acid, so that the concentration is 5%. When neutral, the soluble salts are easily dissolved in neutral solution, mainly calcium, aluminum, etc. In step S4, the preferred concentration of the dilute hydrochloric acid added is 7%. 5% of dilute hydrochloric acid is used as initial solution, 7% is critical value, and soluble salt is dissolved again to separate.
Further, in step S3 and step S5, the cleaning is performed once with clean water, and the solid-liquid mass ratio in the cleaning is 1: (1-3); the first cleaning solution can be recycled for use in the pH adjustment process of step S2; the second cleaning solution can be recycled in the pH value adjusting process of the step S2 or the step S4, so that the waste water can be recycled, the cost is saved, and the environment is further protected.
Further, in step S6, the concentration of the added concentrated sulfuric acid is 88% to 92%, and the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1 (0.5 to 1.5); preferably, the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1:1. when the concentrated sulfuric acid is 88-92%, the tungsten can be effectively leached by acid.
Further, in step S6, the temperature is controlled to be 50-60 ℃ for filter pressing. Since the concentrated sulfuric acid releases heat energy after being added, the reaction effect is influenced by overhigh temperature.
Further, in step S10, the concentration of calcium hydroxide added is 35%.
Further, in step S10, the mixture is stirred and precipitated for 20 to 40 minutes, and then subjected to pressure filtration, preferably for 30 minutes. To provide sufficient time for the reaction to complete its precipitation.
Further, in step S10, the seventh pressure filtrate may be recycled to the step of adding concentrated sulfuric acid in step S6, so that the seventh pressure filtrate is recycled to the enrichment step, and by continuous circulation, the enrichment of trace effective components contained in the seventh pressure filtrate can be realized, thereby reducing the waste of resources and also playing a role in environmental protection.
Further, in step S2, the stirring time is 50 to 70 minutes; in step S4, stirring for 50-70 minutes; in step S6, stirring for 80-100 minutes; in step S8, stirring for 10-20 minutes; in step S9, stirring for 10-20 minutes; the stirring time in step S10 is 10-20 minutes, and the stirring speed in step S2, step S4, step S6, step S8, step S9 and step S10 is 60-80 revolutions per minute. The stirring speed and the stirring time are properly set, so that slag and solution can be fully mixed and reacted, and the enrichment effect of elements such as iron, copper, silver, calcium and the like is enhanced.
Compared with the prior art, the invention has the beneficial effects that:
the method for enriching the iron, copper and silver coprecipitation materials and the calcium sulfate in the low-degree APT slag fully enriches the iron, copper, silver and calcium elements in the original APT slag through four continuous enrichment processes. After the first enrichment process treatment, because the temperature is normal and the pH is neutral, calcium, silicon, tungsten and tin in the original slag are basically insoluble, about 10 percent of iron, copper and silver are added into the first press filtrate along with impurities; then carrying out second enrichment treatment on the first cleaning slag, wherein because of normal temperature and low acidity, silicon, tungsten and tin in the raw materials are not basically subjected to acidolysis, and about 35% of calcium, iron, copper and silver enter the second press filtrate along with impurities thereof; then carrying out a third enrichment treatment on the second cleaning slag, wherein due to the fact that concentrated acid is at normal temperature, about 55% of tungsten, calcium, iron, copper and silver in the raw materials except silicon and tin enter a fourth pressure filtrate along with impurities of the tungsten, the calcium, the iron, the copper and the silver; and then mixing the first press filtrate, the second press filtrate and the fourth press filtrate, and performing fourth enrichment treatment to obtain fifth press filter residue rich in calcium sulfate and seventh press filter residue rich in iron, copper and silver. The iron, copper, silver and calcium elements in the original APT slag are enriched through four enrichment steps, and the comprehensive conversion can be known as follows: the iron content is enriched from 18.83-20.15% to about 40.55-41.72%; the copper content is enriched from 0.28 to 0.33 percent to about 11.22 to 16.34 percent; the silver content is enriched from 66 g/t-78 g/t to 5910 g/t-7855 g/t; the original calcium content is 18.08-19.10%, and the calcium sulfate content in the product obtained by enrichment treatment reaches 88.37-90.45%. Therefore, the four-step continuous enrichment process effectively enriches the elements of iron, copper, silver and calcium, has simple process, strong operability and low production cost, and simultaneously, the cleaning solution and the filter pressing solution generated in the whole enrichment process are recycled, thereby not only reducing the waste of resources, but also reducing the pollution to the environment, and further realizing the win-win of environmental protection, social benefit and enterprise economic benefit.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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.
Example 1
The selected APT slag is Ganzhou tungsten slag, and the content of each enrichment element in the raw slag is as follows: 18.83 percent of iron; 0.28% of copper; 66g/t of silver; the calcium content was 18.08%. Carrying out four continuous enrichment treatments on the APT slag, wherein the specific treatment comprises the following steps:
the first enrichment process comprises the following steps:
s1, adding clear water into the APT slag for ball milling, wherein the solid-liquid mass ratio is 1:1.5, the ball milling fineness is 300 meshes;
s2, under the condition of mechanical stirring, adding dilute hydrochloric acid with the concentration of 4% into the APT slag obtained in the step S1 to adjust the pH value, stirring when the pH value is adjusted to 6, wherein the stirring speed is 60-80 rpm, and after stirring for 50 minutes, performing pressure filtration to realize slag-liquid separation to obtain a first pressure filtrate and a first pressure filtration slag;
s3, storing the first press filtrate obtained in the step S2 for subsequent processes; and (4) washing the first filter-pressing residue obtained in the step (S2) with clear water once, wherein the solid-liquid mass ratio is 1: 2, performing filter-pressing separation to obtain first cleaning slag and first cleaning liquid; wherein the first cleaning solution is recovered and used in the pH value adjusting process of step S2 in order to realize the reuse of the waste water, save the cost and protect the environment.
The second enrichment process comprises the following steps:
s4, under the condition of mechanical stirring, adding dilute hydrochloric acid with the concentration of 4% into the first cleaning slag obtained in the step S3 to adjust the pH value, stirring the first cleaning slag when the pH value is adjusted to 1 at the stirring speed of 60-80 rpm for 60 minutes, and then performing pressure filtration to realize slag-liquid separation to obtain second pressure filtration liquid and second pressure filtration slag;
s5, storing the second press filtrate obtained in the step S4 for subsequent processes; and (4) washing the first filter-pressing residue obtained in the step (S4) with clear water once, wherein the solid-liquid mass ratio is 1: 3, performing filter-pressing separation to obtain second cleaning slag and second cleaning liquid; wherein the second cleaning solution is recovered and used in the pH value adjustment process of step S2 or step S4 in order to realize the reuse of the wastewater, save the cost and protect the environment.
The third enrichment process comprises the following steps:
s6, adding concentrated sulfuric acid with the concentration of 92% into the second cleaning slag obtained in the step S5 under the condition of mechanical stirring, wherein the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1: 0.5, stirring at the stirring speed of 60-80 rpm for 80 minutes, controlling the temperature to be about 55 ℃, and performing filter pressing to realize residue-liquid separation to obtain third filter pressing liquid and third filter pressing residue;
s7, feeding the third filter-pressing residue obtained in the step S6 into a tin recovery process, adjusting the pH value of the third filter-pressing liquid obtained in the step S6 by using the first filter-pressing residue obtained in the step S2, and performing filter-pressing separation when the pH value is adjusted to 0.5 to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue; wherein the fourth filter-press residue is recycled to the step of step S6;
the fourth enrichment process comprises the following steps:
s8, under the condition of mechanical stirring, mixing the first pressure filtrate obtained in the step S3, the second pressure filtrate obtained in the step S5 and the fourth pressure filtrate obtained in the step S7, stirring for 15 minutes at a stirring speed of 60-80 revolutions per minute, and then performing pressure filtration to realize residue-liquid separation to obtain a fifth pressure filtrate and a fifth pressure filtration residue; the fifth filter pressing residue is an enriched calcium sulfate product;
s9, adding iron powder into the fifth pressure filtrate obtained in the step S8 under the condition of mechanical stirring, adjusting the pH value to 2, stirring for 10 minutes at a stirring speed of 60-80 rpm, and then performing pressure filtration to realize slag-liquid separation to obtain a sixth pressure filtrate and sixth pressure filtration slag;
s10, enabling the sixth filter-pressing residue obtained in the step S9 to enter a tungsten recovery process; under the condition of mechanical stirring, adding 35% calcium hydroxide into the sixth pressure filtrate obtained in the step S9, stirring for 10 minutes at a stirring speed of 60-80 rpm when the pH value is 3, precipitating, and performing pressure filtration after precipitating for 30 minutes to realize residue-liquid separation to obtain a seventh pressure filtrate and a seventh pressure filtration residue; and the seventh filter pressing residue is the enriched iron, copper and silver coprecipitation material. In order to sufficiently enrich a trace amount of active ingredients and reduce waste of resources, the seventh filtrate may be recovered and used in the step of concentrating sulfuric acid in step S6.
Through determination, the content of calcium sulfate in the original APT slag in the final product after four times of enrichment is 88.37%; the iron content is 41.35%; the copper content is 13.62%; the silver content is 5910 g/t.
Example 2
The selected APT slag is Chenzhou tungsten slag, and the content of each enrichment element in the raw slag is as follows: 19.42 percent of iron; 0.32% of copper; 71g/t of silver; the calcium content was 19.10%. Carrying out four continuous enrichment treatments on the APT slag, wherein the specific treatment comprises the following steps:
the first enrichment process comprises the following steps:
s1, adding clear water into the APT slag for ball milling, wherein the solid-liquid mass ratio is 1: 2, the ball milling fineness is 300 meshes;
s2, under the condition of mechanical stirring, adding 5% dilute hydrochloric acid into the APT slag obtained in the step S1 to adjust the pH value, stirring when the pH value is adjusted to 7, wherein the stirring speed is 60-80 rpm, and after stirring for 60 minutes, performing pressure filtration to realize slag-liquid separation to obtain a first pressure filtrate and a first pressure filtration slag;
s3, storing the first press filtrate obtained in the step S2 for subsequent processes; and (4) washing the first filter-pressing residue obtained in the step (S2) with clear water once, wherein the solid-liquid mass ratio is 1: 3, performing filter-pressing separation to obtain first cleaning slag and first cleaning liquid; wherein the first cleaning solution is recovered and used in the pH value adjusting process of step S2 in order to realize the reuse of the waste water, save the cost and protect the environment.
The second enrichment process comprises the following steps:
s4, under the condition of mechanical stirring, adding 7% dilute hydrochloric acid into the first cleaning slag obtained in the step S3 to adjust the pH value, stirring the first cleaning slag when the pH value is adjusted to 1 at the stirring speed of 60-80 rpm for 50 minutes, and then performing pressure filtration to realize slag-liquid separation to obtain a second pressure filtration liquid and a second pressure filtration slag;
s5, storing the second press filtrate obtained in the step S4 for subsequent processes; and (4) washing the first filter-pressing residue obtained in the step (S4) with clear water once, wherein the solid-liquid mass ratio is 1: 2, performing filter pressing separation to obtain second cleaning slag and second cleaning liquid; wherein the second cleaning solution is recovered and used in the pH value adjustment process of step S2 or step S4 in order to realize the reuse of the wastewater, save the cost and protect the environment.
The third enrichment process comprises the following steps:
s6, adding concentrated sulfuric acid with the concentration of 88% into the second cleaning slag obtained in the step S5 under the condition of mechanical stirring, wherein the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1:1.5, stirring at the stirring speed of 60-80 rpm for 90 minutes, controlling the temperature to be about 50 ℃, and performing filter pressing to realize residue-liquid separation to obtain third filter pressing liquid and third filter pressing residue;
s7, feeding the third filter-pressing residue obtained in the step S6 into a tin recovery process, adjusting the pH value of the third filter-pressing liquid obtained in the step S6 by using the first filter-pressing residue obtained in the step S2, and performing filter-pressing separation when the pH value is adjusted to 0.5 to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue; wherein the fourth filter-press residue is recycled to the step of step S6;
the fourth enrichment process comprises the following steps:
s8, under the condition of mechanical stirring, mixing the first pressure filtrate obtained in the step S3, the second pressure filtrate obtained in the step S5 and the fourth pressure filtrate obtained in the step S7, stirring at the stirring speed of 60-80 revolutions per minute for 10 minutes, and then performing pressure filtration to realize residue-liquid separation to obtain a fifth pressure filtrate and a fifth pressure filtration residue; the fifth filter pressing residue is an enriched calcium sulfate product;
s9, adding iron powder into the fifth pressure filtrate obtained in the step S8 under the condition of mechanical stirring, adjusting the pH value, and when the pH value is adjusted to 2.5, stirring for 15 minutes at the stirring speed of 60-80 rpm, and then performing pressure filtration to realize slag-liquid separation to obtain sixth pressure filtrate and sixth pressure filter residue;
s10, enabling the sixth filter-pressing residue obtained in the step S9 to enter a tungsten recovery process; under the condition of mechanical stirring, adding 35% calcium hydroxide into the sixth pressure filtrate obtained in the step S9 to enable the pH value to be 2.5, stirring for 15 minutes at a stirring speed of 60-80 rpm to enable the sixth pressure filtrate to be precipitated, and performing pressure filtration after precipitating for 20 minutes to realize residue-liquid separation to obtain a seventh pressure filtrate and a seventh pressure filter residue; and the seventh filter pressing residue is the enriched iron, copper and silver coprecipitation material. In order to sufficiently enrich a trace amount of active ingredients and reduce waste of resources, the seventh filtrate may be recovered and used in the step of concentrating sulfuric acid in step S6.
Through determination, the content of calcium sulfate in the original APT slag in the final product after four times of enrichment is 88.37%; the iron content is 41.35%; the copper content is 13.62%; the silver content is 5910 g/t.
Example 3
The selected APT slag is Fujian tungsten slag, and the content of each enriched element in the raw slag is as follows: 20.15 percent of iron; 0.33% of copper; 78g/t of silver; the calcium content is 18.66%. Carrying out four continuous enrichment treatments on the APT slag, wherein the specific treatment comprises the following steps:
the first enrichment process comprises the following steps:
s1, adding clear water into the APT slag for ball milling, wherein the solid-liquid mass ratio is 1: 2.5, the ball milling fineness is 300 meshes;
s2, under the condition of mechanical stirring, adding 8% dilute hydrochloric acid into the APT slag obtained in the step S1 to adjust the pH value, stirring when the pH value is adjusted to 7, wherein the stirring speed is 60-80 rpm, and after stirring for 70 minutes, performing pressure filtration to realize slag-liquid separation to obtain a first pressure filtrate and a first pressure filtration slag;
s3, storing the first press filtrate obtained in the step S2 for subsequent processes; and (4) washing the first filter-pressing residue obtained in the step (S2) with clear water once, wherein the solid-liquid mass ratio is 1:1, performing filter-pressing separation to obtain first cleaning slag and first cleaning liquid; wherein the first cleaning solution is recovered and used in the pH value adjusting process of step S2 in order to realize the reuse of the waste water, save the cost and protect the environment.
The second enrichment process comprises the following steps:
s4, under the condition of mechanical stirring, adding dilute hydrochloric acid with the concentration of 8% into the first cleaning slag obtained in the step S3 to adjust the pH value, stirring when the pH value is adjusted to 1, wherein the stirring speed is 60-80 rpm, the stirring time is 70 minutes, and then performing filter pressing to realize slag-liquid separation to obtain a second filter pressing liquid and a second filter pressing slag;
s5, storing the second press filtrate obtained in the step S4 for subsequent processes; and (4) washing the first filter-pressing residue obtained in the step (S4) with clear water once, wherein the solid-liquid mass ratio is 1:1, performing filter pressing separation to obtain second cleaning slag and second cleaning liquid; wherein the second cleaning solution is recovered and used in the pH value adjustment process of step S2 or step S4 in order to realize the reuse of the wastewater, save the cost and protect the environment.
The third enrichment process comprises the following steps:
s6, adding concentrated sulfuric acid with the concentration of 90% into the second cleaning slag obtained in the step S5 under the condition of mechanical stirring, wherein the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1:1, stirring at the stirring speed of 60-80 rpm for 100 minutes, controlling the temperature to be about 60 ℃, and performing filter pressing to realize residue-liquid separation to obtain third filter pressing liquid and third filter pressing residue;
s7, feeding the third filter-pressing residue obtained in the step S6 into a tin recovery process, adjusting the pH value of the third filter-pressing liquid obtained in the step S6 by using the first filter-pressing residue obtained in the step S2, and performing filter-pressing separation when the pH value is adjusted to 0.5 to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue; wherein the fourth filter-press residue is recycled to the step of step S6;
the fourth enrichment process comprises the following steps:
s8, under the condition of mechanical stirring, mixing the first pressure filtrate obtained in the step S3, the second pressure filtrate obtained in the step S5 and the fourth pressure filtrate obtained in the step S7, stirring at the stirring speed of 60-80 revolutions per minute for 20 minutes, and then performing pressure filtration to realize residue-liquid separation to obtain a fifth pressure filtrate and a fifth pressure filtration residue; the fifth filter pressing residue is an enriched calcium sulfate product;
s9, adding iron powder into the fifth pressure filtrate obtained in the step S8 under the condition of mechanical stirring, adjusting the pH value, and when the pH value is adjusted to 2.2, stirring for 20 minutes at the stirring speed of 60-80 rpm, and then performing pressure filtration to realize slag-liquid separation to obtain sixth pressure filtrate and sixth pressure filter residue;
s10, enabling the sixth filter-pressing residue obtained in the step S9 to enter a tungsten recovery process; under the condition of mechanical stirring, adding 35% calcium hydroxide into the sixth pressure filtrate obtained in the step S9 to enable the pH value to be 3.5, stirring for 20 minutes at a stirring speed of 60-80 rpm to enable the sixth pressure filtrate to be precipitated, and performing pressure filtration after precipitating for 40 minutes to realize residue-liquid separation to obtain a seventh pressure filtrate and a seventh pressure filter residue; and the seventh filter pressing residue is the enriched iron, copper and silver coprecipitation material. In order to sufficiently enrich a trace amount of active ingredients and reduce waste of resources, the seventh filtrate may be recovered and used in the step of concentrating sulfuric acid in step S6.
Through determination, the calcium sulfate content of the original APT slag in the final product after four times of enrichment is 90.45%; iron content 41.72%; the copper content is 16.34%; the silver content was 7855 g/t.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for enriching iron, copper and silver coprecipitation materials and calcium sulfate in low-degree APT slag is characterized by comprising four continuous enrichment processes:
the first enrichment process comprises the following steps:
s1, adding clear water into the APT slag for ball milling, wherein the ball milling fineness is 300 meshes;
s2, under the condition of mechanical stirring, adding dilute hydrochloric acid into the APT slag obtained in the step S1 to adjust the pH value, continuing stirring when the pH value is adjusted to 6-8, and then performing pressure filtration to realize slag-liquid separation to obtain a first pressure filtrate and a first pressure filtration residue;
s3, storing the first press filtrate obtained in the step S2 for subsequent processes; cleaning the first filter-pressing residue obtained in the step S2 with clear water once, and performing filter-pressing separation to obtain first cleaning residue and first cleaning liquid;
the second enrichment process comprises the following steps:
s4, under the condition of mechanical stirring, adding dilute hydrochloric acid into the first cleaning slag obtained in the step S3 to adjust the pH value, continuing stirring when the pH value is adjusted to 1, and then performing pressure filtration to realize slag-liquid separation to obtain a second pressure filtration liquid and a second pressure filtration slag;
s5, storing the second press filtrate obtained in the step S4 for subsequent processes; cleaning the first filter-pressing residue obtained in the step S4 with clear water once, and performing filter-pressing separation 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 under the condition of mechanical stirring, and performing pressure filtration after stirring to realize slag-liquid separation to obtain a third pressure filtrate and a third pressure filter slag;
s7, feeding the third filter-pressing residue obtained in the step S6 into a tin recovery process, adjusting the pH value of the third filter-pressing liquid obtained in the step S6 by using the first filter-pressing residue obtained in the step S2, and performing filter-pressing separation when the pH value is adjusted to 0.5 to obtain a fourth filter-pressing liquid and a fourth filter-pressing residue; wherein the fourth filter-press residue is recycled to the step of step S6;
the fourth enrichment process comprises the following steps:
s8, under the condition of mechanical stirring, mixing the first pressure filtrate obtained in the step S3, the second pressure filtrate obtained in the step S5 and the fourth pressure filtrate obtained in the step S7, stirring, press-filtering, and realizing residue-liquid separation to obtain a fifth pressure filtrate and fifth pressure-filtered residue; the fifth filter pressing residue is an enriched calcium sulfate product;
s9, adding iron powder into the fifth pressure filtrate obtained in the step S8 under the condition of mechanical stirring, adjusting the pH value through the reaction of iron and acid, continuing stirring when the pH value is adjusted to 2-2.5, and then performing pressure filtration to realize residue-liquid separation to obtain a sixth pressure filtrate and sixth pressure filter residue;
s10, enabling the sixth filter-pressing residue obtained in the step S9 to enter a tungsten recovery process; adding the pH value of calcium hydroxide into the sixth pressure filtrate obtained in the step S9 under the condition of mechanical stirring, continuously stirring and precipitating the sixth pressure filtrate when the pH value is 2.5-3.5, and performing pressure filtration after precipitation to realize residue-liquid separation to obtain seventh pressure filtrate and seventh pressure filter residue; and the seventh filter pressing residue is the enriched iron, copper and silver coprecipitation material.
2. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S1, the liquid is clear water, and the solid-liquid mass ratio of the APT slag to the liquid is 1: 1.5-2.5.
3. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S2 and step S4, the concentration of the dilute hydrochloric acid added is 4% to 8%.
4. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S3 and step S5, the cleaning is performed once with clean water, and the solid-liquid mass ratio during cleaning is 1: 1-3; the first cleaning solution can be recycled for use in the pH adjustment process of step S2; the second cleaning solution may be recycled for use in the pH adjustment process of step S2 or step S4.
5. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S6, 88% -92% of the second cleaning slag and the concentrated sulfuric acid are added, and the mass ratio of the second cleaning slag to the concentrated sulfuric acid is 1 (0.5-1.5).
6. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S6, the temperature is controlled to be 50-60 ℃ for filter pressing.
7. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S10, the concentration of calcium hydroxide added is 35%.
8. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S10, the mixture is stirred and precipitated for 20 to 40 minutes, and then subjected to pressure filtration.
9. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S10, the seventh press filtrate may be recycled for use in the concentrated sulfuric acid process of step S6.
10. The method for enriching iron, copper and silver co-precipitates and calcium sulfate in low-grade APT slag according to claim 1, which is characterized in that: in step S2, stirring for 50-70 minutes; in step S4, stirring for 50-70 minutes; in step S6, stirring for 80-100 minutes; in step S8, stirring for 10-20 minutes; in step S9, stirring for 10-20 minutes; the stirring time in step S10 is 10-20 minutes, and the stirring speed in step S2, step S4, step S6, step S8, step S9 and step S10 is 60-80 revolutions per minute.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305698A (en) * | 2013-06-09 | 2013-09-18 | 南康市恒源循环科技有限公司 | Method for recovering gold, silver, tin and copper from industrial wastes |
| CN104313694A (en) * | 2014-10-10 | 2015-01-28 | 江西高信科技有限公司 | Method for producing gypsum whiskers by using waste residues of wet process tungsten smelting as raw materials |
| CN105154683A (en) * | 2015-08-20 | 2015-12-16 | 湖南世纪垠天新材料有限责任公司 | Method for separating and recycling valuable metal in tungsten slag |
| CN110004294A (en) * | 2019-03-04 | 2019-07-12 | 中南大学 | The processing method of scheelite caustic digestion slag |
-
2019
- 2019-10-17 CN CN201910990077.0A patent/CN110760677B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305698A (en) * | 2013-06-09 | 2013-09-18 | 南康市恒源循环科技有限公司 | Method for recovering gold, silver, tin and copper from industrial wastes |
| CN104313694A (en) * | 2014-10-10 | 2015-01-28 | 江西高信科技有限公司 | Method for producing gypsum whiskers by using waste residues of wet process tungsten smelting as raw materials |
| CN105154683A (en) * | 2015-08-20 | 2015-12-16 | 湖南世纪垠天新材料有限责任公司 | Method for separating and recycling valuable metal in tungsten slag |
| CN110004294A (en) * | 2019-03-04 | 2019-07-12 | 中南大学 | The processing method of scheelite caustic digestion slag |
Non-Patent Citations (4)
| Title |
|---|
| 张立 等: "钨渣酸浸与钠碱熔融回收钽铌的研究", 《稀有金属与硬质合金》 * |
| 李俊杰 等: "钨渣综合利用研究现状", 《矿产保护与利用》 * |
| 肖超 等: "低品位钨渣处理工艺试验研究", 《湖南有色金属》 * |
| 黄芍英 等: "二次磷砷渣酸浸研究", 《稀有金属与硬质合金》 * |
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