CN113621817A - Method for selectively extracting indium from dust of rotary hearth furnace - Google Patents

Method for selectively extracting indium from dust of rotary hearth furnace Download PDF

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Publication number
CN113621817A
CN113621817A CN202110955392.7A CN202110955392A CN113621817A CN 113621817 A CN113621817 A CN 113621817A CN 202110955392 A CN202110955392 A CN 202110955392A CN 113621817 A CN113621817 A CN 113621817A
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leaching
indium
rotary hearth
hearth furnace
primary
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张生富
肖雄
宋明轩
温良英
尹铖
邱贵宝
陈静波
魏志芳
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Chongqing University
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Chongqing University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for selectively extracting indium from dust of a rotary hearth furnace, which comprises the following steps: step 1) crushing and grinding the dedusting ash of the rotary hearth furnace, then uniformly mixing and drying to obtain a raw material for leaching; step 2) putting the raw materials in the step 1) into a sulfuric acid solution for primary leaching treatment to obtain primary leaching filtrate and primary leaching filter residue; step 3) carrying out secondary oxidation leaching on the primary leaching filter residue obtained in the step 2) to obtain oxidation leaching filter residue and oxidation leaching filtrate; step 4) extracting the primary leaching filtrate obtained in the step 2) to obtain an indium loaded organic phase and an extraction liquid; and 5) extracting the oxidation leaching filtrate obtained in the step 3) to obtain an indium loaded organic phase and an extraction liquid. The method can realize effective extraction of the noble metal indium in the fly ash, so that all metal elements in the fly ash can be comprehensively and effectively utilized.

Description

Method for selectively extracting indium from dust of rotary hearth furnace
Technical Field
The invention relates to the technical field of recycling of solid wastes in the steel production process, in particular to a method for selectively extracting indium from dust removed by a rotary hearth furnace.
Background
The iron and steel industry makes a very important contribution to the development of the world basic industry, the yield of the iron and steel industry reflects the national industrialization degree to a certain extent, and the proportion of the crude steel yield in China is more than 50% in the world at present. Blast furnace iron making is the major export source of steel products, which produce over 85% of the pig iron worldwide. With the enlargement of blast furnace iron-making scale in recent years, a large amount of blast furnace gas ash is by-produced: the yield of crude steel in China reaches 10.53 hundred million tons in 2020, and accounts for 56.5 percent in the world. According to statistics, about 20kg of blast furnace gas ash is generated every 1t of steel produced, the blast furnace gas ash not only can cause harm to the environment, but also increases the industrial production cost, and simultaneously, a large amount of iron, carbon and other valuable metal resources are contained in the blast furnace gas ash, so that the method has important significance for comprehensive recycling of high-added-value solid wastes.
The rotary hearth furnace process has an important application prospect in the aspect of treating solid wastes such as blast furnace gas ash and the like, the rotary hearth furnace process utilizes residual carbon in the fly ash to carry out high-temperature reduction, valuable metals are volatilized into a dust removal system after being reduced, metal oxides are formed after cooling and oxidation, unreacted particles and the oxides are blown into the dust removal system by flue gas flow, and finally a mixture of the fly ash is formed. The rotary hearth furnace has advanced process technology, high reduction temperature, short reduction time, good enrichment effect and high grade of metallized pellets, but secondary dust generated by the process still contains a large amount of metal resources, so that the secondary resources of the dust removed from the rotary hearth furnace still need to be efficiently recycled.
In the prior art, methods for recovering valuable metals in the dust removed from the rotary hearth furnace exist, for example, a method for extracting zinc, potassium and sodium by using secondary dust of the rotary hearth furnace is disclosed in the invention patent application with the publication number of CN 102808087A, and the following technologies are disclosed in the method: leaching the secondary dust with water, extracting lead from the leaching residue, extracting with P2O4 and sulfonated kerosene, performing back extraction with dilute sulfuric acid to obtain a zinc sulfate solution, which can meet the requirement of electrolytic zinc extraction, performing evaporative crystallization on raffinate to obtain KCl, repeatedly leaching, and performing fractional crystallization after the KCl solution is saturated to obtain a NaCl product. Also, as disclosed in patent application publication No. CN 106966410 a, a process for treating flue gas dust of a rotary hearth furnace, the process discloses the following techniques: the flue gas dedusting ash, the saturated potassium mother liquor and the diluted potassium mother liquor are mixed and heated to 80-90 ℃ according to the mass ratio of 1:4:1, filtered filtrate is subjected to multistage evaporation crystallization and centrifugal dehydration, and a KCl product with the grade of more than 92% and the water content of less than 4% is obtained after separation and purification.
The above applications mainly focus on the recovery of valuable metals such as zinc, lead, potassium, sodium, etc., and all mainly use experimental research, the process is greatly influenced by different rotary hearth furnace dedusting ash raw materials, the problems of cost environment, etc. are not well solved, the practical popularization and application are limited, the research on extracting the noble metal indium in the dedusting ash is less, indium is a noble metal with very unique and excellent physical and chemical properties, the indium is widely applied to high-tech fields such as electronic computers, energy, photoelectricity, national defense and military, aerospace and aviation, nuclear industry and modern information industry, and is called "vitamin of alloy", in recent years, with the rapid development of information industry, the indium consumption is rapidly increased, the indium market often presents a situation of supply and demand, meanwhile, the limited indium resource is increasingly reduced, the global indium storage capacity is only 5 ten thousand tons, wherein the exploitable indium accounts for 50%, because the content of independent indium ore is very low, metal indium is produced industrially mainly by purifying byproducts of zinc, lead and tin production, the recovery rate is about 50-60%, and the amount of indium really obtained is only 1.5-1.6 ten thousand tons. China is a country with large indium yield and reserve, indium resources are mainly distributed in Yunnan, Guangxi, inner Mongolia, Qinghai and the like, according to statistics of 1.1 ten thousand tons of global indium exploration reserve, 1.6 ten thousand tons of reserve basis, 8000 tons of Chinese exploration reserve, 72.7 percent of percentage, 1 ten thousand tons of reserve basis and 62.5 percent of percentage by weight by the national geological survey bureau, the pure indium yield of China also accounts for more than 50 percent of the world, but a bottleneck cannot be mastered on a key technology all the time, the consumption of indium is mainly exported, the initiative cannot be mastered in high-purity indium and ultra-pure indium markets, and the competitiveness of indium products is not high, so that how to extract various precious metals including indium from rotary hearth furnace dust is realized, and the technical problem which is urgently needed to be solved is also formed.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problems to be solved by the invention are as follows: how to provide one kind not only can realize drawing various noble metals from the rotary hearth furnace dust removal ash, can also realize effectively drawing the noble metal indium in the dust removal ash simultaneously to make each metallic element in the dust removal ash can both be synthesized effectively and utilized, and then reduce environmental pollution, increase enterprise economic benefits's the method of selectively drawing indium from the rotary hearth furnace dust removal ash.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for selectively extracting indium from dust in a rotary hearth furnace comprises the following steps:
step 1) crushing and grinding the dedusting ash of the rotary hearth furnace, then uniformly mixing and drying to obtain a raw material for leaching;
step 2) putting the raw materials in the step 1) into a sulfuric acid solution for primary leaching treatment to obtain primary leaching filtrate and primary leaching filter residue;
step 3) carrying out secondary oxidation leaching on the primary leaching filter residue obtained in the step 2) to obtain oxidation leaching filter residue and oxidation leaching filtrate;
step 4) extracting the primary leaching filtrate obtained in the step 2) to obtain an indium loaded organic phase and an extraction liquid;
and 5) extracting the oxidation leaching filtrate obtained in the step 3) to obtain an indium loaded organic phase and an extraction liquid.
The working principle of the invention is as follows: the invention adopts a three-step indium extraction process of 'primary sulfuric acid leaching, secondary oxidation leaching and normal temperature extraction', wherein, the effective separation of main metal ions can be realized after the primary sulfuric acid leaching and the secondary oxidation leaching are carried out on raw materials, primary leaching filtrate rich in zinc, potassium and sodium and oxidation leaching filter residue rich in lead and bismuth are obtained, then, the primary leaching filtrate and the oxidation leaching filtrate are further extracted, the indium-loaded organic phase and the extract liquid obtained after the extraction treatment are indium ion filtrate with high concentration, and the precipitation form of lead and bismuth is not influenced in the process of the oxidation leaching filter residue obtained by the secondary oxidation leaching treatment, therefore, the method realizes the purpose of extracting various noble metals from the dust removed by a rotary hearth furnace, and simultaneously can realize the effective extraction of the noble metal indium in the dust removed, thereby leading all metal elements in the dust removed to be comprehensively and effectively utilized, thereby reducing the environmental pollution and increasing the economic benefit of enterprises.
Preferably, the rotary hearth furnace dust removal ash in the step 1) is secondary dust obtained after the blast furnace dust removal ash is treated by a rotary hearth furnace process, the rotary hearth furnace dust removal ash is crushed and ground to have a particle size of less than 74 microns, and then the rotary hearth furnace dust removal ash is dried at a temperature of 105 +/-5 ℃ to have a constant weight.
Therefore, the effect of subsequent leaching treatment is improved by crushing and grinding the dust removed from the rotary hearth furnace to less than 74 microns, effective precipitation and extraction of various precious metals are ensured, and simultaneously, moisture in the dust removed from the rotary hearth furnace can be effectively removed by drying treatment.
Preferably, the liquid-solid ratio of the sulfuric acid solution in the step 2) is 5: 1-9: 1mL/g, the time of primary leaching treatment is 1-5 h, and the temperature of the primary leaching treatment is 25-90 ℃.
Therefore, when the raw material is subjected to primary leaching treatment by the material sulfuric acid solution, the liquid-solid ratio of the sulfuric acid solution, the primary leaching treatment time and the primary leaching treatment temperature have great influence on the leaching treatment effect, and the primary leaching treatment effect can be ensured by limiting the parameter range.
Preferably, the sulfuric acid solution is further stirred during the primary leaching treatment in the step 2), and the stirring speed is 0-600 rpm.
Therefore, the sulfuric acid solution is stirred in the primary leaching treatment process, so that the reaction sufficiency between the raw materials and the sulfuric acid solution can be improved, and the leaching treatment effect is improved.
Preferably, the liquid-solid ratio of the sulfuric acid solution in the step 2) is 7:1mL/g, the time of the primary leaching treatment is 3 hours, the temperature of the primary leaching treatment is 90 ℃, the stirring treatment speed is 500rpm, and the concentration of the sulfuric acid solution is 180 g/L.
Thus, research shows that the leaching rate of indium is improved by increasing the liquid-solid ratio of the sulfuric acid solution, and although the improvement effect is not very obvious, the liquidity during stirring treatment is influenced by too small the liquid-solid ratio of the sulfuric acid solution, so that the leaching rate of indium is reduced, therefore, the scheme designs the liquid-solid ratio of the sulfuric acid solution to be 7:1mL/g, and at the moment, the indium can be ensured to have higher leaching rate, and the leaching rate of indium is basically kept unchanged when the liquid-solid ratio of the sulfuric acid solution is further improved.
Meanwhile, by researching the change rule of the primary leaching time and the indium leaching rate, the leaching rate of indium is obviously increased when the primary leaching time is 3 hours, and then the leaching time is continuously increased, so that the leaching rate of indium is basically kept unchanged, and therefore, the primary leaching time is set to be 3 hours.
In addition, by researching the change rule of the primary leaching temperature and the indium leaching rate, the leaching rate of indium is continuously increased when the primary leaching temperature reaches 50 ℃, the leaching rate of indium is basically the highest value when the primary leaching temperature reaches 90 ℃, and the influence of the continuous increase of the temperature on the indium leaching rate is basically unchanged, so that the primary leaching temperature is set to be 90 ℃.
Furthermore, by studying the change rule of the stirring speed and the indium leaching rate, the indium leaching rate is found to be obviously increased when the stirring speed is 500rpm, and the indium leaching rate is basically kept stable with the further increase of the stirring speed, so the stirring speed is set to be 500 rpm.
In conclusion, the scheme limits the liquid-solid state of the sulfuric acid solution in the primary leaching treatment, the primary leaching treatment time, the primary leaching treatment temperature, the stirring treatment speed and the sulfuric acid solution concentration, and can achieve the purpose of maximally improving the indium leaching rate.
Preferably, in the step 3), the primary leached filter residue is subjected to secondary oxidation treatment by adding a nitric acid solution and a sulfuric acid solution, the liquid-solid ratio of the nitric acid solution to the primary leached filter residue is 0.8: 1-1.5: 1mL/g, and the liquid-solid ratio of the sulfuric acid solution to the primary leached filter residue is 5: 1-9: 1 mL/g.
Thus, primary leaching filtrate rich in zinc, potassium and sodium and primary leaching filter residue rich in lead and bismuth are obtained through primary leaching treatment, wherein the leaching rate of indium ions is 36.82%, the leaching rates of zinc, potassium and sodium ions respectively reach 98.03%, 89.44% and 84.23%, the leaching rates of lead and bismuth ions are 0.02% and 12.25%, and secondary oxidation leaching of nitric acid is continuously carried out on residual indium in the primary leaching filter residue, wherein the liquid-solid ratio of nitric acid to the primary oxidation filter residue is 0.8: 1-1.5: 1mL/g, and the liquid-solid ratio of a sulfuric acid solution with the concentration of 180g/L to the primary oxidation filter residue is 5: 1-9: 1mL/g, so that the leaching rate of indium can reach 60.37%, and the leaching rates of bismuth and lead are only 1.84% and 0.15%, thereby realizing effective enrichment of indium.
Preferably, the liquid-solid ratio of the nitric acid solution to the primary leaching filter residue in the step 3) is 1:1mL/g, and the liquid-solid ratio of the sulfuric acid solution to the primary leaching filter residue is 7:1 mL/g.
Thus, the liquid-solid ratio in the secondary oxidation leaching can enable indium to have a high leaching rate.
Preferably, P is used in step 4)2O4And sulfonated kerosene as extraction liquid to extract the primary leaching filtrate, and P2O4The volume fraction of the sulfonated kerosene is 20-40%, the ratio of a water phase to an organic phase in the sulfonated kerosene is 3: 1-5: 1, the extraction time is 6-10 min, and 2-4-stage countercurrent extraction is carried out while keeping the initial pH of primary leaching filtrate unchanged.
Thus, using P2O4And sulfonated kerosene asThe extraction liquid is used for extracting the primary leaching filtrate, the content of each component in the extraction liquid and the value range of the extraction time are limited, so that the extraction effect of the primary leaching filtrate is effectively guaranteed, the extraction rate of indium is further improved through multi-stage countercurrent extraction, and the purpose of improving the recovery rate of indium is further achieved.
Preferably, P in step 4)2O4The volume fraction of the sulfonated kerosene is 30 percent, the ratio of a water phase to an organic phase in the sulfonated kerosene is 4:1, the extraction time is 8min, and 3-stage countercurrent extraction is carried out while keeping the initial pH of primary leaching filtrate unchanged.
Thus, the parameters can ensure the extraction effect of the extraction liquid on the primary leaching filtrate.
Preferably, P is used in step 5)2O4And sulfonated kerosene as extraction liquid to extract the oxidation leaching filtrate, and P2O4The volume fraction of the sulfonated kerosene is 30 percent, the ratio of a water phase to an organic phase in the sulfonated kerosene is 4:1, the extraction time is 8min, and the initial pH of the oxidation leaching filtrate is kept unchanged for carrying out 1-stage countercurrent extraction.
Therefore, the extraction effect of the indium in the secondary oxidation filtrate can be effectively ensured by selecting the extraction liquid and the extraction parameters.
Compared with the prior art, the invention has the following advantages:
the method takes secondary fly ash obtained by treating blast furnace fly ash in a rotary hearth furnace as a raw material, and calculates the comprehensive recovery rate of indium in the fly ash in the rotary hearth furnace in the overall recovery process by a three-step indium extraction process of 'primary sulfuric acid leaching, secondary oxidation leaching and normal temperature extraction'; according to sample analysis, the indium content in 100g of the dedusting ash of the rotary hearth furnace is only 0.0208g, the mass of the indium obtained by the whole recovery process from the raw materials to the extraction filtrate is 0.01426g, the comprehensive recovery rate can reach 68.56%, and meanwhile, zinc, potassium and sodium-rich solution and lead and bismuth-rich filter residue raw materials are obtained. The whole process is simple and easy to implement, all metal elements are comprehensively and effectively utilized, the environmental pollution is reduced, and the economic benefit of enterprises is increased.
Drawings
FIG. 1 is a flow chart of the method for selectively extracting indium from dust in a rotary hearth furnace according to the present invention.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Many kinds of dust can be generated in the smelting process of a steel plant, and blast furnace iron making is the main production mode at present, so that the treatment of blast furnace dust is particularly important. The rotary hearth furnace process is a process for treating blast furnace fly ash with important application prospect, realizes the separation of valuable metals and obtains higher-grade metallized pellets.
As shown in the following table, table 1 and table 2 respectively show the content distribution of each metal element in the blast furnace dust removal ash and the rotary hearth furnace dust removal ash, and it can be seen from table 1 and table 2 that zinc, potassium, sodium and lead in the dust removal ash are main metal elements, and the contents of rare and noble metals such as indium and bismuth in the dust removal ash treated by the rotary hearth furnace process are effectively enriched, so that the extraction of each metal element, especially the rare and noble metals such as indium, from the rotary hearth furnace dust removal ash is more facilitated.
TABLE 1 composition and content of each metal element in blast furnace fly ash
Fe C Zn Pb Cd/Sn Bi In Si/Al/Mg/Ca/F/Cl
30–45 15–20 5–15 1–10 10–2–10–1 10–4–10–2 10–3–10–1 20–30
TABLE 2 composition and content of each metal element in the dust of rotary hearth furnace
In Bi Pb Zn K Na Fe Mg Ca Al
0.0208 0.15 7.23 44.06 8.62 14.06 0.3201 0.2382 0.1896 0.0607
As shown in the attached figure 1, the invention discloses a method for selectively extracting indium from dust in a rotary hearth furnace, which comprises the following steps:
step 1) crushing and grinding the dedusting ash of the rotary hearth furnace, then uniformly mixing and drying to obtain a raw material for leaching;
step 2) putting the raw materials in the step 1) into a sulfuric acid solution for primary leaching treatment to obtain primary leaching filtrate and primary leaching filter residue;
step 3) carrying out secondary oxidation leaching on the primary leaching filter residue obtained in the step 2) to obtain oxidation leaching filter residue and oxidation leaching filtrate;
step 4) extracting the primary leaching filtrate obtained in the step 2) to obtain an indium loaded organic phase and an extraction liquid;
and 5) extracting the oxidation leaching filtrate obtained in the step 3) to obtain an indium loaded organic phase and an extraction liquid.
The working principle of the invention is as follows: the invention adopts a three-step indium extraction process of 'primary sulfuric acid leaching, secondary oxidation leaching and normal temperature extraction', wherein, the effective separation of main metal ions can be realized after the primary sulfuric acid leaching and the secondary oxidation leaching are carried out on raw materials, primary leaching filtrate rich in zinc, potassium and sodium and oxidation leaching filter residue rich in lead and bismuth are obtained, then, the primary leaching filtrate and the oxidation leaching filtrate are further extracted, the indium-loaded organic phase and the extract liquid obtained after the extraction treatment are indium ion filtrate with high concentration, and the precipitation form of lead and bismuth is not influenced in the process of the oxidation leaching filter residue obtained by the secondary oxidation leaching treatment, therefore, the method realizes the purpose of extracting various noble metals from the dust removed by a rotary hearth furnace, and simultaneously can realize the effective extraction of the noble metal indium in the dust removed, thereby leading all metal elements in the dust removed to be comprehensively and effectively utilized, thereby reducing the environmental pollution and increasing the economic benefit of enterprises.
In this embodiment, the rotary hearth furnace fly ash in step 1) is secondary dust obtained by treating the blast furnace fly ash through a rotary hearth furnace process, and the rotary hearth furnace fly ash is pulverized and ground to have a particle size of less than 74 μm, and then dried at a temperature of 105 ± 5 ℃ to a constant weight.
Therefore, the effect of subsequent leaching treatment is improved by crushing and grinding the dust removed from the rotary hearth furnace to less than 74 microns, effective precipitation and extraction of various precious metals are ensured, and simultaneously, moisture in the dust removed from the rotary hearth furnace can be effectively removed by drying treatment.
In the embodiment, the liquid-solid ratio of the sulfuric acid solution in the step 2) is 5: 1-9: 1mL/g, the time of the primary leaching treatment is 1-5 h, and the temperature of the primary leaching treatment is 25-90 ℃.
Therefore, when the raw material is subjected to primary leaching treatment by the material sulfuric acid solution, the liquid-solid ratio of the sulfuric acid solution, the primary leaching treatment time and the primary leaching treatment temperature have great influence on the leaching treatment effect, and the primary leaching treatment effect can be ensured by limiting the parameter range.
In this embodiment, the sulfuric acid solution is further stirred during the primary leaching in step 2), and the stirring speed is 0-600 rpm.
Therefore, the sulfuric acid solution is stirred in the primary leaching treatment process, so that the reaction sufficiency between the raw materials and the sulfuric acid solution can be improved, and the leaching treatment effect is improved.
In the embodiment, the liquid-solid ratio of the sulfuric acid solution in the step 2) is 7:1mL/g, the time of the primary leaching treatment is 3h, the temperature of the primary leaching treatment is 90 ℃, the stirring speed is 500rpm, and the concentration of the sulfuric acid solution is 180 g/L.
Thus, research shows that the leaching rate of indium is improved by increasing the liquid-solid ratio of the sulfuric acid solution, and although the improvement effect is not very obvious, the liquidity during stirring treatment is influenced by too small the liquid-solid ratio of the sulfuric acid solution, so that the leaching rate of indium is reduced, therefore, the scheme designs the liquid-solid ratio of the sulfuric acid solution to be 7:1mL/g, and at the moment, the indium can be ensured to have higher leaching rate, and the leaching rate of indium is basically kept unchanged when the liquid-solid ratio of the sulfuric acid solution is further improved.
Meanwhile, by researching the change rule of the primary leaching time and the indium leaching rate, the leaching rate of indium is obviously increased when the primary leaching time is 3 hours, and then the leaching time is continuously increased, so that the leaching rate of indium is basically kept unchanged, and therefore, the primary leaching time is set to be 3 hours.
In addition, by researching the change rule of the primary leaching temperature and the indium leaching rate, the leaching rate of indium is continuously increased when the primary leaching temperature reaches 50 ℃, the leaching rate of indium is basically the highest value when the primary leaching temperature reaches 90 ℃, and the influence of the continuous increase of the temperature on the indium leaching rate is basically unchanged, so that the primary leaching temperature is set to be 90 ℃.
Furthermore, by studying the change rule of the stirring speed and the indium leaching rate, the indium leaching rate is found to be obviously increased when the stirring speed is 500rpm, and the indium leaching rate is basically kept stable with the further increase of the stirring speed, so the stirring speed is set to be 500 rpm.
In conclusion, the scheme limits the liquid-solid state of the sulfuric acid solution in the primary leaching treatment, the primary leaching treatment time, the primary leaching treatment temperature, the stirring treatment speed and the sulfuric acid solution concentration, and can achieve the purpose of maximally improving the indium leaching rate.
In this embodiment, in step 3), a nitric acid solution and a sulfuric acid solution are added to perform secondary oxidation treatment on the primary leached filter residue, and the liquid-solid ratio of the nitric acid solution to the primary leached filter residue is 0.8: 1-1.5: 1mL/g, and the liquid-solid ratio of the sulfuric acid solution to the primary leached filter residue is 5: 1-9: 1 mL/g.
Thus, primary leaching filtrate rich in zinc, potassium and sodium and primary leaching filter residue rich in lead and bismuth are obtained through primary leaching treatment, wherein the leaching rate of indium ions is 36.82%, the leaching rates of zinc, potassium and sodium ions respectively reach 98.03%, 89.44% and 84.23%, the leaching rates of lead and bismuth ions are 0.02% and 12.25%, and secondary oxidation leaching of nitric acid is continuously carried out on residual indium in the primary leaching filter residue, wherein the liquid-solid ratio of nitric acid to the primary oxidation filter residue is 0.8: 1-1.5: 1mL/g, and the liquid-solid ratio of a sulfuric acid solution with the concentration of 180g/L to the primary oxidation filter residue is 5: 1-9: 1mL/g, so that the leaching rate of indium can reach 60.37%, and the leaching rates of bismuth and lead are only 1.84% and 0.15%, thereby realizing effective enrichment of indium.
In this embodiment, the liquid-solid ratio of the nitric acid solution to the first leaching residue in step 3) is 1:1mL/g, and the liquid-solid ratio of the sulfuric acid solution to the first leaching residue is 7:1 mL/g.
Thus, the liquid-solid ratio in the secondary oxidation leaching can enable indium to have a high leaching rate.
In this example, P is used in step 4)2O4And sulfonated kerosene as extraction liquid to extract the primary leaching filtrate, and P2O4The volume fraction of the sulfonated kerosene is 20-40%, the ratio of a water phase to an organic phase in the sulfonated kerosene is 3: 1-5: 1, the extraction time is 6-10 min, and 2-4-stage countercurrent extraction is carried out while keeping the initial pH of primary leaching filtrate unchanged.
Thus, using P2O4And sulfonated kerosene is used as extraction liquid to extract the primary leaching filtrate, and the content of each component in the extraction liquid and the value range of the extraction time are limited, so that the extraction effect of the primary leaching filtrate is effectively ensured, and meanwhile, the extraction rate of indium is further improved through multi-stage countercurrent extraction, and the purpose of improving the recovery rate of indium is further achieved.
In this embodiment, P in step 4)2O430% by volume of sulfonated coalThe ratio of the water phase to the organic phase in the oil is 4:1, the extraction time is 8min, and 3-stage countercurrent extraction is carried out by keeping the initial pH of the primary leaching filtrate unchanged.
Therefore, the parameters can ensure the extraction effect of the extraction liquid on the primary leaching filtrate, the extraction rate of the indium ions can reach 89.30%, and the extraction rates of zinc, potassium and sodium are only 2.55%, 1.53% and 1.86% respectively, so that the aim of effectively extracting the indium ions is fulfilled.
In this example, P is used in step 5)2O4And sulfonated kerosene as extraction liquid to extract the oxidation leaching filtrate, and P2O4The volume fraction of the sulfonated kerosene is 30 percent, the ratio of a water phase to an organic phase in the sulfonated kerosene is 4:1, the extraction time is 8min, and the initial pH of the oxidation leaching filtrate is kept unchanged for carrying out 1-stage countercurrent extraction.
Therefore, the selection of the extraction liquid and the extraction parameters can effectively ensure the extraction effect on the indium in the secondary oxidation filtrate, the extraction rate of indium ions reaches 93.38%, and the extraction rate of bismuth ions is 47.10%, but because the oxidation leaching rate is very low, the extraction amount of bismuth ions is less, and the purity of indium ions is not influenced.
Compared with the prior art, the invention has the following advantages:
the method takes secondary fly ash obtained by treating blast furnace fly ash in a rotary hearth furnace as a raw material, and calculates the comprehensive recovery rate of indium in the fly ash in the rotary hearth furnace in the overall recovery process by a three-step indium extraction process of 'primary sulfuric acid leaching, secondary oxidation leaching and normal temperature extraction'; according to sample analysis, the indium content in 100g of the dedusting ash of the rotary hearth furnace is only 0.0208g, the mass of the indium obtained by the whole recovery process from the raw materials to the extraction filtrate is 0.01426g, the comprehensive recovery rate can reach 68.56%, and meanwhile, zinc, potassium and sodium-rich solution and lead and bismuth-rich filter residue raw materials are obtained. The whole process is simple and easy to implement, all metal elements are comprehensively and effectively utilized, the environmental pollution is reduced, and the economic benefit of enterprises is increased.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.

Claims (10)

1. A method for selectively extracting indium from dust in a rotary hearth furnace comprises the following steps:
step 1) crushing and grinding the dedusting ash of the rotary hearth furnace, then uniformly mixing and drying to obtain a raw material for leaching;
step 2) putting the raw materials in the step 1) into a sulfuric acid solution for primary leaching treatment to obtain primary leaching filtrate and primary leaching filter residue;
step 3) carrying out secondary oxidation leaching on the primary leaching filter residue obtained in the step 2) to obtain oxidation leaching filter residue and oxidation leaching filtrate;
step 4) extracting the primary leaching filtrate obtained in the step 2) to obtain an indium loaded organic phase and an extraction liquid;
and 5) extracting the oxidation leaching filtrate obtained in the step 3) to obtain an indium loaded organic phase and an extraction liquid.
2. The method for selectively extracting indium from the dust removed from the rotary hearth furnace according to claim 1, wherein the dust removed from the rotary hearth furnace in the step 1) is secondary dust obtained by treating the dust removed from the blast furnace through a rotary hearth furnace process, and the dust removed from the rotary hearth furnace is crushed and ground to have a particle size of less than 74 μm, and then is dried at a temperature of 105 ± 5 ℃ to have a constant weight.
3. The method for selectively extracting indium from dust removed from the rotary hearth furnace according to claim 1, wherein the liquid-solid ratio of the sulfuric acid solution in the step 2) is 5: 1-9: 1mL/g, the time of the primary leaching treatment is 1-5 h, and the temperature of the primary leaching treatment is 25-90 ℃.
4. The method for selectively extracting indium from dust removed from the rotary hearth furnace according to claim 3, wherein the sulfuric acid solution is further subjected to stirring treatment during the primary leaching treatment in the step 2), and the stirring treatment speed is 0-600 rpm.
5. The method for selectively extracting indium from dust removed from the rotary hearth furnace according to claim 4, wherein the liquid-solid ratio of the sulfuric acid solution in the step 2) is 7:1mL/g, the time of the primary leaching treatment is 3h, the temperature of the primary leaching treatment is 90 ℃, the stirring treatment speed is 500rpm, and the concentration of the sulfuric acid solution is 180 g/L.
6. The method for selectively extracting indium from the dedusting ash of the rotary hearth furnace according to claim 1, wherein in the step 3), the primary leaching filter residue is subjected to secondary oxidation treatment by adding a nitric acid solution and a sulfuric acid solution, the liquid-solid ratio of the nitric acid solution to the primary leaching filter residue is 0.8: 1-1.5: 1mL/g, and the liquid-solid ratio of the sulfuric acid solution to the primary leaching filter residue is 5: 1-9: 1 mL/g.
7. The method for selectively extracting indium from the dedusting ash of the rotary hearth furnace according to claim 6, wherein the liquid-solid ratio of the nitric acid solution to the primary leaching filter residue in the step 3) is 1:1mL/g, and the liquid-solid ratio of the sulfuric acid solution to the primary leaching filter residue is 7:1 mL/g.
8. The method for selectively extracting indium from dust removed from the rotary hearth furnace according to claim 1, wherein P is used in the step 4)2O4And sulfonated kerosene as extraction liquid to extract the primary leaching filtrate, and P2O4The volume fraction of the sulfonated kerosene is 20-40%, the ratio of a water phase to an organic phase in the sulfonated kerosene is 3: 1-5: 1, the extraction time is 6-10 min, and 2-4-stage countercurrent extraction is carried out while keeping the initial pH of primary leaching filtrate unchanged.
9. The method for selectively extracting indium from dust removed from the rotary hearth furnace according to claim 8, wherein P in the step 4) is2O4The volume fraction of the sulfonated kerosene is 30 percent, the ratio of a water phase to an organic phase in the sulfonated kerosene is 4:1, the extraction time is 8min, and the initial pH of primary leaching filtrate is kept unchangedLine 3 stage countercurrent extraction.
10. The method for selectively extracting indium from dust removed from the rotary hearth furnace according to claim 1, wherein P is used in the step 5)2O4And sulfonated kerosene as extraction liquid to extract the oxidation leaching filtrate, and P2O4The volume fraction of the sulfonated kerosene is 30 percent, the ratio of a water phase to an organic phase in the sulfonated kerosene is 4:1, the extraction time is 8min, and the initial pH of the oxidation leaching filtrate is kept unchanged for carrying out 1-stage countercurrent extraction.
CN202110955392.7A 2021-08-19 2021-08-19 Method for selectively extracting indium from dust of rotary hearth furnace Pending CN113621817A (en)

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Application publication date: 20211109