CN113787085A - A method for extracting Fe, Zn and Pb in electric furnace dust and utilizing them at high value - Google Patents
A method for extracting Fe, Zn and Pb in electric furnace dust and utilizing them at high value Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
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- Engineering & Computer Science (AREA)
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- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种提取电炉除尘灰中Fe、Zn、Pb并高值化利用的方法，以大宗危废电炉除尘灰作为原料，草酸作为浸出剂，在低温常压的反应条件下进行络合反应，进而达到梯级分离铁、锌资源的目的。在草酸浓度5～30％、液固比10:1～50:1、反应温度30～90℃、反应时间0.5～4h的条件下，电炉除尘灰中Fe浸出率能够达到92％以上，浸出渣中Zn含量(以ZnO计)可以达到36％以上，最终得到草酸亚铁的纯度可以达到97％以上。所述方法工艺简单，能耗低，反应成本少；得到的草酸亚铁、富锌渣具有更高附加值的同时，对环境的影响更小，具有良好的市场应用前景。
The invention discloses a method for extracting Fe, Zn and Pb from electric furnace dust ash and utilizing them at high value. The large hazardous waste electric furnace dust ash is used as raw material, oxalic acid is used as leaching agent, and complexation is carried out under the reaction conditions of low temperature and normal pressure. reaction, and then achieve the purpose of stepwise separation of iron and zinc resources. Under the conditions of oxalic acid concentration of 5-30%, liquid-solid ratio of 10:1-50:1, reaction temperature of 30-90°C, and reaction time of 0.5-4h, the leaching rate of Fe in the electric furnace dust can reach more than 92%, and the leaching slag The Zn content (calculated as ZnO) in the middle can reach more than 36%, and the purity of the final ferrous oxalate can reach more than 97%. The method has the advantages of simple process, low energy consumption and low reaction cost; the obtained ferrous oxalate and zinc-rich slag have higher added value, less impact on the environment, and good market application prospect.
Description
Technical Field
The invention relates to the field of solid waste treatment and resource utilization in the metallurgical industry, in particular to a method for clean extraction, resource utilization and high-value utilization of valuable elements Fe, Zn and Pb in the dust of a large amount of dangerous waste electric furnace dust of a steel enterprise, which is particularly suitable for FeOxThe content is more than or equal to 40.0 percent and mainly comprises Fe3+Is in the form of ZnO with a ZnO content of more than 10.0%, and other main components such as CaO, MgO, and SiO2、Al2O3And the like, the metallurgy iron-containing dust mud with the total content of not more than 10 percent is recycled and utilized in a high-value way.
Background
The steel industry is the national economy basic industry of China and is also the heavy industry with high emission and high consumption. In normal production activities, iron and steel enterprises can generate a large amount of iron-rich solid wastes, such as sintering dust, blast furnace dust, steel making dust mud, iron sheets generated in steel rolling stages and the like. Taking a production line with an annual output of 900 ten thousand tons of crude steel as an example, solid wastes in each process, including iron-containing solid waste products, carbon-containing solid waste products and other solid waste products, are produced in an annual output of approximately 700 thousand tons. The secondary utilization of these solid wastes has become an urgent problem to be solved by various iron and steel enterprises. At present, most enterprises can only select incineration, landfill or stockpiling modes for treatment and disposal of the metallurgical solid wastes due to capital and technical elbows. However, such a rough processing method not only causes a serious waste of resources, but also brings about a serious environmental problem. Therefore, the novel technology for comprehensively utilizing the bulk solid wastes of the iron and steel enterprises is developed, the high-efficiency, high-value and resource utilization of the iron and steel enterprises is realized, and the method has extremely important strategic significance on the sustainable development of the circular economy of the iron and steel enterprises.
The annual output of electric furnace steel in China is about 1 hundred million tons, and about 40-50 kg of electric furnace dust removal ash can be generated when the electric furnace produces 1 ton of steel. According to measurement and calculation, the annual output of the electric furnace dust removal ash in China is nearly 500 ten thousand tons, and the electric furnace dust removal ash becomes an important component in a large amount of dangerous/solid wastes of iron and steel enterprises. At present, iron and steel enterprises treat the electric furnace dust removal ash mainly by mixing the electric furnace dust removal ash into a rotary kiln or a rotary hearth furnace for recycling. However, the electric furnace dust removal ash often contains alkali metal elements such as Na and K, and the direct utilization of the alkali metal elements can corrode a furnace wall lining, so that the service life of equipment is seriously influenced; in addition, the electric furnace dust removal ash contains a large amount of Fe and Zn resources, and the Fe and Zn resources are recycled, so that a new way for supplying the Fe and Zn resources in China can be provided. At present, the recycling of valuable components in electric furnace dust mainly comprises the following methods: the physical method is that main element iron in the electric furnace dust is recycled by magnetic separation and other methods, and other valuable components are enriched in tailings after the magnetic separation, so that the purpose of step recovery is achieved, but the recovery efficiency of the method is low, and the recovery rate of Fe is only about 50%; the pyrogenic process and the wet process are respectively used for treating dust and sludge with high zinc content and high Na and K content, have small applicability and application range, and have no precedent of large-scale industrial utilization in most iron and steel enterprises.
In order to comprehensively recover valuable metal elements in electric furnace dust removal ash, the Chinese patent 'a method for comprehensively recovering silver, lead and iron from electric furnace dust removal ash (CN 201610617875.5)' provides a method for recovering silver, lead and iron in a wet-process step manner, but the method has long process flow and large medicament consumption, and a large amount of production wastewater not only increases the pollution risk, but also increases the cost of environmental management; chinese patent 'a device and (CN201810919589.3) that contains zinc and iron dust mud resource utilization' has proposed a device and method that contains zinc and iron dust mud resource utilization, and this technology has designed a new annular preheating reduction furnace, obtains the reduction molten iron through reduction smelting simultaneously, and the flue gas is collected through the dust remover after waste heat recovery can obtain the zinc oxide product, and this process flow equipment investment cost is high, and the product added value is low, therefore does not obtain large-scale popularization and application in the industry.
At present, iron and steel enterprises pay more and more attention to the comprehensive utilization of Fe resources in iron-rich dust under the influence of the rising price of upstream iron ores. Iron resources in the electric furnace dust removal ash are rich, chemical components are complex, and a targeted process method is selected according to the characteristics of different resources to carry out gradient recycling on valuable components in the dust removal ash. From the actual technical requirements of iron and steel enterprises, the comprehensive new process for removing dust from an electric furnace has the following characteristics: the production flow is simple, and the process cost is low; the recovery rate of valuable elements is high; the environmental pollution is small; high added value of the product and the like. In view of the above, the invention provides a process flow for recovering valuable elements Fe, Zn and Pb of the electric furnace dust removal ash through step separation, aiming at solving the cost problem and the environmental problem of the existing electric furnace dust removal ash treatment process, so as to recycle and highly value-added iron and zinc resources, thereby not only achieving the recycling and harmless treatment of the large amount of dangerous waste electric furnace dust removal ash and realizing the purposes of reducing the source of the electric furnace dust removal ash and controlling the whole process of pollutants, but also bringing actual profits to enterprises by the generated high value-added products and having wide market popularization and application values.
Disclosure of Invention
The invention aims to solve the technical problems of low comprehensive recovery utilization rate, serious secondary pollution, high equipment investment cost, low product added value and the like in the existing electric furnace dust removal comprehensive utilization technology, and provides a method for extracting Fe, Zn and Pb from electric furnace dust removal ash and utilizing the Fe, Zn and Pb in high value, wherein the method has mild process conditions, simple equipment and high Fe leaching rate.
The invention takes electric furnace dust generated in iron and steel enterprises as raw materials, organic acid solution (preferably oxalic acid) as a leaching agent and iron powder as a reducing agent, the three are mixed according to a certain proportion to prepare slurry, and rich iron resources in the electric furnace dust are converted into high value-added product ferrous oxalate by utilizing the complexation reaction between iron ions and organic acid radical ions (such as oxalate radical ions) under the experimental conditions of low temperature and low pressure; the slurry after the reaction is subjected to solid-liquid separation, so that the Zn content in the leaching residue can be greatly improved, and the leaching residue is used as a zinc extraction raw material, so that the raw material treatment capacity in the zinc extraction stage is greatly reduced, and the purity of the obtained zinc product is higher; the tailings after iron extraction, zinc extraction and lead extraction have low content of harmful elements, and can be used as raw materials for preparing ceramic products such as ceramsite, foamed ceramic and the like, so that near zero emission is realized. In order to achieve the purpose, the invention provides a method for extracting Fe, Zn and Pb from electric furnace dust and utilizing Fe, Zn and Pb with high value, which is implemented by adopting the following steps:
(1) adding electric furnace dedusting ash and oxalic acid solution in proportion, and fully and uniformly mixing to form uniformly distributed slurry; then, the slurry is injected into a reactor with constant temperature, and hydrothermal leaching reaction is carried out by controlling leaching temperature, leaching time, oxalic acid concentration, liquid-solid ratio and stirring speed;
(2) carrying out solid-liquid separation on the reaction product in the step (1), and filtering and washing the separation product to respectively obtain iron-rich complex ion leaching solution and leaching residue containing zinc-rich residue and ferrous oxalate;
(3) performing centrifugal separation on the leaching residue obtained in the step (2) by using the density difference between the ferrous oxalate and the zinc-rich residue, and respectively drying the obtained solids to obtain the zinc-rich residue and the ferrous oxalate solid;
(4) and (3) taking the iron-rich complex ion leaching solution obtained in the step (2) as a reaction raw material, oxalic acid as a reactant and Fe powder as a reducing agent to carry out precipitation reaction, and finally obtaining high-purity ferrous oxalate powder by regulating and controlling the precipitation reaction temperature and the precipitation reaction time.
Preferably, in the step (1), the mass concentration of oxalic acid is preferably in the range of 5-30%, and the liquid-solid ratio of the oxalic acid solution to the electric furnace dust is preferably in the range of 10: 1-50: 1; controlling the leaching temperature in the step (1) to be within a range of 30-90 ℃; leaching reaction time is 0.5-4 h; the stirring speed is 200 to 500r/min, preferably 300 to 400 r/min.
Furthermore, the granularity of the raw material of the electric furnace dust removal ash in the step (1) is preferably 50-500 meshes, and preferably 200-300 meshes.
Further, the drying temperature in the step (3) is preferably in the range of 40-90 ℃, preferably in the range of 50-65 ℃, and the drying time is 8-12 hours.
Further, in the precipitation reaction in the step (4), the amount of the added oxalic acid and the iron powder is adjusted according to the content of the Fe element in the leaching solution obtained in the step (2): if the amount of Fe substance in the leaching solution is x mol, the amount of oxalic acid substance is 0.8-2.0 x mol, preferably 1-1.5 x mol; the amount of the reduced iron powder material added is 2 to 5x mol, preferably 3 to 3.5x mol.
Further, in the precipitation reaction in the step (4), the precipitation reaction temperature is 70-90 ℃, and preferably 80-85 ℃; the precipitation reaction time is 2-5 h, preferably 3-4 h; the stirring speed is 200 to 500r/min, preferably 300 to 400 r/min.
Compared with the prior art, the method for extracting Fe, Zn and Pb from the electric furnace dust removal ash and utilizing the Fe, Zn and Pb in the electric furnace dust removal ash in a high-value mode has the following advantages:
(1) compared with the conventional treatment process, the method for extracting Fe, Zn and Pb from the electric furnace dust removal ash and utilizing the Fe, Zn and Pb in the electric furnace dust removal ash in a high-value mode treats the electric furnace dust removal ash through wet oxalic acid complexation, so that the Fe, Zn and Pb resources in the electric furnace dust removal ash are recycled in a gradient mode, the process flow is simple, the production cost is low, and the recovery rate of valuable elements and the purity of products are higher: the dust-removing ash of the electric furnace is fine in granularity, and is subjected to wet leaching treatment without crushing and grinding, so that the ore dressing cost can be reduced by about 50-60%; the recovery rates of main elements Fe, Zn and Pb are all more than 90 percent; through gravity separation and centrifugal separation, the ferrous oxalate and the leaching residue can be highly separated, the separation rate can reach more than 90 percent, and the purity of the obtained ferrous oxalate is stabilized at more than 95 percent; obtaining Zn-Pb alloy through vacuum smelting, wherein the purity of the Zn-Pb alloy can be kept above 90%;
(2) compared with the traditional electric furnace dust removal process, the method is more efficient, economic and environment-friendly: for iron and steel enterprises, zinc-rich raw materials obtained after iron extraction can be directly returned to a rotary hearth furnace or a rotary kiln for zinc recycling, the recovery rate of zinc can be improved by 20-30%, and the purity of the obtained metal zinc can be improved by more than 20%; in addition, the waste water after hydrothermal complex leaching and hydrothermal precipitation reaction can be collected and returned to the electric furnace dedusting ash leaching reaction stage for recycling, so that redundant discharge and pollution are avoided, and the environmental treatment cost is saved by 50-60%;
(3) compared with the traditional electric furnace dust removal process, the method has more general raw material applicability; no new special equipment needs to be developed, and the investment cost is low; the oxalic acid complex leaching method is adopted, the leaching temperature is low, and the overall production process can reduce the energy consumption and gas emission by more than 60%; compared with the conventional process, the high value-added products generated by the project, such as ferrous oxalate, zinc-rich raw materials, cementing materials and the like, can generate 5-7 times of direct profits, are technologies urgently needed by enterprises, and have good market popularization and application values;
drawings
FIG. 1 is a process flow chart of the principle of the method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing the Fe, Zn and Pb with high value;
FIG. 2 is an XRD spectrum of a ferrous oxalate product prepared by the embodiment of the invention (the reaction conditions are oxalic acid solution with concentration of 15%, liquid-solid ratio of 30:1, leaching temperature of 90 ℃, reaction time of 2h and stirring speed of 300 r/min);
FIG. 3 is a diagram showing the particle size distribution of a ferrous oxalate product prepared in an embodiment of the present invention (the reaction conditions include an oxalic acid solution with a concentration of 15%, a liquid-solid ratio of 30:1, a leaching temperature of 90 ℃, a reaction time of 2 hours, and a stirring speed of 300 r/min);
FIG. 4 is a scanning electron microscope picture of a ferrous oxalate product prepared in the embodiment of the present invention under a secondary electron mode (the reaction conditions are oxalic acid solution with a concentration of 15%, liquid-solid ratio of 30:1, leaching temperature of 90 ℃, reaction time of 2h, and stirring speed of 300 r/min).
Detailed Description
For describing the present invention, the method for extracting Fe, Zn, and Pb from the fly ash of an electric furnace and utilizing them in high value will be described in detail with reference to the accompanying drawings and examples.
As shown in a process flow chart of the principle of the method for extracting Fe, Zn and Pb from the electric furnace dust and utilizing the Fe, Zn and Pb in the electric furnace dust in a high-value manner, the method for extracting Fe, Zn and Pb from the electric furnace dust and utilizing the Fe, Zn and Pb in the electric furnace dust in a high-value manner is implemented by the following steps:
(1) adding electric furnace dedusting ash and oxalic acid solution in proportion, and fully and uniformly mixing to form uniformly distributed slurry; then, the slurry is injected into a reactor with constant temperature, and hydrothermal leaching reaction is carried out by controlling leaching temperature, leaching time, organic acid-oxalic acid concentration, liquid-solid ratio and stirring speed; in this step, the reaction conditions were: the mass concentration of the oxalic acid is 5-30%, the liquid-solid ratio of the oxalic acid solution to the electric furnace dust is 10: 1-50: 1, the leaching temperature is 30-90 ℃, the leaching reaction time is 0.5-4 h, and the stirring speed is 200-500 r/min.
(2) And (2) carrying out solid-liquid separation on the reaction product in the step (1), and filtering and washing the separation product to respectively obtain iron-rich complex ion leaching solution and leaching residue I containing zinc-rich residue and ferrous oxalate.
(3) And (3) performing centrifugal separation on the leaching residue obtained in the step (2) by utilizing the density difference between the ferrous oxalate and the zinc-rich residue, and drying the obtained solid for 8-12 hours at 50-65 ℃ respectively to obtain zinc-rich residue II and ferrous oxalate solid.
The zinc-rich slag II can be directly sold to downstream zinc extraction factories as a zinc-rich raw material, and can also be smelted to obtain Zn-Pb alloy.
(4) And (3) taking the iron-rich complex ion leaching solution obtained in the step (2) as a reaction raw material, oxalic acid as a reactant and Fe powder as a reducing agent to carry out precipitation reaction, and finally obtaining high-purity ferrous oxalate powder by regulating and controlling the precipitation reaction temperature and the precipitation reaction time. In the step, the amount of the added oxalic acid and the iron powder is adjusted according to the content of the Fe element in the leaching solution obtained in the step (2): if the amount of Fe substance in the leaching solution is x mol, the amount of oxalic acid substance added is 1-1.5 x mol, and the amount of reduced iron powder substance added is 3-3.5 x mol; the precipitation reaction temperature is 80-85 ℃, the precipitation reaction time is 3-4 h, and the stirring speed is 300-400 r/min.
The invention will be described in detail with reference to specific examples:
example 1:
weighing 1g of iron and steel enterprise electric furnace dust removal ash, preparing oxalic acid solution with the concentration of 15% and the liquid-solid ratio of 30:1, uniformly mixing the solution into evenly distributed slurry, then injecting the slurry into a three-neck flask, and immediately starting reaction. The specific reaction conditions are as follows: the leaching temperature is 90 ℃, the reaction time is 2h, and the stirring speed is 300 r/min.
After the reaction is finished, cooling the leaching solution to room temperature for solid-liquid separation. And filtering and washing the reaction product to obtain an iron-rich complex ion leaching solution A and leaching residues I, and fully separating ferrous oxalate and zinc-rich residues in the leaching residues through centrifugal separation. Through ICP-AES detection, the concentration of Fe ions in the obtained leaching solution A is 1602mg/L, and the leaching rate of Fe element is 92.35% in a conversion manner; the Zn content (calculated by ZnO) in the leaching residue I is 36.51%.
500mL of iron-rich complex ion leaching solution A is selected as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 2.0g of oxalic acid and 2.5g of reduced iron powder, leaching at 85 ℃, reacting for 3h, and stirring at 300 r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and filtering, washing and drying the reaction product to obtain high-purity ferrous oxalate powder. Through ICP-AES detection, the concentration of Fe ions in the obtained tail liquid is 78 mg/L; the purity of the prepared ferrous oxalate powder is 97.32%. The XRD patterns, particle size distributions and scanning electron micrographs (secondary electron patterns) thereof are shown in fig. 2, 3 and 4, and it can be found that: the prepared ferrous oxalate powder has good crystal form, the average grain diameter is 4.31 mu m, and the ferrous oxalate powder is spherical particles with smooth surfaces and regular shapes and can be used as raw materials of synthetic battery materials, medical products and photographic developers.
Example 2:
weighing 1g of iron and steel enterprise electric furnace dust removal ash, preparing 10% oxalic acid solution with a liquid-solid ratio of 50:1, uniformly mixing the solution and the oxalic acid solution into uniformly distributed slurry, injecting the slurry into a three-neck flask, and immediately starting to react. The specific reaction conditions are as follows: the leaching temperature is 90 ℃, the reaction time is 4h, and the stirring speed is 300 r/min.
After the reaction is finished, cooling the leaching solution to room temperature for solid-liquid separation. And filtering and washing the reaction product to obtain an iron-rich complex ion leaching solution A and leaching residues I, and fully separating ferrous oxalate and zinc-rich residues in the leaching residues through centrifugal separation. Through ICP-AES detection, the concentration of Fe ions in the obtained leaching solution A is 1495mg/L, and the leaching rate of Fe element is 86.78% in a conversion manner; the Zn content (calculated by ZnO) in the leaching residue I is 28.75 percent.
500mL of iron-rich complex ion leaching solution A is selected as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 1.5g of oxalic acid and 2.2g of reduced iron powder, leaching at 80 ℃, reacting for 3h, and stirring at 300 r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and filtering, washing and drying the reaction product to obtain high-purity ferrous oxalate powder. Detecting by ICP-AES, wherein the concentration of Fe ions in the obtained tail liquid is 105 mg/L; the purity of the prepared ferrous oxalate powder is 90.15%.
Example 3:
weighing 1g of iron and steel enterprise electric furnace dust removal ash, preparing 20% oxalic acid solution with a liquid-solid ratio of 50:1, uniformly mixing the solution and the oxalic acid solution into uniformly distributed slurry, injecting the slurry into a three-neck flask, and immediately starting to react. The specific reaction conditions are as follows: the leaching temperature is 90 ℃, the reaction time is 1h, and the stirring speed is 300 r/min.
After the reaction is finished, cooling the leaching solution to room temperature for solid-liquid separation. And filtering and washing the reaction product to obtain an iron-rich complex ion leaching solution A and leaching residues I, and fully separating ferrous oxalate and zinc-rich residues in the leaching residues through centrifugal separation. Through ICP-AES detection, the concentration of Fe ions in the obtained leaching solution A is 1539mg/L, and the leaching rate of Fe element is 88.38% in a conversion manner; the Zn content (calculated as ZnO) in the leaching residue I is 29.63 percent.
500mL of iron-rich complex ion leaching solution A is selected as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 1.8g of oxalic acid and 2.5g of reduced iron powder, leaching at 80 ℃, reacting for 3h, and stirring at 300 r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and filtering, washing and drying the reaction product to obtain high-purity ferrous oxalate powder. Through ICP-AES detection, the concentration of Fe ions in the obtained tail liquid is 133 mg/L; the purity of the prepared ferrous oxalate powder is 91.27%.
Example 4:
weighing 1g of iron and steel enterprise electric furnace dust removal ash, preparing oxalic acid solution with the concentration of 5% and the liquid-solid ratio of 30:1, uniformly mixing the solution into evenly distributed slurry, then injecting the slurry into a three-neck flask, and immediately starting reaction. The specific reaction conditions are as follows: the leaching temperature is 90 ℃, the reaction time is 4h, and the stirring speed is 300 r/min.
After the reaction is finished, cooling the leaching solution to room temperature for solid-liquid separation. And filtering and washing the reaction product to obtain an iron-rich complex ion leaching solution A and leaching residues I, and fully separating ferrous oxalate and zinc-rich residues in the leaching residues through centrifugal separation. Through ICP-AES detection, the concentration of Fe ions in the obtained leaching solution A is 1220mg/L, and the leaching rate of Fe element is 70.00% in a conversion way; the Zn content (calculated by ZnO) in the leaching residue I is 23.49%.
500mL of iron-rich complex ion leaching solution A is selected as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 1.3g of oxalic acid and 1.5g of reduced iron powder, leaching at 85 ℃, reacting for 3h, and stirring at 300 r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and filtering, washing and drying the reaction product to obtain high-purity ferrous oxalate powder. Through ICP-AES detection, the concentration of Fe ions in the obtained tail liquid is 147 mg/L; the purity of the prepared ferrous oxalate powder is 88.35%.
Example 5:
weighing 1g of iron and steel enterprise electric furnace dust removal ash, preparing oxalic acid solution with the concentration of 15% and the liquid-solid ratio of 20:1, uniformly mixing the solution into evenly distributed slurry, then injecting the slurry into a three-neck flask, and immediately starting reaction. The specific reaction conditions are as follows: the leaching temperature is 90 ℃, the reaction time is 1.5h, and the stirring speed is 300 r/min.
After the reaction is finished, cooling the leaching solution to room temperature for solid-liquid separation. And filtering and washing the reaction product to obtain an iron-rich complex ion leaching solution A and leaching residues I, and fully separating ferrous oxalate and zinc-rich residues in the leaching residues through centrifugal separation. Through ICP-AES detection, the concentration of Fe ions in the obtained leaching solution A is 1432mg/L, and the leaching rate of Fe element is 82.15% in a conversion way; the Zn content (calculated by ZnO) in the leaching residue I is 25.78 percent.
500mL of iron-rich complex ion leaching solution A is selected as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 1.6g of oxalic acid and 2.0g of reduced iron powder, leaching at 85 ℃, reacting for 3h, and stirring at 300 r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and filtering, washing and drying the reaction product to obtain high-purity ferrous oxalate powder. Through ICP-AES detection, the concentration of Fe ions in the obtained tail liquid is 122 mg/L; the purity of the prepared ferrous oxalate powder is 92.15%.
Example 6:
weighing 1g of iron and steel enterprise electric furnace dust removal ash, preparing oxalic acid solution with the concentration of 15% and the liquid-solid ratio of 30:1, uniformly mixing the solution into evenly distributed slurry, then injecting the slurry into a three-neck flask, and immediately starting reaction. The specific reaction conditions are as follows: the leaching temperature is 80 ℃, the reaction time is 1.5h, and the stirring speed is 300 r/min.
After the reaction is finished, cooling the leaching solution to room temperature for solid-liquid separation. And filtering and washing the reaction product to obtain an iron-rich complex ion leaching solution A and leaching residues I, and fully separating ferrous oxalate and zinc-rich residues in the leaching residues through centrifugal separation. Through ICP-AES detection, the concentration of Fe ions in the obtained leaching solution A is 1594mg/L, which is converted into the leaching rate of the Fe element of 91.85%; the Zn content (calculated by ZnO) in the leaching residue I is 31.05 percent.
500mL of iron-rich complex ion leaching solution A is selected as a reaction raw material to prepare high-purity ferrous oxalate powder, and the specific reaction conditions are as follows: adding 2.0g of oxalic acid and 2.5g of reduced iron powder, leaching at 85 ℃, reacting for 3h, and stirring at 300 r/min. After the reaction is finished, carrying out solid-liquid separation when the solution is cooled to room temperature, and filtering, washing and drying the reaction product to obtain high-purity ferrous oxalate powder. Through ICP-AES detection, the concentration of Fe ions in the obtained tail liquid is 98 mg/L; the purity of the prepared ferrous oxalate powder was 95.33%.
The invention adopts organic acid-oxalic acid as solvent, adopts low-temperature direct leaching, utilizes the strong complexation of oxalate ions to react with Fe in electric furnace dust to form [ Fe (C)2O4)3]3-Entering a solution; subsequently, [ Fe (C) under the action of reduced iron powder2O4)3]3-Reacting with Fe powder to produce high value-added product ferrous oxalate. After a high-added-value ferrous oxalate product is obtained, high-grade zinc-containing tailings obtained through solid-liquid separation can be sold to downstream zinc extraction factories as a zinc-rich raw material, and can also be used as a raw material for vacuum reduction zinc extraction to further obtain a high-added-value Zn-Pb alloy; aiming at the fact that tailings after iron extraction and zinc extraction can be used as raw materials for preparing ceramic products such as ceramsite and foamed ceramic, the gradient comprehensive utilization and near zero emission of electric furnace dust are achieved, energy consumption is low, environmental influence is small, the added value of products is high, and the method has wide market application prospects.
It should be further noted that, in the present invention, oxalic acid is used as the leaching agent in step (1), and other organic acids, such as one of formic acid, acetic acid and citric acid, or a mixture of oxalic acid, formic acid, acetic acid and citric acid, may also be used.
Claims (8)
1. A method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization is characterized by comprising the following steps:
(1) adding electric furnace dedusting ash and oxalic acid solution in proportion, and fully and uniformly mixing to form uniformly distributed slurry; then, the slurry is injected into a reactor with constant temperature, and hydrothermal leaching reaction is carried out by controlling leaching temperature, leaching time, oxalic acid concentration, liquid-solid ratio and stirring speed;
(2) carrying out solid-liquid separation on the reaction product in the step (1), and filtering and washing the separation product to respectively obtain iron-rich complex ion leaching solution and leaching residue containing zinc-rich residue and ferrous oxalate;
(3) performing centrifugal separation on the leaching residue obtained in the step (2) by using the density difference between the ferrous oxalate and the zinc-rich residue, and respectively drying the obtained solids to obtain the zinc-rich residue and the ferrous oxalate solid;
(4) and (3) taking the iron-rich complex ion leaching solution obtained in the step (2) as a reaction raw material, oxalic acid as a reactant and Fe powder as a reducing agent to carry out precipitation reaction, and finally obtaining high-purity ferrous oxalate powder by regulating and controlling the precipitation reaction temperature and the precipitation reaction time.
2. The method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at high value according to claim 1, wherein: in the step (1), the mass concentration of oxalic acid is 5-30%; the liquid-solid ratio of the oxalic acid solution to the electric furnace dust removal ash is 10: 1-50: 1;
3. the method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at high value according to claim 2, wherein: the leaching temperature in the step (1) is 30-90 ℃; leaching reaction time is 0.5-4 h; the stirring speed is 200 to 500 r/min.
4. The method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at high level as claimed in claim 1, 2 or 3, wherein: and (4) drying at the temperature of 40-90 ℃ for 8-12 h in the step (3).
5. The method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at high value according to claim 4, wherein: in the precipitation reaction in the step (4), the amount of the added oxalic acid and the iron powder is adjusted according to the content of the Fe element in the leaching solution obtained in the step (2): if the amount of Fe substances in the leaching solution is x mol, the amount of oxalic acid substances added is 0.8-2.0 x mol; the amount of the reduced iron powder material added is 2 to 5x mol.
6. The method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at high value according to claim 5, wherein: in the precipitation reaction in the step (4), the precipitation reaction temperature is 70-90 ℃, the precipitation reaction time is 2-5 h, and the stirring speed is 200-500 r/min.
7. The method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at high value according to claim 6, wherein: in the precipitation reaction in the step (4), the precipitation reaction temperature is 80-85 ℃, the precipitation reaction time is 3-4 h, and the stirring speed is 300-400 r/min.
8. The method for extracting Fe, Zn and Pb from the fly ash of an electric furnace and utilizing them at a high value according to claim 7, wherein: the drying temperature in the step (3) is 50-65 ℃; the amount of oxalic acid added in the step (4) is 1-1.5 x mol, and the amount of reduced iron powder added is 3-3.5 x mol.
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| CN202111198498.3A CN113787085A (en) | 2021-10-14 | 2021-10-14 | A method for extracting Fe, Zn and Pb in electric furnace dust and utilizing them at high value |
| PCT/CN2022/092438 WO2023060889A1 (en) | 2021-10-14 | 2022-05-12 | Method for extracting fe, zn and pb from electric furnace dedusting ash and high value utilization of same |
| CN202210836286.1A CN115532770B (en) | 2021-10-14 | 2022-07-15 | Method for preparing lithium iron phosphate, a positive electrode material for lithium batteries, using iron scale as raw material |
| CN202210835876.2A CN115463935B (en) | 2021-10-14 | 2022-07-15 | Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid waste in metallurgical industry |
| ZA2023/02411A ZA202302411B (en) | 2021-10-14 | 2023-02-23 | Method for extraction and high-value utilization of fe, zn and pb in electric furnace dedusting ash |
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| CN114315255A (en) * | 2022-01-27 | 2022-04-12 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for preparing high-purity alloy by using electric furnace dust removal ash and recycling tailings |
| WO2023060889A1 (en) * | 2021-10-14 | 2023-04-20 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for extracting fe, zn and pb from electric furnace dedusting ash and high value utilization of same |
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| CN117246987A (en) * | 2023-09-13 | 2023-12-19 | 武汉启钠新能源科技有限公司 | Method for preparing composite sodium iron phosphate positive electrode material by utilizing iron slag solid waste |
| CN118406874B (en) * | 2024-07-04 | 2024-09-10 | 北京高能时代环境技术股份有限公司 | Recycling method for cooperatively disposing lead-containing waste residues through steel dust and mud |
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| CN115532770A (en) | 2022-12-30 |
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