CN110002421B - Method for preparing battery-grade iron phosphate by using sulfuric acid residues - Google Patents
Method for preparing battery-grade iron phosphate by using sulfuric acid residues Download PDFInfo
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- CN110002421B CN110002421B CN201910410771.0A CN201910410771A CN110002421B CN 110002421 B CN110002421 B CN 110002421B CN 201910410771 A CN201910410771 A CN 201910410771A CN 110002421 B CN110002421 B CN 110002421B
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for preparing battery-grade iron phosphate by using pyrite cinder, which is characterized by comprising the following steps of: after ball milling treatment, separating the sulfuric acid residue by high-gradient magnetic separation; after dehydration treatment, leaching the obtained magnetic separation product by using phosphoric acid; the obtained leaching residue is a crude ferric phosphate dihydrate product, the crude ferric phosphate dihydrate product is placed in a mixed acid of phosphoric acid and hydrofluoric acid for leaching and impurity removal, and a solid product is washed and dried to obtain a battery-grade ferric phosphate product; the method uses the sulfuric acid residue industrial waste residue as the raw material to obtain the high-value battery-grade iron phosphate, not only realizes waste utilization, but also obtains higher economic value, and the method has the advantages of simple operation, low production cost and environmental protection, and meets the requirements of industrial production.
Description
Technical Field
The invention relates to a preparation method of high-purity iron phosphate, in particular to a method for preparing battery-grade iron phosphate by using sulfuric acid residue as a raw material, and belongs to the field of mineral processing and hydrometallurgy.
Background
The sulfuric acid residue, also called pyrite cinder, is industrial waste residue produced in the process of producing sulfuric acid. The pyrite cinder contains rich iron and partial elements such as calcium, silicon, copper, sulfur and the like, but the pyrite cinder has low content of nonferrous metals, and metal minerals and gangue minerals are mutually wrapped, so that the comprehensive utilization of the pyrite cinder is limited. About 8000 million tons of sulfuric acid residues are discharged in China every year, and the national accumulated reserves are over hundred million tons. The accumulation of a large amount of sulfate slag wastes land resources and causes serious pollution to the environment. In addition, the utilization rate of the sulfate slag in some developed countries is close to 100%, but the utilization rate of the sulfate slag in China is less than 50%.
At present, the comprehensive utilization approach of the pyrite cinder is mainly used as a raw material of sintered pellets. However, the method is only suitable for some sulfuric acid residues with higher iron grade, and most of the sulfuric acid residues in China have low iron grade and are difficult to meet the requirements of sintering and pelletizing plants. In order to improve the grade of the pyrite cinder, the pyrite cinder is generally treated by adopting a direct ore dressing method, and because metals and gangue in the pyrite cinder are of an embedded structure, the iron grade is further improved, so that the utilization of the pyrite cinder is limited. In addition to the two main comprehensive utilization lines, the pyrite cinder is also used for preparing iron-based pigments, cement and building materials and extracting nonferrous metals in the iron-based pigments, the cement and the building materials, but the comprehensive utilization of the pyrite cinder is limited due to low content of the nonferrous metals in the pyrite cinder, corrosion of equipment in a processing process, low utilization value and the like.
The lithium iron phosphate battery has the advantages of excellent charge and discharge performance, long service life, good thermal stability and the like, thereby having important market share in the market. The iron phosphate is one of the most important raw materials for preparing the iron phosphate, and the preparation method mainly adopts a solution synthesis method, and iron salt and phosphoric acid are used as raw materials to form a dihydrate iron phosphate product. However, the existing iron phosphate preparation process has high cost and needs high-quality iron raw materials.
Disclosure of Invention
Aiming at the problems of comprehensive utilization of sulfuric acid residues, low economic value of a value-added processing process and the like in the prior art, the invention aims to provide the method for preparing the battery-grade iron phosphate with high added value by using the industrial waste residues of the sulfuric acid residues, and the method is simple to operate, low in production cost, environment-friendly and capable of meeting the requirements of industrial production.
In order to realize the technical purpose, the invention provides a method for preparing battery-grade iron phosphate by utilizing sulfuric acid residues, which comprises the steps of carrying out ball milling treatment on the sulfuric acid residues, and then carrying out high-gradient magnetic separation; after dehydration treatment, leaching the obtained magnetic separation product by using phosphoric acid; and leaching the obtained leaching residue to obtain a crude ferric phosphate dihydrate product, and leaching and removing impurities from the crude ferric phosphate dihydrate product in a mixed acid of phosphoric acid and hydrofluoric acid to obtain a battery-grade ferric phosphate product.
In the preferable scheme, the sulfuric acid residue is ball-milled until the fineness of the sulfuric acid residue is more than 80 percent of the mass percentage of the fraction with the fineness less than 0.037 mm. The ball milling process can adopt ball milling means commonly used in the prior art, such as wet ball milling. Under the optimal ball milling condition, the close embedding relation among different components in the pyrite cinder can be destroyed through mechanical force, the subsequent leaching and conversion process of iron is facilitated, and the recovery rate of the iron is improved.
In the preferable scheme, the magnetic field intensity of the high-gradient magnetic separation is 1.0-2.5T. According to the fact that the main phase of iron in the pyrite cinder is ferric oxide, the pyrite cinder belongs to weakly magnetic minerals, and high-gradient magnetic separation is preferentially adopted to realize high-efficiency recovery and enrichment of the iron minerals.
In a preferred embodiment, the phosphoric acid leaching conditions are as follows: the concentration of phosphoric acid is 1.5-4.5 mol/L, the solid-to-solid ratio of a leaching solution is 8-16 mL/g, the leaching temperature is 80-160 ℃, and the leaching time is 4-12 h. The concentration of the phosphoric acid can be controlled to ensure that iron oxide is dissolved and then converted into ferric phosphate dihydrate to be precipitated and enriched in a slag phase in the leaching process, and other impurity metal ions still exist in the leaching solution in the form of metal ions, so that the separation of iron and other metal ions can be realized through simple solid-liquid separation.
In a preferable scheme, the mass percentage concentration of hydrofluoric acid in the phosphoric acid-hydrofluoric acid mixed acid is 1.0-2.5%, and the mass percentage concentration of phosphoric acid is 2.0-4.5%. In the leaching impurity removal process, dilute phosphoric acid with relatively high concentration is adopted and a small amount of hydrofluoric acid is doped, the hydrofluoric acid can play a role in destroying silicate minerals in the sulfuric acid slag, and is beneficial to promoting dissociation and dissolution of metal ions wrapped by gangue minerals such as silicate and the like, and the small amount of phosphoric acid can ensure that newly dissolved metals are converted into ferric phosphate dihydrate, so that after leaching impurity removal, a small amount of gangue such as silicate and the like is removed, a small amount of dissolved iron is converted, and the purity of the product is further improved.
In a preferred scheme, the leaching and impurity removing conditions are as follows: the solid-to-solid ratio of the leaching solution is 3-10 mL/g, the leaching temperature is room temperature, and the leaching time is 3-10 hours. Under the preferable leaching impurity removal condition, minerals such as residual silicate can be fully dissociated, and leached metal ions are converted into ferric phosphate dihydrate, so that the product purity is further improved.
The sulfuric acid residue is waste residue after high-temperature oxidation roasting treatment, wherein iron mainly exists in the form of hematite (ferric oxide), other valuable metals such as calcium, magnesium, copper, nickel, cobalt, lead, zinc and the like mostly enter iron oxide lattices in the form of oxides or doped forms, silicon and aluminum mainly form silicates, aluminates and the like and are in a close embedding and mutual wrapping relationship, and a small amount of sulfate and sulfide are contained in the sulfuric acid residue. In order to realize the separation of impurity elements in the sulfuric acid slag, firstly, the ball milling treatment is carried out, the mechanical energy is adopted to destroy the close distribution relation among different components in the sulfuric acid slag, the iron minerals are promoted to realize the monomer dissociation, the iron minerals mainly exist in a weak magnetic ferric oxide phase, the recovery and enrichment of the iron minerals can be realized through high gradient magnetic separation, and in the process, part of impurity metal elements with finer granularity or existing in a crystal lattice substitution form are optionally remained and mixed in the iron oxide after the magnetic separation. On the basis, phosphoric acid is firstly adopted for leaching, the dissolution of ferric oxide and other metal oxides can be promoted by utilizing the solubility difference of ferric phosphate, copper phosphate, nickel phosphate, cobalt phosphate and the like under different phosphoric acid concentrations and pH conditions in the leaching process through controlling the phosphoric acid concentration adjustment, metal ions are dissolved out and enter a solution, iron ions are selectively precipitated in the form of ferric phosphate dihydrate, and other metal ions still exist in the form of ions, so that the separation of iron and other metal ions can be realized through simple solid-liquid separation. However, the obtained crude product of the ferric phosphate dihydrate also contains silicate minerals and the like which are mixed, and can wrap part of iron ore, and the purity of the ferric phosphate dihydrate is far lower than the battery level requirement.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the invention uses the industrial waste residues of the sulfuric acid residues as raw materials to obtain the high-value battery-grade iron phosphate, thereby not only realizing the utilization of wastes, but also obtaining higher economic value.
2) According to the invention, through ore grinding and magnetic separation, impurity components such as main metals and silicates in the sulfuric acid slag can be removed, the separation and recovery of iron phosphate and main metal impurity elements are realized through the regulation and control of the phosphoric acid leaching process, and finally, silicon-containing oxides in the synthesized product are removed through the impurity removal of a hydrofluoric acid-phosphoric acid mixed solution, so that the battery-grade ferric phosphate dihydrate product is finally prepared.
3) The preparation method of the iron phosphate provided by the invention is simple to operate, low in energy consumption and cost, easy to realize industrial production, and realizes comprehensive utilization of solid wastes while realizing value-added processing of the pyrite cinder.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 XRD pattern of the product prepared in example 1;
FIG. 3 SEM separation of the product prepared in example 1.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Comparative example 1
Leaching phosphoric acid with 60.3% iron grade, 1.2%, 0.8%, 2.3%, 1.2%, 0.8%, 0.6%, 0.4%, 1.0%, 0.1% and 0.1% sodium content of aluminum, calcium, silicon, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium content of 1.2%, 0.8%, 0.6%, 0.4%, 1.0%, 0.1% and 0.1% respectively as raw materials, filtering for solid-liquid separation after leaching, wherein the concentration of the phosphoric acid is 1.5mol/L, the liquid-solid ratio is 16ml/g, the leaching temperature is 80 ℃, and the leaching time is 12 hours; carrying out secondary leaching impurity removal on the solid-phase product, wherein the concentration of hydrofluoric acid in an impurity removing agent is 1.0%, the concentration of phosphoric acid in the impurity removing agent is 4.5%, the solid-to-solid ratio of a leaching solution is 3ml/g, the leaching temperature is room temperature, and the leaching time is 10 hours; and filtering again for solid-liquid separation, and washing the synthesized product with distilled water until the pH value of the filtrate is more than 5 to obtain primary ferric phosphate dihydrate, wherein the purity of the ferric phosphate is 89.3 percent, the median particle size is 10.3 mu m, the recovery rate of iron in the whole process flow is 97.3 percent, the impurity contents of calcium, magnesium, zinc, cobalt, sulfur, potassium and sodium in the product are all lower than 0.005 percent, the contents of copper and aluminum are higher than 0.1 percent, and the silicon content is higher than 1.0 percent.
Comparative example 2
Using sulfuric acid residues (iron grade is 60.3%, and contents of aluminum, calcium, silicon, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are respectively 1.2%, 0.8%, 2.3%, 1.2%, 0.8%, 0.6%, 0.4%, 1.0%, 0.1% and 0.1%) of a certain sulfuric acid plant as raw materials, firstly ball-milling the sulfuric acid residues until the proportion of-0.037 mm is higher than 80%, then placing the sulfuric acid residues in a high-gradient magnetic separator with the magnetic field intensity of 1.0T for magnetic separation, dehydrating the magnetic separation product, leaching the phosphoric acid, wherein the concentration of the phosphoric acid is 1.5mol/L, the liquid-solid ratio is 16ml/g, the leaching temperature is 80 ℃, the leaching time is 12 hours, and filtering the sulfuric acid residues for solid-liquid separation after the leaching is finished; and washing the synthesized product with distilled water until the pH value of the filtrate is more than 5 to obtain primary ferric phosphate dihydrate, wherein the purity of ferric phosphate is 90.2%, the median particle size is 6.21 mu m, the recovery rate of iron in the whole process flow is 95.3%, the impurity content of aluminum, calcium, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium in the product is lower than 0.005%, and the silicon content is lower than 2.0%.
Example 1:
firstly, sulfuric acid slag (iron grade is 60.3%, and contents of aluminum, calcium, silicon, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are respectively 1.2%, 0.8%, 2.3%, 1.2%, 0.8%, 0.6%, 0.4%, 1.0%, 0.1% and 0.1%) of a certain sulfuric acid plant is taken as a raw material, the sulfuric acid slag is ball-milled until the proportion of minus 0.037mm is higher than 80%, and the concentration of ball-milling ore pulp is 40%; placing the mixture in a high-gradient magnetic separator with the magnetic field intensity of 1.0T for magnetic separation, dehydrating the magnetic separation product, leaching the dehydrated product with phosphoric acid, wherein the concentration of the phosphoric acid is 1.5mol/L, the liquid-solid ratio is 16ml/g, the leaching temperature is 80 ℃, the leaching time is 12 hours, and filtering the dehydrated product after the leaching is finished to perform solid-liquid separation; carrying out secondary leaching impurity removal on the solid-phase product, wherein the concentration of hydrofluoric acid in an impurity removing agent is 1.0%, the concentration of phosphoric acid in the impurity removing agent is 4.5%, the solid-to-solid ratio of a leaching solution is 3ml/g, the leaching temperature is room temperature, and the leaching time is 10 hours; and filtering again for solid-liquid separation, and washing the synthesized product with distilled water until the pH of the filtrate is more than 5, thus obtaining a product, namely the battery-grade ferric phosphate dihydrate, wherein the purity of the ferric phosphate is 99.5%, the median particle size is 5.32 mu m, the recovery rate of the iron in the whole process flow is 95.3%, the impurity contents of the products of aluminum, calcium, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are all lower than 0.005%, and the silicon content is lower than 0.1%.
Example 2:
firstly, sulfuric acid slag (iron grade is 60.3%, and contents of aluminum, calcium, silicon, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are respectively 1.2%, 0.8%, 2.3%, 1.2%, 0.8%, 0.6%, 0.4%, 1.0%, 0.1% and 0.1%) of a certain sulfuric acid plant is taken as a raw material, the sulfuric acid slag is ball-milled until the proportion of minus 0.037mm is higher than 90%, and the concentration of ball-milling ore pulp is 50%; placing the mixture in a high-gradient magnetic separator with the magnetic field intensity of 2.5T for magnetic separation, dehydrating the magnetic separation product, leaching the dehydrated product with phosphoric acid, wherein the concentration of the phosphoric acid is 4.5mol/L, the liquid-solid ratio is 8ml/g, the leaching temperature is 160 ℃, the leaching time is 4 hours, and filtering the dehydrated product after the leaching is finished to perform solid-liquid separation; carrying out secondary leaching impurity removal on the solid-phase product, wherein the concentration of hydrofluoric acid in an impurity removing agent is 2.5%, the concentration of phosphoric acid in the impurity removing agent is 2.0%, the solid-to-solid ratio of a leaching solution is 10ml/g, the leaching temperature is room temperature, and the leaching time is 10 hours; and filtering again for solid-liquid separation, and washing the synthesized product with distilled water until the pH value of the filtrate is more than 6 to obtain a product, namely the battery-grade ferric phosphate dihydrate, wherein the purity of the ferric phosphate is 99.2%, the median particle size is 4.68 mu m, the recovery rate of the iron in the whole process flow is 90.2%, the impurity contents of the products of aluminum, calcium, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are all lower than 0.005%, and the silicon content is lower than 0.05%.
Example 3:
firstly, sulfuric acid slag (iron grade is 55.6%, and contents of aluminum, calcium, silicon, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are respectively 2.5%, 4.3%, 2.1%, 0.4%, 0.3%, 0.1%, 1.3%, 0.1% and 0.1%) of a certain sulfuric acid plant is taken as a raw material, the sulfuric acid slag is ball-milled until the proportion of minus 0.037mm is higher than 95%, and the concentration of ball-milled ore pulp is 55%; placing the mixture in a high-gradient magnetic separator with the magnetic field intensity of 1.0T for magnetic separation, dehydrating the magnetic separation product, leaching the dehydrated product with phosphoric acid, wherein the concentration of the phosphoric acid is 3.0mol/L, the liquid-solid ratio is 10ml/g, the leaching temperature is 160 ℃, the leaching time is 4 hours, and filtering the dehydrated product after the leaching is finished to perform solid-liquid separation; carrying out secondary leaching impurity removal on the solid-phase product, wherein the concentration of hydrofluoric acid in an impurity removing agent is 2.5%, the concentration of phosphoric acid in the impurity removing agent is 3.0%, the solid-to-solid ratio of a leaching solution is 8ml/g, the leaching temperature is room temperature, and the leaching time is 10 hours; and filtering again for solid-liquid separation, and washing the synthesized product with distilled water until the pH of the filtrate is more than 5 to obtain a product, namely the battery-grade ferric phosphate dihydrate, wherein the purity of the ferric phosphate is 99.3%, the median particle size is 3.98 mu m, the recovery rate of the iron in the whole process flow is 85.3%, the impurity contents of the products of aluminum, calcium, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are all lower than 0.005%, and the silicon content is lower than 0.1%.
Example 4:
firstly, sulfuric acid slag (iron grade is 55.6%, and contents of aluminum, calcium, silicon, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium are respectively 2.5%, 4.3%, 2.1%, 0.4%, 0.3%, 0.1%, 1.3%, 0.1% and 0.1%) of a certain sulfuric acid plant is taken as a raw material, the sulfuric acid slag is ball-milled until the granularity is 100% and is less than 0.037mm, and the concentration of ball-milled ore pulp is 50%; placing the mixture in a high-gradient magnetic separator with the magnetic field intensity of 2.0T for magnetic separation, dehydrating the magnetic separation product, leaching the dehydrated product with phosphoric acid, wherein the concentration of the phosphoric acid is 2.0mol/L, the liquid-solid ratio is 16ml/g, the leaching temperature is 100 ℃, the leaching time is 4 hours, and filtering the dehydrated product after the leaching is finished to perform solid-liquid separation; carrying out secondary leaching impurity removal on the solid-phase product, wherein the concentration of hydrofluoric acid in an impurity removing agent is 2.5%, the concentration of phosphoric acid in the impurity removing agent is 3.0%, the solid-to-solid ratio of a leaching solution is 8ml/g, the leaching temperature is room temperature, and the leaching time is 6 hours; and filtering again for solid-liquid separation, and washing the synthesized product with distilled water until the pH of the filtrate is more than 5, so as to obtain a product, namely battery-grade ferric phosphate dihydrate, wherein the purity of the ferric phosphate is 99.5%, the median particle size is 4.68 mu m, the recovery rate of iron in the whole process flow is 89.8%, the impurity contents of aluminum, calcium, magnesium, zinc, copper, cobalt, sulfur, potassium and sodium in the product are all lower than 0.005%, and the silicon content is lower than 0.08%.
Claims (4)
1. A method for preparing battery-grade iron phosphate by using pyrite cinder is characterized by comprising the following steps: after ball milling treatment, separating the sulfuric acid residue by high-gradient magnetic separation; after dehydration treatment, leaching the obtained magnetic separation product by using phosphoric acid; the obtained leaching residue is a crude ferric phosphate dihydrate product, and the crude ferric phosphate dihydrate product is placed in a mixed acid of phosphoric acid and hydrofluoric acid for leaching and impurity removal, so that a battery-grade ferric phosphate product is obtained;
the conditions of the phosphoric acid leaching are as follows: the concentration of phosphoric acid is 1.5-4.5 mol/L, the solid-to-solid ratio of a leaching solution is 8-16 mL/g, the leaching temperature is 80-160 ℃, and the leaching time is 4-12 h.
The mass percentage concentration of hydrofluoric acid in the phosphoric acid-hydrofluoric acid mixed acid is 1.0-2.5%, and the mass percentage concentration of phosphoric acid is 2.0-4.5%.
2. The method for preparing battery-grade iron phosphate by using sulfuric acid residues, according to claim 1, is characterized in that: the ball milling fineness of the pyrite cinder meets the condition that the mass percentage content of the particle fraction smaller than 0.037mm is higher than 80%.
3. The method for preparing battery-grade iron phosphate by using sulfuric acid residues, according to claim 1, is characterized in that: the magnetic field intensity of the high-gradient magnetic separation is 1.0-2.5T.
4. The method for preparing battery-grade iron phosphate by using sulfuric acid residues, according to claim 1, is characterized in that: the leaching impurity removal conditions are as follows: the solid-to-solid ratio of the leaching solution is 3-10 mL/g, the leaching temperature is room temperature, and the leaching time is 3-10 hours.
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| CN110304617A (en) * | 2019-08-01 | 2019-10-08 | 湖北昊瑞新能源有限公司 | A kind of preparation method of low cost ferric orthophosphate |
| CN115611250B (en) * | 2021-07-16 | 2024-04-02 | 中国科学院过程工程研究所 | Method for recycling high-purity ferric phosphate from waste lithium iron phosphate positive electrode powder |
| CN114604837B (en) * | 2022-03-30 | 2022-10-21 | 湖北宇浩高科新材料有限公司 | Preparation method of iron phosphate and preparation method of lithium iron phosphate |
| CN116425136B (en) * | 2023-05-06 | 2023-12-19 | 浙江南化防腐设备有限公司 | Method for purifying and recycling battery-grade ferric phosphate from lithium-extracted ferrophosphorus slag |
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| CN101554613A (en) * | 2009-05-19 | 2009-10-14 | 房志强 | Method for recycling industrial waste sulfate slag |
| CN102851486A (en) * | 2012-08-17 | 2013-01-02 | 山东明瑞化工集团有限公司 | Pyrite cinder treatment method |
| CN104402062A (en) * | 2014-11-14 | 2015-03-11 | 贵州大学 | Method for preparing ferric chloride from pyrite cinder |
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