WO2025076819A1 - 一种铁铝渣资源化回收铝和铁的方法 - Google Patents
一种铁铝渣资源化回收铝和铁的方法 Download PDFInfo
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- WO2025076819A1 WO2025076819A1 PCT/CN2023/124513 CN2023124513W WO2025076819A1 WO 2025076819 A1 WO2025076819 A1 WO 2025076819A1 CN 2023124513 W CN2023124513 W CN 2023124513W WO 2025076819 A1 WO2025076819 A1 WO 2025076819A1
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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
- C22B1/00—Preliminary treatment of ores or scrap
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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
- C22B21/00—Obtaining aluminium
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention belongs to the technical field of waste battery recycling and relates to a method for recycling aluminum and iron from iron-aluminum slag.
- the main materials produced are graphite slag, iron-aluminum slag and sponge copper.
- sponge copper can be sold as a product at a low price;
- the main component of graphite slag is the negative electrode powder graphite in the battery powder;
- the iron-aluminum slag has the largest slag volume, and its main components are iron and aluminum, and it also carries a certain amount of valuable heavy metals such as nickel, cobalt and manganese. It is very difficult to recycle or harmlessly dispose of it.
- the industry currently treats iron-aluminum slag as solid waste or hazardous waste.
- Iron and aluminum are metal elements with high content in nature and have high utilization value.
- the iron-aluminum slag produced by the wet process of recycling waste batteries contains a large amount of iron and aluminum. It is very meaningful to be able to separate and recycle this part of iron and aluminum.
- the present invention aims to provide a method for recycling aluminum and iron from iron-aluminum slag.
- the present invention first separates sulfate from the iron-aluminum slag by alkali conversion reaction; then separates aluminum from the iron-aluminum slag after alkali conversion by alkali leaching reaction to obtain an aluminate solution, and then obtains hydroxide.
- the aluminum product is obtained by smelting the aluminum slag, while the iron element remains in the iron slag, thereby achieving the separation of the iron and aluminum elements; then, the iron sulfate product is obtained by using the solubility principle of iron sulfate. Therefore, the method disclosed in the present invention can effectively separate and recover the iron and aluminum elements in the iron and aluminum slag.
- the present invention adopts the following technical solutions:
- the present disclosure provides a method for recycling aluminum and iron from iron-aluminum slag, the method comprising:
- the present invention provides a method for recycling aluminum and iron from iron-aluminum slag.
- sulfate radicals in the iron-aluminum slag are separated by an alkali conversion reaction to obtain a sulfate solution, and then a sulfate product is obtained;
- aluminum elements are separated from the iron-aluminum slag after the alkali conversion by an alkali leaching reaction to obtain an aluminate solution, and then an aluminum hydroxide product is obtained, while the iron element remains in the iron slag, thereby achieving separation of the iron and aluminum elements;
- the iron slag is first acid-dissolved and sulfuric acid is added according to the solubility principle of iron sulfate to obtain an iron sulfate product, and the acid solution can be recycled;
- the method disclosed in the present invention can effectively separate and recover the iron and aluminum elements in the iron-aluminum slag, and can obtain sulfate products, aluminum hydroxide products and ferric sulfate products.
- the products can be sold to generate profits, and the utilization of the iron-aluminum slag can be maximized, which is beneficial to industrial applications.
- the iron-aluminum slag includes the iron-aluminum slag produced by wet recovery of ternary batteries.
- the iron-aluminum slag includes aluminum ions, iron ions, nickel ions, cobalt ions, manganese ions, sulfate ions, Organic matter (COD) and impurities (such as phosphorus and/or fluorine).
- COD Organic matter
- impurities such as phosphorus and/or fluorine
- nickel ions, cobalt ions and manganese ions are precipitated into the iron-aluminum slag after alkali conversion through alkali conversion reaction, and then enter the iron slag through alkali leaching reaction, and then dissolved in acid through acid dissolution, and finally remain in the acid solution.
- the acid solution can be reused in the acid dissolution step or returned to the battery recycling production line to recover nickel, cobalt and manganese.
- the alkaline substance in the first alkali solution in step (1) includes at least one of sodium hydroxide, calcium hydroxide and sodium carbonate.
- the alkaline substance of the first alkali solution when at least one of sodium hydroxide, calcium hydroxide and sodium carbonate is used as the alkaline substance of the first alkali solution, it can undergo an alkali conversion reaction with iron-aluminum slag, and the obtained sulfate solution is a sodium sulfate solution.
- the main chemical components of the iron aluminum slag are iron alum (NaFe 3 (SO 4 ) 2 (OH) 6 ) and aluminum alum (NaAl 3 (SO 4 ) 2 (OH) 6 ).
- iron alum NaFe 3 (SO 4 ) 2 (OH) 6
- aluminum alum NaAl 3 (SO 4 ) 2 (OH) 6
- reaction equation of the iron aluminum slag and sodium hydroxide is as follows:
- step (2) the liquid-to-solid mass ratio of the second alkali solution to the alkali-converted iron-aluminum slag is 5:1.
- the temperature of the alkali leaching reaction in step (2) is 60-80°C, for example, 60°C, 65°C, 70°C, 75°C or 80°C
- the time of the alkali leaching reaction is 2-4h, for example, 2h, 2.5h, 3h, 3.5h or 4h, etc.
- the alkali leaching reaction is carried out at a temperature of 60 to 80° C. for 2 to 4 hours to effectively leach aluminum.
- the Bayer process is a chemical process for producing aluminum oxide from bauxite.
- the Bayer process is used to prepare aluminum hydroxide, which has low energy consumption, low cost, high product purity, and the separated solution can be recycled without wasting alkali, which greatly reduces costs.
- the Bayer process includes the following steps:
- the aluminate solution in step (2) is mixed with seed crystals, and aluminum hydroxide and aluminate mother liquor are obtained after seed separation.
- the obtained aluminum hydroxide product complies with the product standard GB/T4294-2010 and can be sold externally.
- the seed crystals include aluminum hydroxide.
- the amount of the seed crystal added is 0.5 to 1.5 times the theoretical amount required for all aluminum elements in the aluminate solution to be converted into aluminum hydroxide, for example, it can be 0.5 times, 0.7 times, 1 times, 1.2 times, 1.3 times, 1.4 times or 1.5 times, etc. However, it is not limited to the listed values, and other values not listed within the numerical range are also applicable.
- the decomposition rate of aluminum hydroxide is low; if the amount of seed crystals added is too much, the decomposition rate increases only slightly, resulting in waste.
- the seeding temperature is 50-60°C, for example, 50°C, 52°C, 54°C, 56°C, 58°C or 60°C
- the seeding time is 1-10h, for example, 1h, 2h, 4h, 6h, 8h or 10h.
- it is not limited to the listed values, and other values not listed within the numerical range may be used. The same applies to values.
- the aluminum hydroxide can be effectively seeded by performing seeding at a temperature of 50 to 60° C. for 1 to 10 hours.
- the seeding process is accompanied by stirring, and the stirring speed is 150-300 r/min, for example, 150 r/min, 200 r/min, 250 r/min or 300 r/min, etc. However, it is not limited to the listed values, and other values not listed in the numerical range are also applicable.
- the stirring is continued at a rate of 150 to 300 r/min, so that the seed crystals can be fully dispersed in the solution and fully contact the solution.
- the mass concentration of aluminum in the aluminate mother solution is 9 to 12 g/L, for example, 9 g/L, 10 g/L, 11 g/L or 12 g/L.
- the aluminate mother liquor is mixed with the ferroaluminum slag after alkali conversion to carry out alkali leaching reaction, and an aluminate solution and iron slag are obtained after solid-liquid separation.
- the aluminate solution is further subjected to seed separation using the Bayer process to obtain aluminum hydroxide and new aluminate mother liquor.
- the aluminate mother liquor is mixed with the alkali-converted iron-aluminum slag, and no alkali is added, so that the alkali in the solution is recycled and the alkali cost is reduced.
- the aluminate mother liquor can be recycled for many times.
- the sulfate (such as sodium sulfate) and impurities (such as COD and a small amount of phosphorus and fluorine) in the aluminate mother liquor are highly enriched, the impurities are removed and then evaporated and crystallized to obtain sulfate.
- the acid used in the acid dissolution process of step (3) includes sulfuric acid, and the concentration of the acid is 2 to 4 mol/L, for example, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L or 4 mol/L.
- the concentration of the acid is 2 to 4 mol/L, for example, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L or 4 mol/L.
- the solute in the solution obtained by acid dissolution is mainly ferrous sulfate.
- high mass concentration sulfuric acid is added to obtain a saturated solution, and then cooled and crystallized to precipitate ferrous sulfate crystals to achieve resource utilization of iron.
- the recovery rate of ferrous sulfate is 90-99.5% (for example, it can be 90%, 92%, 95% or 98%, etc.). If the mass concentration of sulfuric acid is too low, the ferrous sulfate reaches the solubility and the ferrous sulfate does not precipitate.
- the acid solution after solid-liquid separation in step (3) mainly contains nickel sulfate/cobalt/manganese and acid, which can be returned to the acid dissolution or to the leaching and impurity removal process of the battery recovery production line to achieve comprehensive recovery and utilization of valuable metals.
- the present invention has the following beneficial effects:
- the present invention provides a method for recycling aluminum and iron from iron-aluminum slag.
- sulfate radicals in the iron-aluminum slag are separated by an alkali conversion reaction to obtain a sulfate solution, and then a sulfate product is obtained;
- aluminum elements are separated from the iron-aluminum slag after the alkali conversion by an alkali leaching reaction to obtain an aluminate solution, and then an aluminum hydroxide product is obtained, while the iron element remains in the iron slag, thereby achieving separation of the iron and aluminum elements;
- the iron slag is first acid-dissolved and sulfuric acid is added according to the solubility principle of iron sulfate to obtain an iron sulfate product, and the acid solution can be recycled;
- the method disclosed in the present invention can effectively separate and recover the iron and aluminum elements in the iron and aluminum slag, and obtain sulfate products, aluminum hydroxide products and iron sulfate products, which can be sold to obtain income, and can maximize the utilization of the iron and aluminum slag, which is beneficial to industrial application.
- the method is simple, low in cost, no waste is generated, and the wastewater output is extremely small.
- FIG1 is a schematic diagram of a process for recycling aluminum and iron from iron-aluminum slag provided in one embodiment of the present disclosure.
- the present disclosure provides a method for recycling aluminum and iron from iron-aluminum slag, the process of which is shown in FIG1 , and the method comprises the following steps:
- step (3) treating the sodium aluminate solution in step (2) by the Bayer process to obtain Al(OH) 3 and sodium aluminate mother liquor; adding alkali-converted iron-aluminum slag to the sodium aluminate mother liquor for alkali leaching reaction to obtain a sodium aluminate solution, and continuing to treat the sodium aluminate solution by the Bayer process, and repeating the cycle in this manner; when the sodium aluminate mother liquor becomes a solution containing a large amount of impurity sodium sulfate, the solution is decontaminated, and then evaporated and crystallized to obtain sodium sulfate;
- step (2) Acid dissolving the nickel-iron slag in step (2) and adding sulfuric acid to obtain ferric sulfate crystals. After solid-liquid separation, ferric sulfate and mother liquor are obtained. The mother liquor can be recycled to prepare ferric sulfate crystals and can also be used to recover nickel, cobalt and manganese in battery lines.
- This embodiment provides a method for recycling aluminum and iron from iron-aluminum slag, wherein the mass contents of the components in the iron-aluminum slag are: 0.5% nickel, 56% sulfate, 10.5% aluminum and 14.5% iron, and the rest are trace impurities (F and P) and COD.
- the method comprises the following specific steps:
- the sodium sulfate solution is frozen and crystallized in a freezing reactor at 5°C. After the crystallization is completed, it is quickly centrifuged and dried to obtain alkali solution and sodium sulfate crystals.
- the sodium sulfate recovery rate is 53.57%.
- Alkali leaching process the alkali-converted iron-aluminum slag of the above step (1) is subjected to alkali leaching, and a sodium hydroxide solution is prepared, wherein the amount of sodium hydroxide used is 1.5 times the theoretical amount required for all aluminum elements to be converted into sodium aluminate, the liquid-to-solid (mass) ratio is 5:1, and the leaching temperature is 60° C.
- nickel-iron slag and sodium aluminate solution wherein the nickel content of the nickel-iron slag is 1.0%, the iron content is 29%, and the aluminum content is 6.3%; the aluminum content of the sodium aluminate solution is 14.7 g/L, the ⁇ k is 1.55, and the aluminum leaching rate is 70%;
- step (2) adding 2 mol/L sulfuric acid to the nickel-iron slag obtained in step (2), at a temperature of 60° C., a reaction time of 4 h, and a liquid-to-solid (mass) ratio of 5:1; filtering after the reaction, the iron acid solubility is 80%, and 8 g of waste residue and an acid-dissolved solution are obtained; the acid-dissolved solution contains 46.4 g/L iron and 1.4 g/L nickel; continuing to add an equal volume of 60% sulfuric acid to the acid-dissolved solution, cooling to precipitate iron sulfate crystals, centrifuging to separate the solid and the liquid, the iron recovery rate is 90%, and the solid is the product iron sulfate, which meets the product standard of HG/T4816-2015, and the data are shown in Table 2; wherein the sulfuric acid solution is recycled to the front end acid dissolve or precipitate iron sulfate crystals.
- the sodium sulfate solution is frozen and crystallized in a frozen reactor at 5° C. After the crystallization is completed, it is quickly centrifuged and dried to obtain an alkali solution and sodium sulfate crystals, and the sodium sulfate recovery rate is 71.43%;
- Seeding process adding seed aluminum hydroxide to the sodium aluminate solution obtained in the alkali leaching process in an amount equal to 1 times the theoretical amount of aluminum, stirring at a speed of 200 r/min, and reacting at a temperature of 55° C. for 7 h. After the reaction is completed, filtering is performed to obtain a sodium aluminate mother liquor with an aluminum content of 11.53 g/L and aluminum hydroxide; the aluminum decomposition rate is 41%, and the aluminum hydroxide meets the product standard of GB/T4294-2010.
- Table 1 The specific data are shown in Table 1;
- step (3) (4) adding the ferroaluminum slag after alkali conversion from the alkali conversion process to the sodium aluminate mother liquor obtained in step (3) to reduce ⁇ k to 1.55-1.65 without adding sodium hydroxide, and repeating the alkali leaching and seed separation process;
- This embodiment provides a method for recycling aluminum and iron from iron-aluminum slag, wherein the mass contents of the components in the iron-aluminum slag are: 0.5% nickel, 56% sulfate, 10.5% aluminum and 14.5% iron, and the rest are trace impurities (F and P) and COD.
- the method comprises the following specific steps:
- the sodium sulfate solution is frozen and crystallized in a frozen reactor at 5° C. After the crystallization is completed, it is quickly centrifuged and dried to obtain an alkali solution and sodium sulfate crystals, and the sodium sulfate recovery rate is 89.29%;
- Alkali leaching process the alkali-converted ferroaluminum slag of the above step (1) is subjected to alkali leaching, and a sodium hydroxide solution is prepared, wherein the amount of sodium hydroxide used is 2.5 times the theoretical amount required for all aluminum elements to be converted into sodium aluminate, the liquid-to-solid ratio is 5:1, and the leaching temperature is 80°C, and the stirring reaction is carried out for 2 hours; after the reaction is completed, it is filtered while hot to obtain 35g of nickel-iron slag and sodium aluminate solution, wherein the nickel content of the nickel-iron slag is 1.43%, the iron content is 41.43%, and the aluminum content is 0.7%; the aluminum content of the sodium aluminate solution is 20.52g/L, the ⁇ k is 1.65, and the aluminum leaching rate is 97.7%;
- Seeding process adding seed aluminum hydroxide to the sodium aluminate solution obtained in the alkali leaching process in an amount of 1.5 times the theoretical amount of aluminum, stirring at a speed of 250 r/min, and reacting at a temperature of 50° C. for 8 h. After the reaction is completed, filtering is performed to obtain a sodium aluminate mother liquor with an aluminum content of 11.13 g/L and aluminum hydroxide; the aluminum decomposition rate is 47%, and the aluminum hydroxide meets the product standard GB/T4294-2010.
- Table 1 The specific data are shown in Table 1;
- step (3) (4) adding the ferroaluminum slag after alkali conversion from the alkali conversion process to the sodium aluminate mother liquor obtained in step (3) to reduce ⁇ k to 1.55-1.65 without adding sodium hydroxide, and repeating the alkali leaching and seed separation process;
- step (2) Add 4 mol/L sulfuric acid to the nickel-iron slag obtained in step (2), the temperature is 60° C., and the reaction time is 4h, liquid-solid ratio 5:1; after the reaction was completed, it was filtered, the iron acid solubility was 98.6%, and 1g of waste residue and acid solution were obtained; the acid solution contained 81.65g/L iron and 2.82g/L nickel; an equal volume of 98% sulfuric acid was continued to be added to the acid solution, and iron sulfate crystals were precipitated after cooling. The solid and liquid were separated by centrifugation, and the iron recovery rate was 99.5%. The solid was the product iron sulfate, which met the product standard of HG/T4816-2015, and the data are shown in Table 2; the sulfuric acid solution was recycled to dissolve in the front end acid or precipitate iron sulfate crystals.
- Alkali leaching process Add sodium hydroxide solution with a theoretical amount of aluminum element to the washed aluminum slag. At this time, aluminum alum and iron alum react with sodium hydroxide to obtain sodium aluminate solution and nickel-iron slag. The leaching rate of aluminum is only 25%;
- Example 1 compared with the aluminum leaching rate and iron recovery rate of Example 1, the method of Comparative Example 1 cannot effectively separate and recover aluminum and iron, the recovery rates of the two are low, and no sodium sulfate product is recovered.
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Abstract
一种铁铝渣资源化回收铝和铁的方法,所述方法包括:(1)将铁铝渣与第一碱液混合进行碱转反应,固液分离后,得到硫酸盐溶液和碱转后铁铝渣;(2)将所述碱转后铁铝渣和第二碱液混合进行碱浸反应,固液分离后,得到铝酸盐溶液和铁渣;(3)对所述铁渣进行酸溶,然后加入硫酸使硫酸铁析出,固液分离后,得到硫酸铁晶体和酸溶液。采用上述方法可有效分离并回收铁铝渣中的铁铝元素。
Description
本公开属于废旧电池回收技术领域,涉及一种铁铝渣资源化回收铝和铁的方法。
近年来电池发展迅猛,广泛应用于数码电子、智能电网、电动汽车和大规模储能材料等多个领域。然而,电池循环寿命始终有限,意味着废旧电池的产生量也在逐年增加,废旧电池的回收成为必不可少的产业链。
目前的湿法回收三元电池工艺中,主要产生的材料为石墨渣、铁铝渣和海绵铜。其中,海绵铜可以作为产品低价出售;石墨渣的主要成分为电池粉中的负极粉石墨;铁铝渣的渣量最大,主要成分为铁铝,同时夹带一定量的有价重金属的镍钴锰,无论资源化还是无害化难度很高,现行业对铁铝渣都以固废或危废处置。
铁铝是自然界中含量较高的金属元素,有较高的利用价值,废旧电池回收的湿法工艺产生的铁铝渣含有大量铁铝,能够将这部分铁铝分离出来并回收是非常有意义的。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
针对现有技术存在的不足,本公开的目的在于提供一种铁铝渣资源化回收铝和铁的方法。本公开首先通过碱转反应分离出铁铝渣中的硫酸根;然后通过碱浸反应从碱转后铁铝渣中分离出铝元素,得到铝酸盐溶液,进而可获得氢氧
化铝产品,而铁元素仍留在铁渣中,由此可实现铁铝元素的分离;之后利用硫酸铁溶解度原理,得到硫酸铁产品。因此,采用本公开的方法可有效分离并回收铁铝渣中的铁铝元素。
为达此目的,本公开采用以下技术方案:
第一方面,本公开提供一种铁铝渣资源化回收铝和铁的方法,所述方法包括:
(1)将铁铝渣与第一碱液混合进行碱转反应,固液分离后,得到硫酸盐溶液和碱转后铁铝渣;
(2)将所述碱转后铁铝渣和第二碱液混合进行碱浸反应,固液分离后,得到铝酸盐溶液和铁渣;
(3)对所述铁渣进行酸溶,然后加入硫酸使硫酸铁析出,固液分离后,得到硫酸铁晶体和酸溶液。
本公开提供了一种铁铝渣资源化回收铝和铁的方法,首先,通过碱转反应分离出铁铝渣中的硫酸根,可得到硫酸盐溶液,进而获得硫酸盐产品;然后通过碱浸反应从碱转后铁铝渣中分离出铝元素,得到铝酸盐溶液,进而可获得氢氧化铝产品,而铁元素仍留在铁渣中,由此可实现铁铝元素的分离;之后利用硫酸铁溶解度原理,先对铁渣进行酸溶再加入硫酸,得到硫酸铁产品,同时酸溶液可进行回收利用;
综上,采用本公开的方法,可有效分离并回收铁铝渣中的铁铝元素,可得到硫酸盐产品、氢氧化铝产品和硫酸铁产品,所述产品可外售获得收益,能够最大化利用铁铝渣,利于工业应用。
在一个实施方式中,所述铁铝渣包括湿法回收三元电池产生的铁铝渣。所述铁铝渣中包括铝离子、铁离子、镍离子、钴离子、锰离子、硫酸根离子、有
机物(COD)和杂质(例如磷和/或氟)。其中,镍离子、钴离子和锰离子经碱转反应形成沉淀进入碱转后铁铝渣中,然后经碱浸反应进入铁渣中,再经过酸溶溶解于酸中,最后留存在酸溶液中,酸溶液可回用酸溶步骤或是回到电池回收产线回收镍钴锰工序。
作为本公开一种可选的技术方案,步骤(1)所述第一碱液中的碱性物质包括氢氧化钠、氢氧化钙和碳酸钠中的至少一种。
本公开中,当采用氢氧化钠、氢氧化钙和碳酸钠中的至少一种作为第一碱液的碱性物质时,可与铁铝渣进行碱转反应,得到的硫酸盐溶液即为硫酸钠溶液。
铁铝渣主要化学成分为铁矾(NaFe3(SO4)2(OH)6)与铝矾(NaAl3(SO4)2(OH)6),示例性地,铁铝渣与氢氧化钠的反应方程式如下:
NaAl3(SO4)2(OH)6(s)+6NaOH(aq)=2Na2SO4(aq)+3NaAl(OH)4(aq);
NaFe3(SO4)2(OH)6(s)+3NaOH(aq)=2Na2SO4(aq)+3Fe(OH)3(s);
碱的用量会将铁矾结构破坏转化,铝矾中的硫酸钠也会少量转出来,从而得到硫酸钠;转化后的硫酸铝或是氢氧化铝夹带在碱转后铁铝渣中。
在一个实施方式中,步骤(1)所述第一碱液的浓度为20~40g/L,例如可以是20g/L、25g/L、30g/L、35g/L或40g/L等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,若第一碱液的浓度过低,则硫酸钠转化率过低;若第一碱液的浓度过高,则会使得部分铝元素进入硫酸盐溶液中,造成铝元素损失。
在一个实施方式中,步骤(1)所述第一碱液与铁铝渣的液固质量比为8:1。
在一个实施方式中,步骤(1)所述碱转反应的温度为60~80℃,例如可以是60℃、65℃、70℃、75℃或80℃等,所述碱转反应的时间为2~4h,例如可以
是2h、2.5h、3h、3.5h或4h等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,在60~80℃的温度下进行2~4h的碱转反应,可以提高硫酸钠转化率。
本公开中,在上述条件的共同作用下,碱转反应后得到的硫酸盐溶液中,硫酸盐(如硫酸钠)的浸出率在50~90%之间,例如可以是50%、60%、70%、80%或90%等。
在一个实施方式中,步骤(1)所述碱转后铁铝渣中,铝元素质量含量为15~25%(例如可以是15%、18%、20%或22%等),铁元素质量含量为20~30%(例如可以是20%、22%、25%或28%等),镍元素质量含量0.5~1.0%(例如可以是0.5%、0.7%、0.8%或0.9%等)。
作为本公开一种可选的技术方案,对步骤(1)所述硫酸盐溶液进行冷冻结晶,析出硫酸盐。该硫酸盐可外售。
本公开中,采用冷冻结晶析出硫酸盐,可以使硫酸盐不带其他杂质。硫酸盐的回收率为50~90%。析出硫酸盐后的溶液为碱性,该溶液可回到水处理大系统对废水进行调值。
在一个实施方式中,所述冷冻结晶的温度为2~5℃,例如可以是2℃、2.5℃、3℃、3.5℃、4℃、4.5℃或5℃等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
作为本公开一种可选的技术方案,步骤(2)所述第二碱液中的碱性物质包括氢氧化钠、氢氧化钙和碳酸钠中的至少一种。
本公开中,采用氢氧化钠、氢氧化钙和碳酸钠中的至少一种作为第二碱液中的碱性物质,可以与碱转后铁铝渣进行碱浸反应,得到的铝酸盐溶液即为铝
酸钠溶液。
在一个实施方式中,步骤(2)所述第二碱液中的碱性物质的用量为铝元素全部转化为铝酸盐所需理论量的1.5~2.5倍,例如可以是1.5倍、1.7倍、2倍、2.2倍、2.3倍、2.4倍或2.5倍等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
需要说明的是,“铝元素全部转化为铝酸盐”中的铝元素,是指碱转后铁铝渣中的铝元素。
本公开中,若第二碱液中的碱性物质的用量过少,则铝的浸出率不高;若第二碱液中的碱性物质的用量过多,浸出效果并不会提升,导致试剂的浪费。
作为本公开一种可选的技术方案,步骤(2)所述第二碱液和碱转后铁铝渣的液固质量比为5:1。
在一个实施方式中,步骤(2)所述碱浸反应的温度为60~80℃,例如可以是60℃、65℃、70℃、75℃或80℃等,所述碱浸反应的时间为2~4h,例如可以是2h、2.5h、3h、3.5h或4h等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,在60~80℃的温度下进行2~4h的碱浸反应,可以有效浸出铝。
作为本公开一种可选的技术方案,步骤(2)所述铝酸盐溶液的苛性比αk为1.55~1.6,例如可以是1.55、1.56、1.57、1.58、1.59或1.6等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,铝酸盐溶液的苛性比αk为1.55~1.6,有利于后续拜耳法处理铝酸盐溶液的进行,具有该苛性比范围的铝酸盐溶液适合进行种分。
在一个实施方式中,所述铝酸盐溶液中铝元素的质量浓度为10~25g/L,例如可以是10g/L、12g/L、15g/L、18g/L、20g/L或22g/L等。
在一个实施方式中,所述铁渣中,铝元素质量含量为0.5~7.0%(例如可以是0.5%、1%、2%、3%、4%、5%、6%或6.5%等),铁元素质量含量为25~45%(例如可以是25%、30%、35%或40%等),镍元素质量含量为1.0~1.5%(例如可以是1.0%、1.1%、1.2%、1.3%或1.4%等)。
作为本公开一种可选的技术方案,采用拜耳法处理步骤(2)所述铝酸盐溶液,得到氢氧化铝。
拜耳法是一种从铝土矿生产氧化铝的化工工艺。本公开中,采用拜耳法制备氢氧化铝,能耗低,成本低,产品纯度高,分离后的溶液可循环使用,不浪费碱量,大大降低成本。
作为本公开一种可选的技术方案,所述拜耳法包括以下步骤:
将步骤(2)所述铝酸盐溶液和晶种混合,种分后得到氢氧化铝和铝酸盐母液。
本公开中,得到的氢氧化铝产品符合GB/T4294-2010产品标准,可外售。
在一个实施方式中,所述晶种包括氢氧化铝。
在一个实施方式中,所述晶种的加入量为铝酸盐溶液中铝元素全部转化为氢氧化铝所需理论量的0.5~1.5倍,例如可以是0.5倍、0.7倍、1倍、1.2倍、1.3倍、1.4倍或1.5倍等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,若晶种的加入量过少,则氢氧化铝分解率较低;若晶种的加入量过多,则分解率增长有限,造成浪费。
在一个实施方式中,所述种分的温度为50~60℃,例如可以是50℃、52℃、54℃、56℃、58℃或60℃等,所述种分的时间1~10h,例如可以是1h、2h、4h、6h、8h或10h等。但并不仅限于所列举的数值,该数值范围内其他未列举的数
值同样适用。
本公开中,在50~60℃的温度下进行1~10h的种分,可以有效种分出氢氧化铝。
在一个实施方式中,所述种分的过程中伴有搅拌,所述搅拌的速度为150~300r/min,例如可以是150r/min、200r/min、250r/min或300r/min等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,种分的过程中以150~300r/min的速率持续搅拌,可以充分地使晶种分散在溶液中与溶液充分接触。
在一个实施方式中,所述铝酸盐母液中铝元素的质量浓度为9~12g/L。例如可以是9g/L、10g/L、11g/L或12g/L等。
在一个实施方式中,将所述铝酸盐母液与碱转后铁铝渣混合进行碱浸反应,固液分离后得到铝酸盐溶液和铁渣,继续采用拜耳法对所述铝酸盐溶液进行种分,得到氢氧化铝和新的铝酸盐母液。
本公开中,采用铝酸盐母液与碱转后铁铝渣混合,无需加入碱,使得溶液中碱循环利用,减少用碱成本。铝酸盐母液可多次循环使用。待循环至铝酸盐母液中硫酸盐(如硫酸钠)及杂质(如COD和少量磷、氟)富集较高时,对其除杂处理,再蒸发结晶得到硫酸盐。
在一个实施方式中,所述铝酸盐母液与碱转后铁铝渣混合进行碱浸反应后,得到的铝酸盐溶液的苛性比αk为1.55~1.65。例如可以是1.55、1.57、1.58、1.6或1.65等。
作为本公开一种可选的技术方案,步骤(3)所述酸溶的过程中采用的酸包括硫酸,所述酸的浓度为2~4mol/L,例如可以是2mol/L、2.5mol/L、3mol/L、3.5mol/L或4mol/L等。但并不仅限于所列举的数值,该数值范围内其他未列举
的数值同样适用。
本公开中,采用浓度为2~4mol/L的硫酸进行酸溶时,铁的酸溶率为80~98.6%(例如可以是80%、85%、90%或95%等)。酸溶的过程中采用的酸浓度过低,会导致硫酸铁处于溶液状态,加入硫酸后硫酸铁不析出;酸溶的过程中采用的酸浓度过高,则析出硫酸铁过后剩余硫酸过多。
在一个实施方式中,步骤(3)所述硫酸的质量浓度为60~98%,例如可以是60%、70%、80%、98%或90%等。但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
本公开中,酸溶得到的溶液中溶质主要为硫酸铁,利用硫酸铁溶解度原理,加入高质量浓度的硫酸得到饱和溶液,再冷却结晶析出硫酸铁晶体,实现铁的资源化。当步骤(3)所述硫酸的质量浓度为60~98%时,硫酸铁回收率为90~99.5%(例如可以是90%、92%、95%或98%等)。若硫酸的质量浓度过低,则硫酸铁达到溶解度,硫酸铁不析出。
步骤(3)固液分离后的酸溶液中主要包含硫酸镍/钴/锰和酸,可返回酸溶或回到电池回收产线浸出除杂工序,实现有价金属的综合回收利用。
作为本公开一种可选的技术方案,所述方法具体包括以下步骤:
(Ⅰ)将铁铝渣与浓度为20~40g/L的第一碱液混合,在60~80℃下进行碱转反应2~4h,固液分离后,得到硫酸盐溶液和碱转后铁铝渣,所述硫酸盐溶液在2~5℃下进行冷冻结晶,析出硫酸盐;
(Ⅱ)将所述碱转后铁铝渣和第二碱液混合进行碱浸反应,固液分离后,得到苛性比αk为1.55~1.6的铝酸盐溶液和铁渣,所述铝酸盐溶液和晶种混合,种分后得到氢氧化铝和铝酸盐母液;
其中,第二碱液中的碱性物质的用量为铝元素全部转化为铝酸盐所需理论
量的1.5~2.5倍,碱浸反应的温度为60~80℃,时间为2~4h,所述晶种的加入量为铝酸盐溶液中铝元素全部转化为氢氧化铝所需理论量的0.5~1.5倍,所述种分的温度为50~60℃,时间1~10h;
(Ⅲ)采用浓度为2~4mol/L的硫酸对所述铁渣进行酸溶,然后加入质量浓度为60~98%的硫酸使硫酸铁析出,固液分离后,得到硫酸铁晶体和酸溶液。
本公开所述的数值范围不仅包括上述列举的点值,还包括没有列举出的上述数值范围之间的任意的点值,限于篇幅及出于简明的考虑,本公开不再穷尽列举所述范围包括的具体点值。
与现有技术相比,本公开的有益效果为:
本公开提供了一种铁铝渣资源化回收铝和铁的方法,首先,通过碱转反应分离出铁铝渣中的硫酸根,可得到硫酸盐溶液,进而获得硫酸盐产品;然后通过碱浸反应从碱转后铁铝渣中分离出铝元素,得到铝酸盐溶液,进而可获得氢氧化铝产品,而铁元素仍留在铁渣中,由此可实现铁铝元素的分离;之后利用硫酸铁溶解度原理,先对铁渣进行酸溶再加入硫酸,得到硫酸铁产品,同时酸溶液可进行回收利用;
综上,采用本公开的方法,可有效分离并回收铁铝渣中的铁铝元素,可得到硫酸盐产品、氢氧化铝产品和硫酸铁产品,所述产品可外售获得收益,能够最大化利用铁铝渣,利于工业应用。并且方法简单,成本低,无废料产生,且废水产量极少。
在阅读并理解了附图和详细描述后,可以明白其他方面。
附图用来提供对本文技术方案的进一步理解,并且构成说明书的一部分,与本申请的实施例一起用于解释本文的技术方案,并不构成对本文技术方案的
限制。
图1为本公开一个实施方式提供的铁铝渣资源化回收铝和铁的流程示意图。
下面通过具体实施方式来进一步说明本公开的技术方案。
在一个实施方式中,本公开提供了一种铁铝渣资源化回收铝和铁的方法,其流程如图1所示,所述方法包括以下步骤:
(1)向铁铝渣中加入NaOH溶液,进行碱转,得到硫酸钠溶液和碱转后铁铝渣,对硫酸钠溶液进行冷冻结晶,得到硫酸钠;
(2)对步骤(1)所述碱转后铁铝渣进行碱浸,得到镍铁渣和铝酸钠溶液;
(3)采用拜耳法处理步骤(2)所述铝酸钠溶液,得到Al(OH)3和铝酸钠母液;向铝酸钠母液中加入碱转后铁铝渣进行碱浸反应后,又得到铝酸钠溶液,继续采用拜耳法处理铝酸钠溶液,按此方式循环;待铝酸钠母液变为含较多杂质硫酸钠的溶液时,对该溶液进行除杂,然后蒸发结晶,得到硫酸钠;
(4)对步骤(2)所述镍铁渣进行酸溶,并加入硫酸,制得硫酸铁结晶,固液分离之后,获得硫酸铁和母液,母液可回用制备硫酸铁结晶,还可用于电池线回收镍钴锰。
实施例1
本实施例提供了一种铁铝渣资源化回收铝和铁的方法,铁铝渣中的各成分质量含量为:0.5%镍、56%硫酸盐、10.5%铝和14.5%铁的铁铝渣,其余为微量杂质(F和P)及COD,所述方法包括以下具体步骤:
(1)碱转工序:取100g上述铁铝渣于烧杯中,配置20g/L氢氧化钠溶液,以固定液固(质量)比8:1将铁铝渣搅成浆料,温度60℃,反应4h,反应结束后趁热过滤,得到约70g碱转后铁铝渣与硫酸钠溶液,其中,碱转后铁铝渣中
镍含量0.71%,铁含量20.71%,铝含量15%;硫酸钠溶液在5℃的冷冻反应釜中进行冷冻结晶,结晶结束后迅速进行离心干燥得到碱液与硫酸钠晶体,硫酸钠回收率53.57%;
(2)碱浸工序:对上述步骤(1)的碱转后铁铝渣进行碱浸,配置氢氧化钠溶液,氢氧化钠用量为铝元素全部转化为铝酸钠所需理论量的1.5倍,液固(质量)比5:1,浸出温度60℃搅拌反应2h;反应结束后趁热过滤,得到50g镍铁渣和铝酸钠溶液,其中,镍铁渣中镍含量1.0%,铁含量29%,铝含量6.3%;铝酸钠溶液铝含量14.7g/L,αk为1.55,铝的浸出率为70%;
(3)种分工序:向碱浸工序得到的铝酸钠溶液中,加入晶种氢氧化铝,加入量为铝的0.5倍理论量,搅拌转速150r/min,60℃反应6h,反应结束后过滤,得到铝含量为9.85g/L的铝酸钠母液和氢氧化铝;铝分解率为33%,氢氧化铝符合GB/T4294-2010产品标准,具体数据如表1所示;
(4)向步骤(3)得到的铝酸钠母液中加入碱转工序的碱转后铁铝渣,降低αk至1.55~1.65,无需再加氢氧化钠,重复碱浸与种分工序;碱浸至种分为一次循环,当铝酸钠母液杂质富集较多硫酸钠、COD和少量磷、氟,外排至水处理大系统进行除杂处理并提取硫酸钠晶体;
(5)向步骤(2)得到的镍铁渣加入2mol/L的硫酸,温度60℃,反应时间4h,液固(质量)比5:1;反应结束后过滤,铁酸溶率为80%,得到8g废渣和酸溶后溶液;酸溶后溶液含46.4g/L铁、1.4g/L镍;向酸溶后溶液继续加入等体积60%硫酸,冷却后析出硫酸铁晶体,对其离心分离固体与液体,铁回收率为90%,固体为产品硫酸铁,符合HG/T4816-2015的产品标准,数据如表2所示;其中硫酸溶液回用前端酸溶或析出硫酸铁晶体。
实施例2
本实施例提供了一种铁铝渣资源化回收铝和铁的方法,铁铝渣中的各成分质量含量为:0.5%镍、56%硫酸盐、10.5%铝和14.5%铁的铁铝渣,其余为微量杂质(F和P)及COD,所述方法包括以下具体步骤:
(1)碱转工序:取100g上述铁铝渣于烧杯中,配置30g/L氢氧化钠溶液,以液固比8:1将铁铝渣搅成浆料,温度70℃,反应3h,反应结束后趁热过滤,得到约60g碱转后铁铝渣与硫酸钠溶液,其中,碱转后铁铝渣镍含量0.83%,铁含量24.17%,铝含量17.5%;硫酸钠溶液在5℃的冷冻反应釜中进行冷冻结晶,结晶结束后迅速进行离心干燥得到碱液与硫酸钠晶体,硫酸钠回收率71.43%;
(2)碱浸工序:对上述步骤(1)的碱转后铁铝渣进行碱浸,配置氢氧化钠溶液,氢氧化钠用量为铝元素全部转化为铝酸钠所需理论量的2倍,液固比5:1,浸出温度70℃搅拌反应2h;反应结束后趁热过滤,得到40g镍铁渣和铝酸钠溶液,其中,镍铁渣中镍含量为1.25%,铁含量36.25%,铝含量1.8%;铝酸钠溶液铝含量19.55g/L,αk为1.60,铝的浸出率为93.1%;
(3)种分工序:向碱浸工序得到的铝酸钠溶液中,加入晶种氢氧化铝,加入量为铝的1倍理论量,搅拌转速200r/min,温度为55℃反应7h,反应结束后过滤,得到铝含量为11.53g/L的铝酸钠母液和氢氧化铝;铝分解率为41%,氢氧化铝符合GB/T4294-2010产品标准,具体数据如表1所示;
(4)向步骤(3)得到的铝酸钠母液中加入碱转工序的碱转后铁铝渣,降低αk至1.55~1.65,无需再加氢氧化钠,重复碱浸与种分工序;
(5)向步骤(2)得到的镍铁渣加入3mol/L的硫酸,温度60℃,反应时间4h,液固比5:1;反应结束后过滤,铁酸溶率为90%,得到3g废渣和酸溶液;酸溶液含65.25g/L铁、2.81g/L镍;酸溶液继续加入等体积80%硫酸,冷却后析出硫酸铁晶体,对其离心分离固体与液体,铁回收率为92%,固体为产品硫酸
铁,符合HG/T4816-2015的产品标准,数据如表2所示;其中硫酸溶液回用前端酸溶或析出硫酸铁晶体。
实施例3
本实施例提供了一种铁铝渣资源化回收铝和铁的方法,铁铝渣中的各成分质量含量为:0.5%镍、56%硫酸盐、10.5%铝和14.5%铁的铁铝渣,其余为微量杂质(F和P)及COD,所述方法包括以下具体步骤:
(1)碱转工序:取100g上述铁铝渣于烧杯中,配置40g/L氢氧化钠溶液,以液固比8:1将铁铝渣搅成浆料,温度80℃,反应2h,反应结束后趁热过滤,得到约50g碱转后铁铝渣与硫酸钠溶液,其中,碱转后铁铝渣镍含量1.0%,铁含量29%,铝含量21%;硫酸钠溶液在5℃的冷冻反应釜中进行冷冻结晶,结晶结束后迅速进行离心干燥得到碱液与硫酸钠晶体,硫酸钠回收率89.29%;
(2)碱浸工序:对上述步骤(1)的碱转铁铝渣进行碱浸,配置氢氧化钠溶液,氢氧化钠用量为铝元素全部转化为铝酸钠所需理论量的2.5倍,液固比5:1,浸出温度80℃搅拌反应2h;反应结束后趁热过滤,得到35g镍铁渣和铝酸钠溶液,其中,镍铁渣中镍含量为1.43%,铁含量41.43%,铝含量0.7%;铝酸钠溶液铝含量20.52g/L,αk为1.65,铝的浸出率为97.7%;
(3)种分工序:向碱浸工序得到的铝酸钠溶液中,加入晶种氢氧化铝,加入量为铝的1.5倍理论量,搅拌转速250r/min,温度为50℃反应8h,反应结束后过滤,得到铝含量为11.13g/L的铝酸钠母液和氢氧化铝;铝分解率为47%,氢氧化铝符合GB/T4294-2010产品标准,具体数据如表1所示;
(4)向步骤(3)得到的铝酸钠母液中加入碱转工序的碱转后铁铝渣,降低αk至1.55~1.65,无需再加氢氧化钠,重复碱浸与种分工序;
(5)向步骤(2)得到的镍铁渣加入4mol/L的硫酸,温度60℃,反应时间
4h,液固比5:1;反应结束后过滤,铁酸溶率为98.6%,得到1g废渣和酸溶液;酸溶液含81.65g/L铁、2.82g/L镍;酸溶液继续加入等体积98%硫酸,冷却后析出硫酸铁晶体,对其离心分离固体与液体,铁回收率为99.5%,固体为产品硫酸铁,符合HG/T4816-2015的产品标准,数据如表2所示;其中硫酸溶液回用前端酸溶或析出硫酸铁晶体。
表1
表2
由表1和表2的数据可知,实施例1-3得到的氢氧化铝产品和硫酸铁产品均符合标准,可进行外售。采用本公开的方法,实现了有效分离并回收铁铝渣中
的铁铝元素。
实施例4
本实施例与实施例1的区别在于,碱转工序中,氢氧化钠溶液的浓度调整为18g/L,其余制备方法和参数与实施例1完全相同;使得硫酸钠回收仅有30%,氟、磷杂质均留在碱转后铁铝渣中。
实施例5
本实施例与实施例3的区别在于,碱转工序中,氢氧化钠溶液的浓度调整为42g/L,其余制备方法和参数与实施例3完全相同;使得硫酸钠溶液中含有0.1g/L的铝元素,对铁铝渣中铝元素造成损失。
实施例6
本实施例与实施例1的区别在于,碱浸工序中,氢氧化钠用量为铝元素全部转化为铝酸钠所需理论量的1.2倍,其余制备方法和参数与实施例1完全相同;使得铝的浸出率仅35%。
实施例7
本实施例与实施例3的区别在于,碱浸工序中,氢氧化钠用量为铝元素全部转化为铝酸钠所需理论量的2.7倍,其余制备方法和参数与实施例3完全相同;其铝浸出率与实施例3的相差不大。
对比例1
本对比例提供了一种铁铝渣资源化回收铝和铁的方法,铁铝渣与实施例1的相同,所述方法包括以下具体步骤:
(1)使用80℃热水搅洗铁铝渣,硫酸钠仅洗出8%,得到水洗后铁铝渣;
(2)碱浸工序:向水洗后铝渣加入铝元素理论量的氢氧化钠溶液,此时铝矾和铁矾均与氢氧化钠反应,得到铝酸钠溶液和镍铁渣,铝的浸出率仅只有
25%;
(3)种分:向铝酸钠溶液加入理论量的氢氧化铝晶种,但步骤(2)得到的铝酸钠溶液铝含量过低,导致氢氧化铝产率较低;
(4)向镍铁渣加入1mol/L的硫酸,铁的酸溶率只有50%,得到1g废渣和酸溶后溶液;酸溶后溶液再加入等体积50%的硫酸进行沉淀,铁的回收率仅有67%。
分析:
由实施例1-3的结果可知,采用本公开的方法,可实现有效分离并回收铁铝渣中的铁铝元素,铝的浸出率和铁回收率较高,且氢氧化铝产品和硫酸铁产品均符合标准,同时可回收硫酸钠产品。
由实施例1、3和实施例4-5结果可知,若碱转工序中氢氧化钠溶液的浓度过低,会硫酸钠转化率过低;若碱转工序中氢氧化钠溶液的浓度过高,会导致硫酸钠溶液中残留铝元素,造成铝回收量损失。
由实施例1、3和实施例6-7结果可知,若碱浸工序中氢氧化钠用量过少,会铝的浸出率较低;若碱浸工序中氢氧化钠用量过多,铝浸出率提升有限,且会使溶液中碱过多。
由实施例1和对比例1结果可知,与实施例1的铝浸出率和铁回收率相比,采用对比例1的方法,无法有效分离回收铝和铁,二者的回收率较低,且未回收硫酸钠产品。
Claims (18)
- 一种铁铝渣资源化回收铝和铁的方法,所述方法包括:(1)将铁铝渣与第一碱液混合进行碱转反应,固液分离后,得到硫酸盐溶液和碱转后铁铝渣;(2)将所述碱转后铁铝渣和第二碱液混合进行碱浸反应,固液分离后,得到铝酸盐溶液和铁渣;(3)对所述铁渣进行酸溶,然后加入硫酸使硫酸铁析出,固液分离后,得到硫酸铁晶体和酸溶液。
- 根据权利要求1所述的方法,其中,步骤(1)所述第一碱液中的碱性物质包括氢氧化钠、氢氧化钙和碳酸钠中的至少一种。
- 根据权利要求1或2所述的方法,其中,步骤(1)所述第一碱液的浓度为20~40g/L。
- 根据权利要求1-3任一项所述的方法,其中,步骤(1)所述碱转反应的温度为60~80℃,所述碱转反应的时间为2~4h。
- 根据权利要求1-4任一项所述的方法,其中,对步骤(1)所述硫酸盐溶液进行冷冻结晶,析出硫酸盐。
- 根据权利要求1-5任一项所述的方法,其中,步骤(2)所述第二碱液中的碱性物质包括氢氧化钠、氢氧化钙和碳酸钠中的至少一种。
- 根据权利要求1-6任一项所述的方法,其中,步骤(2)所述第二碱液中的碱性物质的用量为铝元素全部转化为铝酸盐所需理论量的1.5~2.5倍。
- 根据权利要求1-7任一项所述的方法,其中,步骤(2)所述碱浸反应的温度为60~80℃,所述碱浸反应的时间为2~4h。
- 根据权利要求1-8任一项所述的方法,其中,步骤(2)所述铝酸盐溶液的苛性比αk为1.55~1.6。
- 根据权利要求1-9任一项所述的方法,其中,采用拜耳法处理步骤(2)所述铝酸盐溶液,得到氢氧化铝。
- 根据权利要求10所述的方法,其中,所述拜耳法包括以下步骤:将步骤(2)所述铝酸盐溶液和晶种混合,种分后得到氢氧化铝和铝酸盐母液。
- 根据权利要求11所述的方法,其中,所述晶种包括氢氧化铝。
- 根据权利要求11或12所述的方法,其中,所述晶种的加入量为铝酸盐溶液中铝元素全部转化为氢氧化铝所需理论量的0.5~1.5倍。
- 根据权利要求11-13任一项所述的方法,其中,所述种分的温度为50~60℃,所述种分的时间1~10h。
- 根据权利要求11-14任一项所述的方法,其中,所述种分的过程中伴有搅拌,所述搅拌的速度为150~300r/min。
- 根据权利要求1-15任一项所述的方法,其中,步骤(3)所述酸溶的过程中采用的酸包括硫酸,所述酸的浓度为2~4mol/L。
- 根据权利要求1-16任一项所述的方法,其中,步骤(3)所述硫酸的质量浓度为60~98%。
- 根据权利要求1-17任一项所述的方法,其中,所述方法具体包括以下步骤:(Ⅰ)将铁铝渣与浓度为20~40g/L的第一碱液混合,在60~80℃下进行碱转反应2~4h,固液分离后,得到硫酸盐溶液和碱转后铁铝渣,所述硫酸盐溶液在2~5℃下进行冷冻结晶,析出硫酸盐;(Ⅱ)将所述碱转后铁铝渣和第二碱液混合进行碱浸反应,固液分离后,得到苛性比αk为1.55~1.6的铝酸盐溶液和铁渣,所述铝酸盐溶液和晶种混合,种 分后得到氢氧化铝和铝酸盐母液;其中,第二碱液中的碱性物质的用量为铝元素全部转化为铝酸盐所需理论量的1.5~2.5倍,碱浸反应的温度为60~80℃,时间为2~4h,所述晶种的加入量为铝酸盐溶液中铝元素全部转化为氢氧化铝所需理论量的0.5~1.5倍,所述种分的温度为50~60℃,时间1~10h;(Ⅲ)采用浓度为2~4mol/L的硫酸对所述铁渣进行酸溶,然后加入质量浓度为60~98%的硫酸使硫酸铁析出,固液分离后,得到硫酸铁晶体和酸溶液。
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