WO2023246500A1 - 铝电解废料的锂盐回收方法及回收设备 - Google Patents

铝电解废料的锂盐回收方法及回收设备 Download PDF

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Publication number
WO2023246500A1
WO2023246500A1 PCT/CN2023/098544 CN2023098544W WO2023246500A1 WO 2023246500 A1 WO2023246500 A1 WO 2023246500A1 CN 2023098544 W CN2023098544 W CN 2023098544W WO 2023246500 A1 WO2023246500 A1 WO 2023246500A1
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WIPO (PCT)
Prior art keywords
solid
lithium
aluminum electrolysis
lithium salt
dissolution
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PCT/CN2023/098544
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English (en)
French (fr)
Inventor
陈开斌
杜婷婷
刘建军
史志荣
李若楠
王珣
崔梦倩
孙丽贞
尹大伟
罗钟生
李冬生
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中国铝业股份有限公司
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Publication of WO2023246500A1 publication Critical patent/WO2023246500A1/zh

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present disclosure relates to the field of aluminum electrolysis, and in particular to a lithium salt recovery method and recovery equipment for aluminum electrolysis waste.
  • Aluminum electrolysis waste mainly includes overhaul slag and electrolyte.
  • Overhaul slag is the waste residue produced during the repair of damaged aluminum electrolytic cells.
  • Electrolyte includes the electrolyte fished out from the electrolytic cell during the electrolysis process and the electrolyte obtained after carbon slag flotation, etc., all of which contain relatively large amounts of High content of lithium.
  • Lithium is an important strategic resource and is widely used in production and living fields such as mobile phones, computers, new energy vehicles, and energy storage.
  • Some embodiments of the present disclosure provide a lithium salt recovery method and recovery equipment for aluminum electrolysis waste materials, which do not require roasting, adding acid or alkali, and can simplify the lithium salt recovery process.
  • a method for recovering lithium salts from aluminum electrolysis waste includes: mixing powder of aluminum electrolysis waste with water and a lithium extraction agent to dissolve the lithium salt to obtain a dissolution slurry, wherein the aluminum
  • the electrolysis waste includes aluminum electrolysis overhaul slag and electrolyte; the dissolution slurry is subjected to multi-stage impurity removal to obtain lithium salt.
  • a lithium salt recovery equipment for aluminum electrolysis waste materials which is applied to the lithium salt recovery method of aluminum electrolysis waste materials described in the first aspect, including: a crusher; a pulverizer.
  • the inlet of the powder machine is connected with the outlet of the crusher; the inlet of the dissolution tank is
  • the material port is provided with a two-way valve or a three-way valve.
  • One of the two-way valve or the three-way valve is connected to the discharge port of the pulverizer, and the other is used to inject the lithium extraction agent; the impurity removal system, the The inlet of the impurity removal system is connected with the outlet of the dissolution tank.
  • Figure 1 shows a schematic flow chart of a lithium salt recovery method for aluminum electrolysis waste according to some embodiments of the present disclosure
  • Figure 2 shows a schematic structural block diagram of a lithium salt recovery equipment for aluminum electrolysis waste according to some embodiments of the present disclosure
  • Figure 3 shows a schematic structural diagram of a dissolution tank according to some embodiments of the present disclosure.
  • Figure 4 shows a schematic structural diagram of another lithium salt recovery equipment for aluminum electrolysis waste according to some embodiments of the present disclosure.
  • relational terms such as first, second, etc. are only used to distinguish one entity or operation from another entity or operation and do not necessarily require or imply the existence of any such entity or operation. an actual relationship or sequence.
  • the terms “comprises,””comprises,” or any other variations thereof are intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus that includes a list of elements includes not only those elements, but also those not expressly listed other elements, or elements inherent to the process, method, article or equipment.
  • an element defined by the statement “comprises a" does not exclude the presence of additional identical elements in a process, method, article, or apparatus that includes the stated element. technique
  • the term "more than two" includes two or more than two situations.
  • the present disclosure provides a lithium salt recovery method for aluminum electrolysis waste materials.
  • Figure 1 is a schematic flow chart of a lithium salt recovery method for aluminum electrolysis waste materials provided by an embodiment of the present disclosure.
  • the lithium salt recovery method includes: S100: Mix the powder of aluminum electrolysis waste with water and lithium extraction agent to dissolve the lithium salt and obtain a dissolution slurry.
  • the aluminum electrolysis waste includes aluminum electrolysis overhaul slag and electrolyte. .
  • the electrolyte is in solid form at room temperature.
  • the powder of aluminum electrolysis overhaul slag or electrolyte or overhaul slag and electrolyte mixture can be mixed with water first, and then a lithium extraction agent can be added.
  • the lithium extraction agent can remove the aluminum electrolysis waste.
  • the lithium in the powder is dissolved in the liquid to obtain a dissolution slurry.
  • the lithium extraction agent can include salts, such as sulfate or chloride salts, etc., which can replace the lithium of lithium fluoride in the powder of aluminum electrolysis waste with lithium salts that are soluble in water, which facilitates the subsequent purification and removal of impurities from the lithium salts.
  • S200 Perform multi-stage impurity removal on the dissolution slurry to obtain lithium salt. Multi-stage impurity removal can include precipitation, solid-liquid conversion or crystallization, solid-liquid separation, etc.
  • Aluminum electrolysis waste mainly includes overhaul slag and electrolyte. Overhaul slag is the waste residue produced during the repair of damaged aluminum electrolytic cells.
  • Electrolyte includes the electrolyte fished out from the electrolytic cell during the electrolysis process and the electrolyte obtained after carbon slag flotation, etc., all of which contain relatively large amounts of High content of lithium.
  • the amount of aluminum electrolytic waste produced increases year by year.
  • it contains 0.5%-2% lithium, mainly in the form of lithium fluoride.
  • Lithium is an important strategic resource. It is widely used in production and living fields such as mobile phones, computers, new energy vehicles, and energy storage.
  • my country's lithium resources are relatively abundant, but more than 80% exist in salt lakes. The composition of salt lakes is complex and the cost of extracting lithium is high.
  • Aluminum electrolysis waste has relatively simple composition, few impurities, and high lithium content, so it has a very high recycling value.
  • the lithium salt recovery method of aluminum electrolysis waste involves grinding the aluminum electrolysis waste to obtain aluminum electrolysis waste powder, mixing the aluminum electrolysis waste powder with water, and then adding a lithium extracting agent to remove the aluminum electrolysis waste.
  • the lithium fluoride in the waste powder is converted into lithium salt dissolved in water, and then the lithium salt is obtained through multi-stage impurity removal and purification.
  • There is no need to add acid or alkali to dissolve the lithium salt which can avoid corrosion of the equipment during the lithium recovery process and extend the service life of the equipment.
  • it can avoid the dissolution of more impurities to reduce the impurity removal process, further simplify the lithium recovery process, and can Avoid the generation of toxic hydrogen fluoride gas and environmental pollution.
  • step S100 may also include: grinding aluminum electrolytic waste to obtain powder of aluminum electrolytic waste. Specifically, it can be divided into two steps. First, perform preliminary crushing, and then perform powdering to obtain aluminum electrolytic waste powder.
  • the lithium extraction agent includes one of calcium sulfate, magnesium sulfate, calcium chloride, and magnesium chloride. Using only one of calcium sulfate, magnesium sulfate, calcium chloride and magnesium chloride can reduce the dissolution of excess impurities, avoid increasing the impurity removal process, further simplify the lithium recovery process, and reduce recovery costs.
  • the solid-liquid ratio of the powder material of aluminum electrolysis waste material and water ranges from 1:3 to 1:5, and the lithium extraction agent
  • the amount of agent added is 1.8 to 2.2 times the theoretical value of the lithium extraction agent required to completely react with lithium and fluorine in the powder of aluminum electrolysis waste.
  • the dissolution reaction time is 1 to 2 hours, and the reaction temperature range is 80 to 95°C.
  • the aluminum electrolysis waste can be aluminum electrolysis overhaul slag raw materials, electrolyte raw materials, aluminum electrolysis overhaul slag and electrolyte mixed raw materials, crushed by a crusher and then discharged, and the crushed materials are added to the pulverizer through transportation equipment.
  • Internal powder making the particle size of the powder discharged from the powder mill is controlled below 0.5mm.
  • the solid-liquid ratio is controlled at 1:3 ⁇ 1:5, which can be 1:3, 1:4, 1:5, which can be adjusted according to the lithium salt content in the overhaul slag.
  • the calculated lithium extraction agent is added to the dissolution tank through the feed inlet.
  • the lithium extraction agent can be calcium sulfate, magnesium sulfate, calcium chloride and magnesium chloride.
  • the inlet of aluminum electrolytic waste powder and lithium extracting agent can be switched through a two-way valve or a three-way valve.
  • the amount of lithium extraction agent added is based on the sum of the lithium content and the fluorine content in the overhaul slag, and the theoretical value is calculated based on the complete reaction at a molar ratio of 1:1.
  • the added amount is 1.8-2.2 times the theoretical value, which can be 1.8 times or 1.9 times. , 2.0 times, 2.1 times or 2.2 times.
  • the dissolution reaction time range is 1-2 hours, which can be 1.0 hours, 1.5 hours or 2.0 hours.
  • the dissolution reaction temperature range is 80-95°C, which can be 80°C, 85°C, 90 °C or 95 °C, the amount of lithium extraction agent, reaction time and reaction temperature can be adjusted according to the lithium salt content in the overhaul slag.
  • the material inlet and water injection port of the dissolution tank can be equipped with one-way valves, which can only flow in one direction, and will automatically close after each material is added.
  • step S200 may include: performing a first solid-liquid separation on the dissolution slurry to obtain a first dissolution liquid.
  • the liquid separated from solid-liquid contains lithium salt.
  • the lithium extraction agent is calcium sulfate
  • the dissolved lithium salt is lithium sulfate.
  • the pH value of the first eluate is controlled at 11 to 12, and precipitation is performed.
  • Impurities such as magnesium, calcium, aluminum, and iron can be precipitated and removed in solid form.
  • the precipitated mixed solution is subjected to a second solid-liquid separation to obtain a second dissolution solution.
  • Use a resin adsorption column or a filter membrane to remove impurities from the second eluate to obtain a third eluate.
  • the resin adsorption column or filter membrane can adsorb calcium salts and magnesium salts for further impurity removal and purification.
  • the third eluate is concentrated and crystallized to remove impurities to obtain Crystal mixture. Concentration can be membrane concentration or evaporation concentration. Crystallization can be freeze crystallization. The temperature can be controlled below zero.
  • the lithium extraction agent is calcium sulfate, sodium sulfate crystals can be obtained. Sodium sulfate crystals can be used as a by-product of lithium recovery. Purification of lithium salts.
  • the crystallization mixture is subjected to the third solid-liquid separation to obtain the fourth eluate.
  • a solid crude lithium salt Add the substitution reactant to the fourth eluate to cause a substitution reaction, and evaporate and precipitate in an environment of 90 to 100°C for 1.5 to 2.5 hours to obtain a solid crude lithium salt.
  • the replacement can be sodium carbonate solution, which undergoes a displacement reaction with lithium sulfate to obtain lithium carbonate.
  • Lithium carbonate is a solid lithium salt. After evaporation and precipitation, a solid crude lithium salt can be obtained. The solid crude lithium salt is washed and dried in sequence to obtain the lithium salt. Washing and drying can further remove impurities on the surface of the solid crude lithium salt and further purify it to obtain a relatively pure lithium salt.
  • step S100 before step S100, it also includes: when the fluorine content of the powder of aluminum electrolytic waste is greater than 5000 mg/L, performing solid-liquid separation after fluorine extraction and washing of the powder of aluminum electrolytic waste, A fluorine-containing solution and a solid slag are obtained, wherein the solid slag is used for mixing with water and a lithium extraction agent; the fluorine-containing solution is evaporated and crystallized to obtain a fluorine salt.
  • Fluoride salt can be used as a by-product of lithium recycling to improve the utilization of aluminum electrolysis waste.
  • a lithium salt recovery device for aluminum electrolysis waste is provided, which is applied to the lithium salt recovery method of aluminum electrolysis waste described in the first aspect.
  • Figure 2 shows a lithium salt recovery equipment for aluminum electrolysis waste provided by an embodiment of the present disclosure. Schematic structural block diagram of salt recovery equipment. As shown in Figure 2, the lithium salt recovery equipment includes: crusher 101; pulverizer 102, the inlet of the pulverizer is connected with the outlet of the crusher; dissolution tank 103, the inlet of the dissolution tank is set There is a two-way valve or a three-way valve.
  • One of the two-way valves or the three-way valve is connected to the discharge port of the pulverizer, and the other is used to inject the lithium extraction agent; the impurity removal system 400, the inlet of the impurity removal system is connected to The discharge port of the dissolution tank is connected.
  • the lithium salt recovery equipment for aluminum electrolytic waste grinds and prepares samples of aluminum electrolytic waste to obtain powder of aluminum electrolytic waste, mixes the powder of aluminum electrolytic waste with water, and then adds a lithium extracting agent.
  • the lithium fluoride in the powder of aluminum electrolysis waste is converted into lithium salt dissolved in water, and then the lithium salt is obtained through multi-stage impurity removal and purification.
  • There is no need to add acid or alkali to dissolve the lithium salt which can avoid corrosion of the equipment during the lithium recovery process and extend the service life of the equipment.
  • it can avoid the dissolution of more impurities to reduce the impurity removal process, further simplify the lithium recovery process, and can Avoid the generation of toxic hydrogen fluoride gas and environmental pollution.
  • FIG. 3 is a schematic structural diagram of a dissolution tank provided by an embodiment of the present disclosure.
  • the dissolution tank includes: a dissolution reaction chamber 210, which is used to accommodate the powder of aluminum electrolysis waste, lithium extraction agent and water.
  • the dissolution reaction chamber 210 is connected with a material inlet 202, a water injection port 203, and a slurry guide. Outlet 208, overflow port 205 and liquid level gauge port 204.
  • the first heating chamber 220 at least partially encloses
  • the dissolution reaction chamber 210 and the first heating chamber 220 include a first injection port 207, a first overflow port 201 and a thermometer port 206.
  • the stirring paddle 301 is inserted into the dissolution reaction chamber 210.
  • the stirring paddle 301 is provided with a second heating chamber 230.
  • the second heating chamber 230 is connected with a second injection port 302 and a second overflow port 303.
  • the stirring paddle 301 includes a blade. 304 and partition 305.
  • the first heating chamber 220 and the second heating chamber 230 are used to accommodate hot water and/or hot steam.
  • the first heating chamber 220 and the second heating chamber 230 containing hot water and/or hot steam may provide the dissolution reaction chamber 210 with Temperature environment of 80°C ⁇ 95°C.
  • the entire lithium salt dissolution process is carried out in the dissolution tank 103, which can be a vertical tank; a second heating chamber 230 is provided on the outer wall, which can realize jacketed indirect heating, and steam or hot water can be injected from the first injection tank.
  • the inlet 207 is injected and overflows from the first overflow port 201.
  • the first injection port 207 is located at the bottom and the first overflow port 201 is located at the top.
  • the stirring paddle 301 is hollow and is provided with a partition 305.
  • a heat source is introduced for auxiliary heating.
  • the heat source is steam or hot water.
  • the paddle 304 is arc-shaped. The heat source circulates without dead ends.
  • the steam or hot water flows along the partition 305 throughout the stirring paddle 301.
  • the internal flow of the stirring paddle 301 makes the internal temperature of the stirring paddle 301 uniform, and the slurry in the dissolution tank 103 is evenly heated by the rotation of the stirring paddle 301.
  • the stirring paddle 301 is provided with a second injection port 302 and a second overflow port 303, both of which are located on the upper part of the stirring paddle 301. , steam or hot water flows in through the second injection port 302, flows out from the second overflow port 303, and then flows in from the second injection port 302 after external heat exchange.
  • the inner lining of the dissolution tank 103 and the stirring paddle 301 are made of steel-lined anti-corrosion tetrafluoroethylene.
  • the stirring paddle 301 continues to work to fully react the overhaul slag raw material and the lithium extraction agent.
  • the reaction temperature and liquid level in the dissolution tank 103 are monitored through the thermometer port 206 and the liquid level meter port 204.
  • FIG. 4 is a schematic structural diagram of another lithium salt recovery equipment for aluminum electrolysis waste provided by an embodiment of the present disclosure.
  • the impurity removal system 400 includes: a first solid-liquid separator 104, which is connected to the dissolution tank 103; a sedimentation tank 105, which is connected to the liquid outlet of the first solid-liquid separator 104 and is used to utilize sodium hydroxide.
  • the pH value of the first dissolution liquid is controlled between 11 and 12, and precipitation is performed;
  • the second solid-liquid separator 106 is connected to the liquid outlet of the sedimentation tank 105;
  • the filter 107 is connected to the liquid outlet of the second solid-liquid separator 106
  • the port is connected;
  • the filter can be a resin adsorption column or a filter membrane.
  • the crystallizer 108 is connected with the outlet of the filter 107; the third solid-liquid separator 109 is connected with the liquid outlet of the crystallizer 108; the lithium precipitation tank 110 is connected with the liquid outlet of the third solid-liquid separator 109.
  • the fourth solid-liquid separator 111 is connected to the discharge port of the lithium precipitation tank 110; the scrubber 112 is connected to the solid discharge port of the fourth solid-liquid separator 111; drying Machine 113 is connected with the solid discharge port of the scrubber 112.
  • the lithium salt of aluminum electrolysis waste provided by embodiments of the present disclosure
  • the recovery equipment also includes: a fluoride removal system, which includes a reverse scrubber 401, a fifth solid-liquid separator 402 and an evaporator 403 connected in sequence; the feed inlet of the reverse scrubber 401 is connected to the pulverizer 102 The outlet is connected; the solid outlet of the fifth solid-liquid separator 402 is connected with the inlet of the dissolution tank 103, and the liquid outlet of the fifth solid-liquid separator 402 is connected with the evaporator 403.
  • a fluoride removal system which includes a reverse scrubber 401, a fifth solid-liquid separator 402 and an evaporator 403 connected in sequence; the feed inlet of the reverse scrubber 401 is connected to the pulverizer 102 The outlet is connected; the solid outlet of the fifth solid-liquid separator 402 is connected with the inlet of the dissolution tank 103, and the liquid outlet of the fifth solid-liquid separator 402 is connected with the
  • the overhaul slag can be first passed through the crusher 101 and the pulverizer 102 for sample preparation, and then passed through the reverse scrubber 401 to remove fluorine, and then passed through the fifth solid-liquid separator.
  • 402 performs solid-liquid separation, adds the filter residue to the dissolution tank 103 for lithium extraction and dissolution, and the filtrate is crystallized through the evaporator 403 to obtain a fluoride salt product.

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Abstract

本公开提供了铝电解废料的锂盐回收方法及回收设备,属于铝电解领域。该方法包括:将铝电解废料的粉料与水和提锂剂混合,以溶出锂盐,得到溶出浆液,其中,所述铝电解废料包括铝电解大修渣和电解质;对所述溶出浆液进行多级除杂,得到锂盐。

Description

铝电解废料的锂盐回收方法及回收设备
相关申请的交叉引用
本公开要求于2022年6月20日提交、申请号为2022107227256名称为“铝电解废料的锂盐回收方法及回收设备”的中国专利申请的优先权,其全部内容通过引用合并于此。
技术领域
本公开涉及铝电解领域,特别涉及铝电解废料的锂盐回收方法及回收设备。
背景技术
铝电解废料主要包括大修渣、电解质,大修渣是铝电解槽破损维修过程产生的废渣,电解质包括电解过程从电解槽中捞出的电解质以及炭渣浮选后得到的电解质等,其中均含有较高含量的锂。随着我国铝产量的提高,铝电解废料的产生量逐年增加,根据电解铝企业的不同,其中含有不同比例的锂,主要以氟化锂的形式存在。锂是重要的战略资源,广泛应用于手机、电脑、新能源汽车、储能等生产生活领域。
然而,现有提锂方法大多采用加酸、加碱或焙烧法以提高锂盐转化率,但均存在流程长、溶出液杂质含量高、除杂工艺复杂等问题。
发明内容
本公开的一些实施方式提供了一种铝电解废料的锂盐回收方法及回收设备,无需焙烧、加酸或加碱,能够简化锂盐回收的流程。
依据本公开的第一方面,提供了一种铝电解废料的锂盐回收方法,包括:将铝电解废料的粉料与水和提锂剂混合,以溶出锂盐,得到溶出浆液,所述铝电解废料包括铝电解大修渣和电解质;对所述溶出浆液进行多级除杂,得到锂盐。
依据本公开的第二方面,提供了一种铝电解废料的锂盐回收设备,应用于第一方面所述的铝电解废料的锂盐回收方法,包括:破碎机;制粉机,所述制粉机的入料口与所述破碎机的出料口连通;溶出槽,所述溶出槽的入 料口设置有两通阀或三通阀,所述两通阀或三通阀的一通与所述制粉机的出料口连通,另一通用于注入提锂剂;除杂系统,所述除杂系统的入料口与所述溶出槽的出料口连通。
附图说明
为了更清楚地说明本公开实施例中的技术方案,下面将对实施例描述中所需要使用的附图作一简单地介绍,显而易见地,下面描述中的附图是本公开的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。
图1示出了依据本公开一些实施方式的一种铝电解废料的锂盐回收方法的示意性流程图;
图2示出了依据本公开一些实施方式的一种铝电解废料的锂盐回收设备的示意性结构框图;
图3示出了依据本公开一些实施方式的一种溶出槽的示意性结构图;以及
图4示出了依据本公开一些实施方式的另一种铝电解废料的锂盐回收设备的示意性结构图。
具体实施方式
为了更好的理解本说明书实施例提供的技术方案,下面通过附图以及具体实施例对本说明书实施例的技术方案做详细的说明,应当理解本说明书实施例以及实施例中的具体特征是对本说明书实施例技术方案的详细的说明,而不是对本说明书技术方案的限定,在不冲突的情况下,本说明书实施例以及实施例中的技术特征可以相互组合。
在本公开中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。术 语“两个以上”包括两个或大于两个的情况。
第一方面,本公开提供了一种铝电解废料的锂盐回收方法,图1为本公开实施例提供的一种铝电解废料的锂盐回收方法示意性流程图。如图1所示,锂盐回收方法包括:S100:将铝电解废料的粉料与水和提锂剂混合,以溶出锂盐,得到溶出浆液,所述铝电解废料包括铝电解大修渣和电解质。电解质在常温下是固体形态,示例性的,可以将铝电解大修渣或电解质或大修渣和电解质混合料的粉料与水先进行混合,之后加入提锂剂,提锂剂可以将铝电解废料的粉料中的锂溶解在液体内,得到溶出浆料。提锂剂可以包括盐类,例如硫酸盐或氯化盐等,可以将铝电解废料的粉料中氟化锂的锂置换为能够溶于水的锂盐,便于后续的锂盐提纯除杂。S200:对溶出浆液进行多级除杂,得到锂盐。多级除杂可以包括沉淀、固液转化或结晶、固液分离等。铝电解废料主要包括大修渣、电解质,大修渣是铝电解槽破损维修过程产生的废渣,电解质包括电解过程从电解槽中捞出的电解质以及炭渣浮选后得到的电解质等,其中均含有较高含量的锂。随着我国铝产量的提高,铝电解废料的产生量逐年增加,根据电解铝企业的不同,其中含有0.5%-2%的锂,主要以氟化锂的形式存在,锂是重要的战略资源,广泛应用于手机、电脑、新能源汽车、储能等生产生活领域。我国锂资源相对丰富,但80%以上存在于盐湖中,盐湖成分复杂,提锂成本较高。铝电解废料成分相对简单,杂质少,锂含量较高,具有相当高的回收利用价值。
现有提锂方法大多采用加酸或加碱或焙烧法,以提高锂盐转化率,但均存在流程长、溶出液杂质含量高、除杂工艺复杂、对设备要求高等问题,硫酸和碱液不仅属于危险废物,而且具有较强的反应性,在溶出过程会将原料中的多种杂质共同溶出,后续除杂困难,且加酸以及焙烧存在有毒氟化氢气体产生等环保问题,作业环境差,环境污染严重。另外,酸或碱对于设备的腐蚀严重,设备的维修周期变短,设备损耗增加。本公开实施例提供的铝电解废料的锂盐回收方法,对铝电解废料进行破磨得到铝电解废料的粉料,将铝电解废料的粉料与水混合,再加入提锂剂,将铝电解废料的粉料中的氟化锂转换为溶于水的锂盐,再经过多级除杂提纯得到锂盐。无需进行原料的焙烧,简化锂回收流程。无需加酸或加碱进行锂盐的溶出,可以避免锂回收过程对于设备的腐蚀,提高设备使用寿命,另外可以避免更多杂质的溶出,以减少除杂流程,进一步简化锂回收流程,以及可以避免有毒氟化氢气体产生,避免造成环境污染。
在一些实施方式中,步骤S100之前,还可以包括:将铝电解废料破磨,得到铝电解废料的粉料。具体的可以分为两步,先进行初步破碎,再进行制粉,得到铝电解废料的粉料。
在一些实施方式中,提锂剂包括硫酸钙、硫酸镁、氯化钙和氯化镁中的一种。只采用硫酸钙、硫酸镁、氯化钙和氯化镁中的一种,可以减少多余的杂质溶出,避免增加除杂流程,进一步简化锂回收流程,且能够降低回收成本。
在一些实施方式中,在将铝电解废料的粉料与水和提锂剂混合的步骤中,铝电解废料的粉料与水的固液比的范围为1:3~1:5,提锂剂的加入量是与铝电解废料的粉料中锂和氟完全反应所需提锂剂的理论值的1.8~2.2倍。溶出反应时间为1~2小时,反应温度范围为80~95℃。
示例性的,将铝电解废料可以是铝电解大修渣原料、电解质原料、铝电解大修渣和电解质的混合原料,通过破碎机破碎后出料,通过输运设备将破碎好的料加入制粉机内制粉,制粉机出料的粒度控制在0.5mm以下。先通过注水口向溶出槽中加水,随后通过入料口向溶出槽中加入铝电解废料的粉料,固液比控制在1:3~1:5,可以是1:3、1:4、1:5,可以根据大修渣中锂盐含量加以调整,最后通过入料口向溶出槽中加入计算得到的提锂剂,提锂剂可以是硫酸钙、硫酸镁、氯化钙和氯化镁中的一种,铝电解废料的粉料和提锂剂的入料口可以通过两通阀或三通阀转换实现。提锂剂加入量以大修渣中锂含量与氟含量之和为基数,按照摩尔比1:1完全反应计算出理论值,加入量为理论值的1.8-2.2倍,可以是1.8倍、1.9倍、2.0倍、2.1倍或2.2倍,溶出反应时间范围为1-2小时,可以是1.0小时、1.5小时或2.0小时,溶出反应温度范围为80-95℃,可以是80℃、85℃、90℃或95℃,提锂剂加入量、反应时间和反应温度可以根据大修渣中锂盐含量加以调整。溶出槽的入料口和注水口可以设置有单向阀,只能单向流入,每种物料添加完毕后自动关闭。
在一些实施方式中,步骤S200,可以包括:对溶出浆液进行第一次固液分离,得到第一溶出液。固液分离的液体内含有锂盐,在提锂剂为硫酸钙的情况下,溶出的锂盐为硫酸锂。利用氢氧化钠,将第一溶出液的pH值控制在11~12,进行沉淀。可以将镁、钙、铝、铁等杂质以固体形式沉淀去除。对沉淀后的混合液进行第二次固液分离,得到第二溶出液。利用树脂吸附柱或过滤膜对第二溶出液进行除杂,得到第三溶出液。树脂吸附柱或过滤膜可以吸附钙盐和镁盐,进一步除杂提纯。对第三溶出液进行浓缩结晶除杂,得到 结晶混合液。浓缩可以是膜浓缩或蒸发浓缩,结晶可以是冷冻结晶,温度可以控制在零度以下,在提锂剂为硫酸钙的情况下,可以得到硫酸钠结晶,硫酸钠结晶可以作为锂回收的副产品,也是对锂盐的提纯。对结晶混合液进行第三次固液分离,得到第四溶出液。在第四溶出液中加入置换反应物,以发生置换反应,并在90~100℃的环境中蒸发沉淀1.5~2.5小时,得到固体粗锂盐。置换物可以是碳酸钠溶液,与硫酸锂发生置换反应,得到碳酸锂,碳酸锂是固体锂盐,经过蒸发沉淀可以得到固体粗锂盐。对固体粗锂盐依次进行水洗和烘干,得到锂盐。水洗和烘干可以进一步去除固体粗锂盐表面的杂质,进一步提纯,得到较为纯净的锂盐。
在一些实施方式中,步骤S100之前,还包括:在铝电解废料的粉料的含氟量大于5000mg/L的情况下,对铝电解废料的粉料进行提氟洗涤后,进行固液分离,得到含氟溶液和固体渣,其中,固体渣用于与水和提锂剂进行混合;对含氟溶液进行蒸发结晶,得到氟盐。氟盐可以作为锂回收的副产品,提高铝电解废料的利用率。
第二方面,提供了一种铝电解废料的锂盐回收设备,应用于第一方面所述的铝电解废料的锂盐回收方法,图2为本公开实施例提供的一种铝电解废料的锂盐回收设备的示意性结构框图。如图2所示,所述锂盐回收设备包括:破碎机101;制粉机102,制粉机的入料口与破碎机的出料口连通;溶出槽103,溶出槽的入料口设置有两通阀或三通阀,两通阀或三通阀的一通与制粉机的出料口连通,另一通用于注入提锂剂;除杂系统400,除杂系统的入料口与溶出槽的出料口连通。
本公开实施例提供的铝电解废料的锂盐回收设备,对铝电解废料进行破磨制样得到铝电解废料的粉料,将铝电解废料的粉料与水混合,再加入提锂剂,将铝电解废料的粉料中的氟化锂转换为溶于水的锂盐,再经过多级除杂提纯得到锂盐。无需进行原料的焙烧,简化锂回收流程。无需加酸或加碱进行锂盐的溶出,可以避免锂回收过程对于设备的腐蚀,提高设备使用寿命,另外可以避免更多杂质的溶出,以减少除杂流程,进一步简化锂回收流程,以及可以避免有毒氟化氢气体产生,避免造成环境污染。
在一些实施方式中,图3为本公开实施例提供的一种溶出槽的示意性结构图。如图3所示,所述溶出槽包括:溶出反应腔210,用于容纳铝电解废料的粉料、提锂剂和水,溶出反应腔210连通有入料口202、注水口203、浆液导出口208、溢流口205和液位计口204。第一加热腔220,至少部分包裹 溶出反应腔210,第一加热腔220包括第一注入口207、第一溢出口201和温度计口206。搅拌桨301,插设于溶出反应腔210内,搅拌桨301内设置有第二加热腔230,第二加热腔230连通有第二注入口302和第二溢出口303,搅拌桨301包括桨叶304和隔板305。第一加热腔220和第二加热腔230用于容纳热水和/或热蒸汽,容纳有热水和/或热蒸汽的第一加热腔220和第二加热腔230可以为溶出反应腔210提供80℃~95℃的温度环境。
示例性的,整个锂盐溶出过程在溶出槽103内进行,溶出槽103可以为立式槽;外壁设置第二加热腔230,可以实现夹套式间接加热,蒸汽或热水可以从第一注入口207注入,从第一溢出口201溢出,第一注入口207位于底端,第一溢出口201位于顶端,外界完成热交换后再从第一注入口207流入。搅拌桨301中空并设置有隔板305,通入热源辅助加热,热源为蒸气或热水,桨叶304为弧形,热源流通无死角,蒸气或热水沿着隔板305在整个搅拌桨301内流动,使搅拌桨301内部温度均匀,通过搅拌桨301的转动对溶出槽103内的浆液均匀加热,搅拌桨301设置有第二注入口302和第二溢出口303,均位于搅拌桨301上部,蒸气或热水通过第二注入口302流入,第二溢出口303流出,外界热交换后再从第二注入口302流入。溶出槽103内衬及搅拌桨301的材质为钢衬防腐四氟乙烯。在溶出反应过程中,搅拌桨301持续工作,使大修渣原料和提锂剂充分反应,反应过程通过温度计口206和液位计口204监测溶出槽103内的反应温度和液位高低。
在一些实施方式中,图4为本公开实施例提供的另一种铝电解废料的锂盐回收设备的示意性结构图。如图4所示,除杂系统400包括:第一固液分离机104,与溶出槽103连通;沉淀罐105,与第一固液分离机104的出液口连通,用于利用氢氧化钠将第一溶出液的pH值控制在11~12,进行沉淀;第二固液分离机106,与沉淀罐105的出液口连通;过滤器107,与第二固液分离机106的出液口连通;过滤器可以是树脂吸附柱或过滤膜。结晶器108,与过滤器107的出口连通;第三固液分离机109,与结晶器108的出液口连通;沉锂槽110,与第三固液分离机109的出液口连通,用于发生置换反应得到固体粗锂盐;第四固液分离机111,与沉锂槽110的出料口连通;洗涤器112,与第四固液分离机111的固体出料口连通;烘干机113,与洗涤器112的固体出料口连通。将粗碳酸锂经洗涤器112多级反向洗涤提纯后,得到工业级碳酸锂产品,洗涤液循环使用。
在一些实施方式中,参考图4,本公开实施例提供的铝电解废料的锂盐 回收设备,还包括:除氟系统,除氟系统包括依次连接的反向洗涤器401、第五固液分离机402和蒸发器403;反向洗涤器401的入料口与制粉机102的出料口连通;第五固液分离机402的固体出料口与溶出槽103的入料口连通,第五固液分离机402的液体出料口与蒸发器403连通。
若大修渣原料中氟含量过高,超过5000mg/L,可先将大修渣通过破碎机101和制粉机102制样后,通过反向洗涤器401提氟后,通过第五固液分离机402进行固液分离,将滤渣加入溶出槽103进行提锂溶出,滤液通过蒸发器403结晶得到氟盐产品。
需要说明的是,在上述实施例中,对各个实施例的描述都各有侧重,某个实施例中没有详细描述的部分,可以参见其它实施例的相关描述。
以上实施例仅用以说明本公开的技术方案,而非对其限制;尽管参照前述实施例对本公开进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本公开各实施例技术方案的精神和范围。
尽管已描述了本说明书的优选实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例作出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本说明书范围的所有变更和修改。
显然,本领域的技术人员可以对本说明书进行各种改动和变型而不脱离本说明书的精神和范围。这样,倘若本说明书的这些修改和变型属于本说明书权利要求及其等同技术的范围之内,则本说明书也意图包含这些改动和变型在内。

Claims (10)

  1. 一种铝电解废料的锂盐回收方法,包括:
    将铝电解废料的粉料与水和提锂剂混合,以溶出锂盐,得到溶出浆液,其中,所述铝电解废料包括铝电解大修渣和电解质;
    对所述溶出浆液进行多级除杂,得到锂盐。
  2. 根据权利要求1所述的铝电解废料的锂盐回收方法,其中,所述提锂剂包括硫酸钙、硫酸镁、氯化钙和氯化镁中的一种;
    所述铝电解废料的粉料的粒度小于0.5mm。
  3. 根据权利要求1所述的铝电解废料的锂盐回收方法,其中,在所述将铝电解废料的粉料与水和提锂剂混合的步骤中,所述铝电解废料的粉料与水的固液比的范围为1:3~1:5,所述提锂剂的加入量是与所述铝电解废料的粉料中锂和氟完全反应所需所述提锂剂的理论值的1.8~2.2倍。
  4. 根据权利要求3所述的铝电解废料的锂盐回收方法,其中,在所述将所述铝电解废料的粉料与水和提锂剂混合的步骤中,溶出反应时间为1~2小时,反应温度范围为80~95℃。
  5. 根据权利要求1所述的铝电解废料的锂盐回收方法,其中,所述对所述溶出浆液进行多级除杂,得到锂盐,包括:
    对所述溶出浆液进行第一次固液分离,得到第一溶出液;
    利用氢氧化钠,将所述第一溶出液的pH值控制在11~12,进行沉淀;
    对沉淀后的混合液进行第二次固液分离,得到第二溶出液;
    利用树脂吸附柱或过滤膜对所述第二溶出液进行除杂,得到第三溶出液;
    对所述第三溶出液进行浓缩结晶除杂,得到结晶混合液;
    对所述结晶混合液进行第三次固液分离,得到第四溶出液;
    在所述第四溶出液中加入置换反应物,以发生置换反应,并在90~100℃的环境中蒸发沉淀1.5~2.5小时,得到固体粗锂盐;
    对所述固体粗锂盐依次进行水洗和烘干,得到锂盐。
  6. 根据权利要求1所述的铝电解废料的锂盐回收方法,其中,所述将所述铝电解废料的粉料与水和提锂剂混合之前,还包括:
    在所述铝电解废料的粉料的含氟量大于5000mg/L的情况下,对所述铝电解废料的粉料进行提氟洗涤后,进行固液分离,得到含氟溶液和固体渣,其中,所述固体渣用于与水和所述提锂剂进行混合;
    对所述含氟溶液进行蒸发结晶,得到氟盐。
  7. 一种铝电解废料的锂盐回收设备,应用于如权利要求1-6中任一项所述的铝电解废料的锂盐回收方法,包括:
    破碎机;
    制粉机,所述制粉机的入料口与所述破碎机的出料口连通;
    溶出槽,所述溶出槽的入料口设置有两通阀或三通阀,所述两通阀或三通阀的一通与所述制粉机的出料口连通,另一通用于注入提锂剂;
    除杂系统,所述除杂系统的入料口与所述溶出槽的出料口连通。
  8. 根据权利要求7所述的铝电解废料的锂盐回收设备,其中,所述溶出槽包括:
    溶出反应腔,用于容纳所述铝电解废料的粉料、所述提锂剂和水,所述溶出反应腔连通有入料口、注水口、浆液导出口、溢流口和液位计口;
    第一加热腔,至少部分包裹所述溶出反应腔,所述第一加热腔包括第一注入口、第一溢出口和温度计口;
    搅拌桨,插设于所述溶出反应腔内,所述搅拌桨内设置有第二加热腔,所述第二加热腔连通有第二注入口和第二溢出口,所述搅拌桨包括桨叶和隔板;
    所述第一加热腔和所述第二加热腔用于容纳热水和/或热蒸汽。
  9. 根据权利要求7所述的铝电解废料的锂盐回收设备,其中,所述除杂系统包括:
    第一固液分离机,与所述溶出槽连通;
    沉淀罐,与所述第一固液分离机的出液口连通,用于利用氢氧化钠将第一溶出液的pH值控制在11~12,进行沉淀;
    第二固液分离机,与所述沉淀罐的出液口连通;
    过滤器,与所述第二固液分离机的出液口连通;
    结晶器,与所述过滤器的出口连通;
    第三固液分离机,与所述结晶器的出液口连通;
    沉锂槽,与所述第三固液分离机的出液口连通,用于发生置换反应得到固体粗锂盐;
    第四固液分离机,与所述沉锂槽的出料口连通;
    洗涤器,与所述第四固液分离机的固体出料口连通;
    烘干机,与所述洗涤器的固体出料口连通。
  10. 根据权利要求7所述的铝电解废料的锂盐回收设备,还包括:
    除氟系统,所述除氟系统包括依次连接的反向洗涤器、第五固液分离机和蒸发器;
    所述反向洗涤器的入料口与所述制粉机的出料口连通;
    [0034]所述第五固液分离机的固体出料口与所述溶出槽的入料口连通,所述第五固液分离机的液体出料口与所述蒸发器连通。
PCT/CN2023/098544 2022-06-20 2023-06-06 铝电解废料的锂盐回收方法及回收设备 WO2023246500A1 (zh)

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