WO2017181759A1 - Method for manufacturing anhydrous lithium chloride using lithium-containing wastewater - Google Patents
Method for manufacturing anhydrous lithium chloride using lithium-containing wastewater Download PDFInfo
- Publication number
- WO2017181759A1 WO2017181759A1 PCT/CN2017/072970 CN2017072970W WO2017181759A1 WO 2017181759 A1 WO2017181759 A1 WO 2017181759A1 CN 2017072970 W CN2017072970 W CN 2017072970W WO 2017181759 A1 WO2017181759 A1 WO 2017181759A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- chloride
- waste liquid
- containing waste
- sodium
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
Definitions
- the present invention relates to the technical field of lithium chloride preparation, and more particularly to a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid.
- Lithium chloride is an important lithium salt product. In recent years, it has been widely used as a mutagen in pharmaceutical, food, environmental protection and other industries. It can be used to cultivate high-yield strains, synthetic pharmaceutical intermediates, and genetic modification of strains. It can also be used for the extraction and purification of isolated RNA and a small amount of plasmid DNA; it is also an important cationic additive in organic structure analysis; in medicine, it can be used for the treatment of diabetes and applied to genetic research; In the field of materials, it can be applied to the production of chitin. In addition, electrolytic production of lithium metal is the largest consumption of lithium chloride, and it is also the only industrial method for producing lithium metal. Metallic lithium and its alloys and compounds have a wide range of applications in many fields such as metallurgical industry, battery, ceramics, glass, chemical, aerospace, and atomic energy industries.
- the preparation methods of lithium chloride mainly include solvent extraction method, ion exchange adsorption method, salting out method and conversion method, and the conversion method is generally divided into ore direct conversion method, lithium carbonate or lithium hydroxide conversion method, lithium sulfate conversion method and Lithium hydroxide direct chlorination method, in which lithium carbonate or lithium hydroxide conversion method is the most important industrial method, most of the lithium chloride in China is produced by this method.
- the raw material cost is high and the impurity sodium and potassium are difficult to be separated.
- the separation of sodium and potassium by solvent extraction or ion exchange has an ideal separation effect, but the production cost is high and economically unreasonable.
- lithium-containing waste liquid produced in the production process of pharmaceutical intermediates as raw material to prepare anhydrous lithium chloride can greatly reduce the cost of raw materials and solve problems such as wastewater discharge and environmental pollution. Therefore, it is necessary to provide a method for preparing anhydrous lithium chloride by utilizing a lithium-containing waste liquid produced in the production process of a pharmaceutical intermediate.
- an object of the present invention is to provide a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid with a simple process, low production cost, high lithium recovery rate, and environmental friendliness.
- the invention provides a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid containing at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions and chloride ions.
- the method includes the following steps:
- the refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids and filtered to remove the sodium chloride and potassium chloride solids to obtain a lithium chloride clear solution;
- An embodiment of a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to the present invention wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate, wherein the lithium-containing waste liquid
- the lithium ion concentration is 10 to 35 g/L
- the chloride ion concentration is 80 to 200 g/L
- the sodium ion concentration is 1 to 15 g/L
- the sulfate ion concentration is 0.5 to 5 g/L
- the magnesium ion concentration is 0.1 to 2 g/ L
- the calcium ion concentration is 0.2 to 4 g/L
- the potassium ion concentration is 0.01 to 0.2 g/L.
- the hydrogen peroxide in the step A, has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
- step B An embodiment of a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in step B
- the concentration of the ruthenium chloride solution is 50 to 200 g/L, and the reaction time is 30 to 120 min.
- a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid in the step C, the sodium carbonate solution has a concentration of 50 to 200 g/L, and the reaction temperature is 20 to 60 ° C, and the reaction time is It is 30 to 240 minutes.
- the sodium ion concentration in the lithium chloride supernatant is less than 1 g/L, and the potassium ion concentration is less than 0.5. g/L.
- the sodium fine preparation is Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 and The sodium concentrate preparation is added in an amount of 25 to 30 times the mass of the sodium in the lithium chloride supernatant.
- a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid in the step E, the reaction temperature is 40 to 95 ° C, the reaction time is 2 to 8 hours, and the pore diameter is 0.5 to 0.5 after the reaction.
- a 1 ⁇ m microfiltration membrane was used for filtration.
- the sodium ion concentration in the high-concentration lithium chloride solution is less than 0.02 g/L.
- step F placing the high concentration lithium chloride solution in a titanium crucible and in an oven at 200 to 250 ° C Dry down.
- the method for preparing anhydrous lithium chloride by using lithium-containing waste liquid has the following advantages: 1) simple process and low production cost; 2) high lithium recovery rate; 3) anhydrous water prepared Lithium chloride can reach the battery level standard; 4)
- the raw material used is the lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate, and the raw material cost is low; 5)
- the method is environmentally friendly and the environmental protection pressure is small.
- the present invention provides a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid, and the lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate is removed from the residual organic phase by hydrogen peroxide, and then the ruthenium chloride is first removed.
- Sulfate ion, sodium carbonate is added to the mother liquor, and a trace amount of calcium ions, magnesium ions and barium ions are removed by stirring, and the precipitate is filtered to obtain a refined mother liquid, which is concentrated by evaporation and filtered to remove sodium chloride and potassium chloride, and then heated.
- the obtained lithium chloride clear solution is added to the sodium fine preparation and stirred and filtered to obtain a high concentration lithium chloride solution, which is dried to obtain a battery-grade anhydrous lithium chloride product.
- the lithium-containing waste liquid according to the present invention contains at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions, and chloride ions. More preferably, the lithium-containing waste liquid is a lithium-containing waste liquid produced in the production process of a pharmaceutical intermediate.
- the lithium-containing waste liquid has a lithium ion concentration of 10 to 35 g/L, a chloride ion concentration of 80 to 200 g/L, a sodium ion concentration of 1 to 15 g/L, and a sulfate ion concentration of 0.5 to 5 g/L, a magnesium ion concentration of 0.1 to 2 g/L, a calcium ion concentration of 0.2 to 4 g/L, and a potassium ion concentration of 0.01 to 0.2 g/L, but the present invention is not limited thereto.
- the method of preparing anhydrous lithium chloride using a lithium-containing waste liquid includes the following multiple steps.
- Hydrogen peroxide was added to the lithium-containing waste liquid to remove residual organic phase.
- Hydrogen peroxide has strong oxidizing properties and can effectively decompose the organic phase remaining in the lithium-containing waste liquid.
- the hydrogen peroxide has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
- the sulfate ion can be precipitated by adding a ruthenium chloride or ruthenium chloride solution, and the sulfate ion can be removed by filtration.
- the concentration of the ruthenium chloride solution is from 50 to 200 g/L and the reaction time is from 30 to 120 min.
- a sodium carbonate or sodium carbonate solution is added to the mother liquor and filtered to obtain a refined mother liquor.
- the metal cation can be precipitated by adding sodium carbonate or sodium carbonate solution, and the purified mother liquid can be removed by filtration.
- the sodium carbonate solution has a concentration of 50 to 200 g/L, a reaction temperature of 20 to 60 ° C, and a reaction time of 30 to 240 minutes.
- the refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids, and the sodium chloride and potassium chloride solids are removed by filtration to obtain a lithium chloride clear solution;
- sodium chloride and potassium chloride in the mother liquor can be precipitated, and a large amount of potassium ions and sodium ions can be removed by filtration.
- the obtained lithium chloride supernatant has a sodium ion concentration of less than 1 g/L and a potassium ion concentration of less than 0.5 g/L.
- a sodium concentrate preparation is added to the lithium chloride supernatant, and the reaction is stirred and filtered to obtain a high concentration lithium chloride solution.
- the main function of the sodium concentrate preparation is to deeply remove the residual impurity sodium in the lithium chloride supernatant.
- the sodium concentrate preparation may be Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 , and the sodium concentrate preparation is added in an amount of 25 to 30 times the sodium mass in the lithium chloride supernatant.
- the amount of sodium in the lithium chloride supernatant can be determined by ICP or the like before adding the sodium concentrate preparation, and then the amount of the sodium concentrate preparation added can be calculated.
- the reaction temperature is controlled to be 40 to 95 ° C and the reaction time is 2 to 8 h.
- the lithium chloride supernatant may be heated to the above reaction temperature, and then the sodium refined preparation is added for the reaction, and After the reaction, filtration was carried out using a microfiltration membrane having a pore diameter of 0.5 to 1 ⁇ m.
- the sodium ion concentration in the obtained high-concentration lithium chloride solution is less than 0.02 g/L.
- a high-concentration lithium chloride solution can be placed in a titanium crucible and dried in an oven at 200 to 250 ° C to obtain a battery-grade standard anhydrous lithium chloride.
- lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate
- the lithium ion concentration in the lithium-containing waste liquid is 25 g/L
- the chloride ion concentration is 150 g. /L, sodium ion concentration 10 g / L, sulfate ion concentration 3 g / L, magnesium ion concentration 0.1 g / L, calcium ion concentration 0.2 g / L, potassium ion concentration 0.01 g / L.
- lithium-containing waste liquid is a lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate
- the lithium ion concentration in the lithium-containing waste liquid is 30 g/L
- the chloride ion concentration is 120 g. /L, sodium ion concentration 8 g / L, sulfate ion concentration 4 g / L, magnesium ion concentration 2 g / L, calcium ion concentration 0.5 g / L, potassium ion concentration 0.1 g / L.
- lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate
- the lithium ion concentration in the lithium-containing waste liquid is 20 g/L
- the chloride ion concentration is 100 g. /L, sodium ion concentration 12g / L, sulfate ion concentration 2g / L, magnesium ion concentration of 0.5g / L, calcium ion concentrated
- the degree was 4 g/L and the potassium ion concentration was 0.2 g/L.
- the method for preparing anhydrous lithium chloride by using lithium-containing waste liquid has the following advantages: 1) simple process and low production cost; 2) high lithium recovery rate; 3) anhydrous chlorination prepared Lithium can reach the battery level standard; 4)
- the raw materials used are lithium-containing waste liquid produced during the production of pharmaceutical intermediates, and the raw material cost is low; 5)
- the method is environmentally friendly and has low environmental protection pressure.
- the invention is not limited to the specific embodiments described above.
- the invention extends to any new feature or any new combination disclosed in this specification, as well as any novel method or process steps or any new combination disclosed.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A method for manufacturing anhydrous lithium chloride using lithium-containing wastewater, wherein the lithium-containing wastewater at least contains a lithium ion, calcium ion, magnesium ion, sodium ion, potassium ion, sulfate ion, and chloride ion. The method comprises the following steps: A. adding hydrogen peroxide to the lithium-containing wastewater to remove a residual organic phase; B. adding barium chloride or a solvent thereof for a reaction, and then filtering to obtain a mother liquor; C. adding sodium carbonate or a solvent thereof to the mother liquor, and then filtering to obtain a refined mother liquor; D. implementing evapo-concentration of the refined mother liquor to precipitate solid sodium chloride and potassium chloride, then removing the solid sodium chloride and potassium chloride to obtain a purified lithium chloride solution; E. adding a sodium refining agent into the purified lithium chloride solution, mixing and reacting to obtain a highly concentrated lithium chloride solution; F. and oven drying the highly concentrated lithium chloride solution to obtain the anhydrous lithium chloride. The method has simple techniques, low production costs, high lithium recovery rate, and is environmentally friendly.
Description
本发明涉及氯化锂制备的技术领域,更具体地讲,涉及一种利用含锂废液制备无水氯化锂的方法。The present invention relates to the technical field of lithium chloride preparation, and more particularly to a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid.
氯化锂是一种重要的锂盐产品,近年来,其作为诱变剂广泛应用于医药、食品、环保等行业,可用于培育高产菌株、合成医药中间体以及对菌种进行遗传改造等,还可用于分离提取RNA及少量质粒DNA的提取和纯化;在有机结构分析方面,其又是一种重要的阳离子添加剂;在医学上,其可以用于治疗糖尿病并应用于遗传研究等;在新材料领域,其可以应用于甲壳素的生产。此外,电解生产金属锂是氯化锂消耗量最大的方面,亦是当前生产金属锂的唯一工业方法。金属锂及其合金和化合物在冶金工业、电池、陶瓷、玻璃、化工、航天工业、原子能工业等许多领域均具有广泛的应用。Lithium chloride is an important lithium salt product. In recent years, it has been widely used as a mutagen in pharmaceutical, food, environmental protection and other industries. It can be used to cultivate high-yield strains, synthetic pharmaceutical intermediates, and genetic modification of strains. It can also be used for the extraction and purification of isolated RNA and a small amount of plasmid DNA; it is also an important cationic additive in organic structure analysis; in medicine, it can be used for the treatment of diabetes and applied to genetic research; In the field of materials, it can be applied to the production of chitin. In addition, electrolytic production of lithium metal is the largest consumption of lithium chloride, and it is also the only industrial method for producing lithium metal. Metallic lithium and its alloys and compounds have a wide range of applications in many fields such as metallurgical industry, battery, ceramics, glass, chemical, aerospace, and atomic energy industries.
目前,氯化锂的制备方法主要有溶剂萃取法、离子交换吸附法、盐析法和转化法,转化法一般分为矿石直接转化法、碳酸锂或氢氧化锂转化法、硫酸锂转化法和氢氧化锂直接氯化法,其中碳酸锂或氢氧化锂转化法是最主要的工业方法,我国大部分氯化锂就是以此方法生产的。但无论上述哪种方法均存在原料成本高、杂质钠钾难分离的问题,采用溶剂萃取或离子交换分离钠钾虽分离效果理想,但生产成本高,经济上不合理。At present, the preparation methods of lithium chloride mainly include solvent extraction method, ion exchange adsorption method, salting out method and conversion method, and the conversion method is generally divided into ore direct conversion method, lithium carbonate or lithium hydroxide conversion method, lithium sulfate conversion method and Lithium hydroxide direct chlorination method, in which lithium carbonate or lithium hydroxide conversion method is the most important industrial method, most of the lithium chloride in China is produced by this method. However, regardless of the above methods, there is a problem that the raw material cost is high and the impurity sodium and potassium are difficult to be separated. The separation of sodium and potassium by solvent extraction or ion exchange has an ideal separation effect, but the production cost is high and economically unreasonable.
利用医药中间体生产过程中产生的含锂废液为原料制备无水氯化锂可以极大的降低原料成本并解决其废水排放及环境污染等问题。因此,有必要提供一种能够利用医药中间体生产过程中产生的含锂废液制备无水氯化锂的方法。
The use of lithium-containing waste liquid produced in the production process of pharmaceutical intermediates as raw material to prepare anhydrous lithium chloride can greatly reduce the cost of raw materials and solve problems such as wastewater discharge and environmental pollution. Therefore, it is necessary to provide a method for preparing anhydrous lithium chloride by utilizing a lithium-containing waste liquid produced in the production process of a pharmaceutical intermediate.
发明内容Summary of the invention
为了解决现有技术中存在的问题,本发明的目的是提供一种工艺简单、生产成本低、锂回收率高且环境友好的利用含锂废液制备无水氯化锂的方法。In order to solve the problems existing in the prior art, an object of the present invention is to provide a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid with a simple process, low production cost, high lithium recovery rate, and environmental friendliness.
本发明提供了一种利用含锂废液制备无水氯化锂的方法,所述含锂废液中至少含有锂离子、钙离子、镁离子、钠离子、钾离子、硫酸根离子和氯离子,所述方法包括以下步骤:The invention provides a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid containing at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions and chloride ions. The method includes the following steps:
A、向所述含锂废液中加入双氧水,以去除残余有机相;A, adding hydrogen peroxide to the lithium-containing waste liquid to remove residual organic phase;
B、再加入氯化钡或氯化钡溶液并且在反应后过滤得到母液;B, further adding barium chloride or barium chloride solution and filtering after the reaction to obtain a mother liquor;
C、向所述母液中加入碳酸钠或碳酸钠溶液并且在反应后过滤得到精制母液;C, adding sodium carbonate or sodium carbonate solution to the mother liquor and filtering to obtain a refined mother liquor after the reaction;
D、将所述精制母液蒸发浓缩至析出氯化钠和氯化钾固体并过滤除去所述氯化钠和氯化钾固体,得到氯化锂清液;D, the refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids and filtered to remove the sodium chloride and potassium chloride solids to obtain a lithium chloride clear solution;
E、向所述氯化锂清液中加入钠精制剂,搅拌反应后过滤得到高浓度氯化锂溶液;E, adding a sodium fine preparation to the lithium chloride clear solution, stirring the reaction and filtering to obtain a high concentration lithium chloride solution;
F、将所述高浓度氯化锂溶液烘干后得到无水氯化锂。F. Drying the high concentration lithium chloride solution to obtain anhydrous lithium chloride.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,所述含锂废液为医药中间体的生产过程中产生的含锂废液,其中,所述含锂废液中的锂离子浓度为10~35g/L、氯离子浓度为80~200g/L、钠离子浓度1~15g/L、硫酸根离子浓度为0.5~5g/L、镁离子浓度为0.1~2g/L、钙离子浓度为0.2~4g/L、钾离子浓度为0.01~0.2g/L。An embodiment of a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to the present invention, wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate, wherein the lithium-containing waste liquid The lithium ion concentration is 10 to 35 g/L, the chloride ion concentration is 80 to 200 g/L, the sodium ion concentration is 1 to 15 g/L, the sulfate ion concentration is 0.5 to 5 g/L, and the magnesium ion concentration is 0.1 to 2 g/ L, the calcium ion concentration is 0.2 to 4 g/L, and the potassium ion concentration is 0.01 to 0.2 g/L.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤A中,所述双氧水的质量浓度为10~50%,反应时间为10~50min。According to one embodiment of the method for preparing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in the step A, the hydrogen peroxide has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤B
中,所述氯化钡溶液的浓度为50~200g/L,反应时间为30~120min。An embodiment of a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in step B
The concentration of the ruthenium chloride solution is 50 to 200 g/L, and the reaction time is 30 to 120 min.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤C中,所述碳酸钠溶液的浓度为50~200g/L,反应温度为20~60℃,反应时间为30~240min。According to an embodiment of the present invention, a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid, in the step C, the sodium carbonate solution has a concentration of 50 to 200 g/L, and the reaction temperature is 20 to 60 ° C, and the reaction time is It is 30 to 240 minutes.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤D中,所述氯化锂清液中的钠离子浓度低于1g/L,钾离子浓度低于0.5g/L。According to one embodiment of the method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to the present invention, in the step D, the sodium ion concentration in the lithium chloride supernatant is less than 1 g/L, and the potassium ion concentration is less than 0.5. g/L.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤E中,所述钠精制剂为Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3并且所述钠精制剂的加入量为所述氯化锂清液中钠质量的25~30倍。An embodiment of a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in the step E, the sodium fine preparation is Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 and The sodium concentrate preparation is added in an amount of 25 to 30 times the mass of the sodium in the lithium chloride supernatant.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤E中,反应温度为40~95℃,反应时间为2~8h,并且在反应后利用孔径为0.5~1μm的微滤膜进行过滤。According to an embodiment of the present invention, a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid, in the step E, the reaction temperature is 40 to 95 ° C, the reaction time is 2 to 8 hours, and the pore diameter is 0.5 to 0.5 after the reaction. A 1 μm microfiltration membrane was used for filtration.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤E中,所述高浓度氯化锂溶液中的钠离子浓度低于0.02g/L。According to one embodiment of the method for producing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in step E, the sodium ion concentration in the high-concentration lithium chloride solution is less than 0.02 g/L.
根据本发明利用含锂废液制备无水氯化锂的方法的一个实施例,在步骤F中,将所述高浓度氯化锂溶液置于钛坩埚内并在烘炉内于200~250℃下烘干。An embodiment of a method for preparing anhydrous lithium chloride using a lithium-containing waste liquid according to the present invention, in step F, placing the high concentration lithium chloride solution in a titanium crucible and in an oven at 200 to 250 ° C Dry down.
与现有技术相比,本发明的利用含锂废液制备无水氯化锂的方法具有以下优点:1)工艺简单、生产成本低;2)锂回收率高;3)所制备的无水氯化锂可达电池级标准;4)所采用的原料为医药中间体生产过程中产生的含锂废液,原料成本低;5)该法属环境友好型,环保压力小。Compared with the prior art, the method for preparing anhydrous lithium chloride by using lithium-containing waste liquid has the following advantages: 1) simple process and low production cost; 2) high lithium recovery rate; 3) anhydrous water prepared Lithium chloride can reach the battery level standard; 4) The raw material used is the lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate, and the raw material cost is low; 5) The method is environmentally friendly and the environmental protection pressure is small.
本说明书中公开的所有特征,或公开的所有方法或过程中的步骤,除了互相排斥的特征和/或步骤以外,均可以以任何方式组合。
All of the features disclosed in this specification, or steps in all methods or processes disclosed, may be combined in any manner other than mutually exclusive features and/or steps.
本说明书中公开的任一特征,除非特别叙述,均可被其他等效或具有类似目的的替代特征加以替换。即,除非特别叙述,每个特征只是一系列等效或类似特征中的一个例子而已。Any feature disclosed in this specification, unless specifically stated otherwise, may be replaced by other equivalents or alternative features having similar purposes. That is, unless specifically stated, each feature is only one example of a series of equivalent or similar features.
概括地讲,本发明提供了一种利用含锂废液制备无水氯化锂的方法,将医药中间体生产过程中产生的含锂废液经双氧水去除残余有机相,先加入氯化钡除去硫酸根离子,母液中再加入碳酸钠经搅拌过滤除去微量的钙离子、镁离子、钡离子,过滤沉淀物后得到精制母液,对其蒸发浓缩并过滤除去氯化钠和氯化钾,再加热所得氯化锂清液并加入钠精制剂搅拌过滤得到高浓度氯化锂溶液,经干燥后得到电池级无水氯化锂产品。Broadly speaking, the present invention provides a method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid, and the lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate is removed from the residual organic phase by hydrogen peroxide, and then the ruthenium chloride is first removed. Sulfate ion, sodium carbonate is added to the mother liquor, and a trace amount of calcium ions, magnesium ions and barium ions are removed by stirring, and the precipitate is filtered to obtain a refined mother liquid, which is concentrated by evaporation and filtered to remove sodium chloride and potassium chloride, and then heated. The obtained lithium chloride clear solution is added to the sodium fine preparation and stirred and filtered to obtain a high concentration lithium chloride solution, which is dried to obtain a battery-grade anhydrous lithium chloride product.
下面对本发明利用含锂废液制备无水氯化锂的方法进行详细的说明。The method for preparing anhydrous lithium chloride using the lithium-containing waste liquid of the present invention will be described in detail below.
其中,本发明所涉及的含锂废液中至少含有锂离子、钙离子、镁离子、钠离子、钾离子、硫酸根离子和氯离子。更优选地,所述含锂废液为医药中间体的生产过程中产生的含锂废液。根据本发明的一个实施例,所述含锂废液中的锂离子浓度为10~35g/L、氯离子浓度为80~200g/L、钠离子浓度1~15g/L、硫酸根离子浓度为0.5~5g/L、镁离子浓度为0.1~2g/L、钙离子浓度为0.2~4g/L、钾离子浓度为0.01~0.2g/L,但本发明不限于此。The lithium-containing waste liquid according to the present invention contains at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions, and chloride ions. More preferably, the lithium-containing waste liquid is a lithium-containing waste liquid produced in the production process of a pharmaceutical intermediate. According to an embodiment of the present invention, the lithium-containing waste liquid has a lithium ion concentration of 10 to 35 g/L, a chloride ion concentration of 80 to 200 g/L, a sodium ion concentration of 1 to 15 g/L, and a sulfate ion concentration of 0.5 to 5 g/L, a magnesium ion concentration of 0.1 to 2 g/L, a calcium ion concentration of 0.2 to 4 g/L, and a potassium ion concentration of 0.01 to 0.2 g/L, but the present invention is not limited thereto.
根据本发明的示例性实施例,所述利用含锂废液制备无水氯化锂的方法包括以下多个步骤。According to an exemplary embodiment of the present invention, the method of preparing anhydrous lithium chloride using a lithium-containing waste liquid includes the following multiple steps.
步骤A:Step A:
向含锂废液中加入双氧水,以去除残余有机相。Hydrogen peroxide was added to the lithium-containing waste liquid to remove residual organic phase.
双氧水具有强氧化性,能够有效分解含锂废液中残留的有机相。Hydrogen peroxide has strong oxidizing properties and can effectively decompose the organic phase remaining in the lithium-containing waste liquid.
根据本发明的优选实施例,双氧水的质量浓度为10~50%,反应时间为10~50min。
According to a preferred embodiment of the invention, the hydrogen peroxide has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
步骤B:Step B:
再加入氯化钡或氯化钡溶液并且在反应后过滤得到母液。Further, a solution of ruthenium chloride or ruthenium chloride is added and after the reaction, it is filtered to obtain a mother liquid.
由于含锂废液中通常含有一定量的硫酸根离子,因此可以通过加入氯化钡或氯化钡溶液能够使硫酸根离子成为沉淀,进而可以通过过滤去除硫酸根离子。Since the lithium-containing waste liquid usually contains a certain amount of sulfate ions, the sulfate ion can be precipitated by adding a ruthenium chloride or ruthenium chloride solution, and the sulfate ion can be removed by filtration.
根据本发明的优选实施例,氯化钡溶液的浓度为50~200g/L,反应时间为30~120min。According to a preferred embodiment of the invention, the concentration of the ruthenium chloride solution is from 50 to 200 g/L and the reaction time is from 30 to 120 min.
步骤C:Step C:
向母液中加入碳酸钠或碳酸钠溶液并且在反应后过滤得到精制母液。A sodium carbonate or sodium carbonate solution is added to the mother liquor and filtered to obtain a refined mother liquor.
由于含锂废液中还含有微量的钙离子、镁离子以及步骤B加入的钡离子,因此可以通过加入碳酸钠或碳酸钠溶液使上述金属阳离子成为沉淀,进而可以通过过滤去除并得到精制母液。Since the lithium-containing waste liquid further contains a trace amount of calcium ions, magnesium ions, and cesium ions added in the step B, the metal cation can be precipitated by adding sodium carbonate or sodium carbonate solution, and the purified mother liquid can be removed by filtration.
根据本发明的优选实施例,碳酸钠溶液的浓度为50~200g/L,反应温度为20~60℃,反应时间为30~240min。According to a preferred embodiment of the present invention, the sodium carbonate solution has a concentration of 50 to 200 g/L, a reaction temperature of 20 to 60 ° C, and a reaction time of 30 to 240 minutes.
步骤D:Step D:
将精制母液蒸发浓缩至析出氯化钠和氯化钾固体并过滤除去所述氯化钠和氯化钾固体,得到氯化锂清液;The refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids, and the sodium chloride and potassium chloride solids are removed by filtration to obtain a lithium chloride clear solution;
通过将精制母液蒸发至接近共饱和点,可以使母液中的氯化钠和氯化钾析出,进而通过过滤实现对大量钾离子和钠离子的去除。By evaporating the refined mother liquor to near the point of co-saturation, sodium chloride and potassium chloride in the mother liquor can be precipitated, and a large amount of potassium ions and sodium ions can be removed by filtration.
根据本发明,所得氯化锂清液中的钠离子浓度低于1g/L,钾离子浓度低于0.5g/L。According to the present invention, the obtained lithium chloride supernatant has a sodium ion concentration of less than 1 g/L and a potassium ion concentration of less than 0.5 g/L.
步骤E:Step E:
向氯化锂清液中加入钠精制剂,搅拌反应后过滤得到高浓度氯化锂溶液。
A sodium concentrate preparation is added to the lithium chloride supernatant, and the reaction is stirred and filtered to obtain a high concentration lithium chloride solution.
其中,钠精制剂的主要作用是深度除去氯化锂清液中剩余的杂质钠。根据本发明的优选实施例,钠精制剂可以为Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3,并且钠精制剂的加入量为氯化锂清液中钠质量的25~30倍,例如,具体可以在添加钠精制剂之前先用ICP等手段检测获得氯化锂清液中的钠质量之后,再计算得到钠精制剂的加入量。Among them, the main function of the sodium concentrate preparation is to deeply remove the residual impurity sodium in the lithium chloride supernatant. According to a preferred embodiment of the present invention, the sodium concentrate preparation may be Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 , and the sodium concentrate preparation is added in an amount of 25 to 30 times the sodium mass in the lithium chloride supernatant. For example, specifically, the amount of sodium in the lithium chloride supernatant can be determined by ICP or the like before adding the sodium concentrate preparation, and then the amount of the sodium concentrate preparation added can be calculated.
优选地,在本步骤中,需控制反应温度为40~95℃且反应时间为2~8h,具体可以先将氯化锂清液加热至上述反应温度之后再加入钠精制剂进行反应,并且在反应后利用孔径为0.5~1μm的微滤膜进行过滤。其中,所得高浓度氯化锂溶液中的钠离子浓度低于0.02g/L。Preferably, in this step, the reaction temperature is controlled to be 40 to 95 ° C and the reaction time is 2 to 8 h. Specifically, the lithium chloride supernatant may be heated to the above reaction temperature, and then the sodium refined preparation is added for the reaction, and After the reaction, filtration was carried out using a microfiltration membrane having a pore diameter of 0.5 to 1 μm. Among them, the sodium ion concentration in the obtained high-concentration lithium chloride solution is less than 0.02 g/L.
步骤F:Step F:
最后,将高浓度氯化锂溶液烘干后得到无水氯化锂。Finally, the high concentration lithium chloride solution is dried to obtain anhydrous lithium chloride.
具体地,可以将高浓度氯化锂溶液置于钛坩埚内并在烘炉内于200~250℃下烘干,即可得到电池级标准的无水氯化锂。Specifically, a high-concentration lithium chloride solution can be placed in a titanium crucible and dried in an oven at 200 to 250 ° C to obtain a battery-grade standard anhydrous lithium chloride.
下面结合示例对本发明含锂废液制备无水氯化锂的方法作进一步说明。The method for preparing anhydrous lithium chloride of the lithium-containing waste liquid of the present invention will be further described below with reference to examples.
示例1:Example 1:
取含锂废液500mL,其中,该含锂废液为医药中间体的生产过程中产生的含锂废液,并且该含锂废液中的锂离子浓度为25g/L、氯离子浓度为150g/L、钠离子浓度10g/L、硫酸根离子浓度为3g/L、镁离子浓度为0.1g/L、钙离子浓度为0.2g/L、钾离子浓度为0.01g/L。Taking 500 mL of lithium-containing waste liquid, wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate, and the lithium ion concentration in the lithium-containing waste liquid is 25 g/L, and the chloride ion concentration is 150 g. /L, sodium ion concentration 10 g / L, sulfate ion concentration 3 g / L, magnesium ion concentration 0.1 g / L, calcium ion concentration 0.2 g / L, potassium ion concentration 0.01 g / L.
向上述含锂废液中加入质量浓度为10%的双氧水并在常温下搅拌反应20min;再加入浓度为50g/L的氯化钡溶液,经搅拌使硫酸根离子沉淀,过滤得到母液;向所得母液中加入浓度为150g/L的碳酸钠溶液,并在30℃搅拌反应50min,过滤除去微量的钙离子、镁离子、钡离子,得到精制母液;将精制
母液蒸发至接近共饱和点并析出大量的氯化钠和氯化钾固体,过滤除去氯化钠和氯化钾固体,得到氯化锂清液;将氯化锂清液加热至50℃,再加入15g钠精制剂并搅拌反应2h,之后经0.5μm微滤膜过滤,得到高纯度氯化锂溶液;将所得氯化锂溶液置于钛坩埚内并于烘炉内在200℃下烘干得到电池级无水氯化锂。Adding 10% by mass of hydrogen peroxide to the above lithium-containing waste liquid and stirring the reaction at normal temperature for 20 minutes; adding a cerium chloride solution having a concentration of 50 g/L, and precipitating the sulfate ion by stirring, and filtering to obtain a mother liquid; A sodium carbonate solution having a concentration of 150 g/L was added to the mother liquor, and the reaction was stirred at 30 ° C for 50 min, and a trace amount of calcium ions, magnesium ions, and cesium ions were removed by filtration to obtain a purified mother liquid;
The mother liquor is evaporated to near the point of co-saturation and a large amount of sodium chloride and potassium chloride solids are precipitated, and the sodium chloride and potassium chloride solids are removed by filtration to obtain a lithium chloride supernatant; the lithium chloride supernatant is heated to 50 ° C, and then 15 g of sodium essence preparation was added and stirred for 2 h, and then filtered through a 0.5 μm microfiltration membrane to obtain a high-purity lithium chloride solution; the obtained lithium chloride solution was placed in a titanium crucible and dried in an oven at 200 ° C to obtain a battery. Grade anhydrous lithium chloride.
示例2:Example 2:
取含锂废液500mL,其中,该含锂废液为医药中间体的生产过程中产生的含锂废液,并且该含锂废液中的锂离子浓度为30g/L、氯离子浓度为120g/L、钠离子浓度8g/L、硫酸根离子浓度为4g/L,镁离子浓度为2g/L、钙离子浓度为0.5g/L、钾离子浓度为0.1g/L。Taking 500 mL of lithium-containing waste liquid, wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in the production process of the pharmaceutical intermediate, and the lithium ion concentration in the lithium-containing waste liquid is 30 g/L, and the chloride ion concentration is 120 g. /L, sodium ion concentration 8 g / L, sulfate ion concentration 4 g / L, magnesium ion concentration 2 g / L, calcium ion concentration 0.5 g / L, potassium ion concentration 0.1 g / L.
向上述含锂废液中加入质量浓度为50%的双氧水并在常温下搅拌反应50min;再加入浓度为200g/L的氯化钡溶液,经搅拌使硫酸根离子沉淀,过滤得到母液;向所得母液中加入浓度为130g/L的碳酸钠溶液,并在60℃搅拌反应120min,过滤除去微量的钙离子、镁离子、钡离子,得到精制母液;将精制母液蒸发至接近共饱和点并析出大量的氯化钠和氯化钾固体,过滤除去氯化钠和氯化钾固体,得到氯化锂清液;将氯化锂清液加热至75℃,再加入7.5g钠精制剂并搅拌反应6h,之后经0.5μm微滤膜过滤,得到高纯度氯化锂溶液;将所得氯化锂溶液置于钛坩埚内并于烘炉内在250℃下烘干得到电池级无水氯化锂。Adding 50% by mass of hydrogen peroxide to the above lithium-containing waste liquid and stirring the reaction at normal temperature for 50 min; adding a cerium chloride solution having a concentration of 200 g/L, and precipitating the sulfate ion by stirring, and filtering to obtain a mother liquid; A sodium carbonate solution having a concentration of 130 g/L was added to the mother liquor, and the reaction was stirred at 60 ° C for 120 min, and a trace amount of calcium ions, magnesium ions, and cesium ions were removed by filtration to obtain a purified mother liquid; the refined mother liquid was evaporated to near the co-saturation point and a large amount of precipitate was precipitated. Solid sodium chloride and potassium chloride, filtered to remove solids of sodium chloride and potassium chloride to obtain a clear lithium chloride solution; the lithium chloride supernatant was heated to 75 ° C, and then 7.5 g of sodium fine preparation was added and stirred for 6 h. After that, it was filtered through a 0.5 μm microfiltration membrane to obtain a high-purity lithium chloride solution; the obtained lithium chloride solution was placed in a titanium crucible and dried in an oven at 250 ° C to obtain a battery-grade anhydrous lithium chloride.
示例3:Example 3:
取含锂废液500mL,其中,该含锂废液为医药中间体的生产过程中产生的含锂废液,并且该含锂废液中的锂离子浓度为20g/L、氯离子浓度为100g/L、钠离子浓度12g/L、硫酸根离子浓度为2g/L,镁离子浓度为0.5g/L、钙离子浓
度为4g/L、钾离子浓度为0.2g/L。Taking 500 mL of lithium-containing waste liquid, wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate, and the lithium ion concentration in the lithium-containing waste liquid is 20 g/L, and the chloride ion concentration is 100 g. /L, sodium ion concentration 12g / L, sulfate ion concentration 2g / L, magnesium ion concentration of 0.5g / L, calcium ion concentrated
The degree was 4 g/L and the potassium ion concentration was 0.2 g/L.
向上述含锂废液中加入质量浓度为30%的双氧水并在常温下搅拌反应50min;再加入浓度为100g/L的氯化钡溶液,经搅拌使硫酸根离子沉淀,过滤得到母液;向所得母液中加入浓度为160g/L的碳酸钠溶液,并在40℃搅拌反应240min,过滤除去微量的钙离子、镁离子、钡离子,得到精制母液;将精制母液蒸发至接近共饱和点并析出大量的氯化钠和氯化钾固体,过滤除去氯化钠和氯化钾固体,得到氯化锂清液;将氯化锂清液加热至65℃,再加入5g钠精制剂并搅拌反应8h,之后经0.5μm微滤膜过滤,得到高纯度氯化锂溶液;将所得氯化锂溶液置于钛坩埚内并于烘炉内在220℃下烘干得到电池级无水氯化锂。Adding 30% by mass of hydrogen peroxide to the lithium-containing waste liquid and stirring the reaction at normal temperature for 50 min; adding a cerium chloride solution having a concentration of 100 g/L, and precipitating the sulfate ion by stirring, and filtering to obtain a mother liquid; A sodium carbonate solution having a concentration of 160 g/L was added to the mother liquor, and the reaction was stirred at 40 ° C for 240 min, and a trace amount of calcium ions, magnesium ions, and cesium ions were removed by filtration to obtain a purified mother liquid; the refined mother liquid was evaporated to near the co-saturation point and a large amount was precipitated. Solid sodium chloride and potassium chloride, filtered to remove solids of sodium chloride and potassium chloride to obtain a clear lithium chloride solution; the lithium chloride supernatant was heated to 65 ° C, and then 5 g of sodium fine preparation was added and stirred for 8 h. Then, it was filtered through a 0.5 μm microfiltration membrane to obtain a high-purity lithium chloride solution; the obtained lithium chloride solution was placed in a titanium crucible and dried in an oven at 220 ° C to obtain a battery-grade anhydrous lithium chloride.
综上所述,本发明的利用含锂废液制备无水氯化锂的方法具有以下优点:1)工艺简单、生产成本低;2)锂回收率高;3)所制备的无水氯化锂可达电池级标准;4)所采用的原料为医药中间体生产过程中产生的含锂废液,原料成本低;5)该法属环境友好型,环保压力小。In summary, the method for preparing anhydrous lithium chloride by using lithium-containing waste liquid has the following advantages: 1) simple process and low production cost; 2) high lithium recovery rate; 3) anhydrous chlorination prepared Lithium can reach the battery level standard; 4) The raw materials used are lithium-containing waste liquid produced during the production of pharmaceutical intermediates, and the raw material cost is low; 5) The method is environmentally friendly and has low environmental protection pressure.
本发明并不局限于前述的具体实施方式。本发明扩展到任何在本说明书中披露的新特征或任何新的组合,以及披露的任一新的方法或过程的步骤或任何新的组合。
The invention is not limited to the specific embodiments described above. The invention extends to any new feature or any new combination disclosed in this specification, as well as any novel method or process steps or any new combination disclosed.
Claims (10)
- 一种利用含锂废液制备无水氯化锂的方法,其特征在于,所述含锂废液中至少含有锂离子、钙离子、镁离子、钠离子、钾离子、硫酸根离子和氯离子,所述方法包括以下步骤:A method for preparing anhydrous lithium chloride by using lithium-containing waste liquid, characterized in that the lithium-containing waste liquid contains at least lithium ions, calcium ions, magnesium ions, sodium ions, potassium ions, sulfate ions and chloride ions The method includes the following steps:A、向所述含锂废液中加入双氧水,以去除残余有机相;A, adding hydrogen peroxide to the lithium-containing waste liquid to remove residual organic phase;B、再加入氯化钡或氯化钡溶液并且在反应后过滤得到母液;B, further adding barium chloride or barium chloride solution and filtering after the reaction to obtain a mother liquor;C、向所述母液中加入碳酸钠或碳酸钠溶液并且在反应后过滤得到精制母液;C, adding sodium carbonate or sodium carbonate solution to the mother liquor and filtering to obtain a refined mother liquor after the reaction;D、将所述精制母液蒸发浓缩至析出氯化钠和氯化钾固体并过滤除去所述氯化钠和氯化钾固体,得到氯化锂清液;D, the refined mother liquid is concentrated by evaporation to precipitate sodium chloride and potassium chloride solids and filtered to remove the sodium chloride and potassium chloride solids to obtain a lithium chloride clear solution;E、向所述氯化锂清液中加入钠精制剂,搅拌反应后过滤得到高浓度氯化锂溶液;E, adding a sodium fine preparation to the lithium chloride clear solution, stirring the reaction and filtering to obtain a high concentration lithium chloride solution;F、将所述高浓度氯化锂溶液烘干后得到无水氯化锂。F. Drying the high concentration lithium chloride solution to obtain anhydrous lithium chloride.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,所述含锂废液为医药中间体的生产过程中产生的含锂废液,其中,所述含锂废液中的锂离子浓度为10~35g/L、氯离子浓度为80~200g/L、钠离子浓度1~15g/L、硫酸根离子浓度为0.5~5g/L、镁离子浓度为0.1~2g/L、钙离子浓度为0.2~4g/L、钾离子浓度为0.01~0.2g/L。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein the lithium-containing waste liquid is a lithium-containing waste liquid produced in a production process of a pharmaceutical intermediate, wherein The lithium ion concentration in the lithium-containing waste liquid is 10 to 35 g/L, the chloride ion concentration is 80 to 200 g/L, the sodium ion concentration is 1 to 15 g/L, the sulfate ion concentration is 0.5 to 5 g/L, and the magnesium ion concentration is 0.1 to 2 g/L, a calcium ion concentration of 0.2 to 4 g/L, and a potassium ion concentration of 0.01 to 0.2 g/L.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤A中,所述双氧水的质量浓度为10~50%,反应时间为10~50min。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step A, the hydrogen peroxide has a mass concentration of 10 to 50% and a reaction time of 10 to 50 minutes.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤B中,所述氯化钡溶液的浓度为50~200g/L,反应时间为30~120min。 The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step B, the concentration of the ruthenium chloride solution is 50 to 200 g/L, and the reaction time is 30 ~. 120min.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤C中,所述碳酸钠溶液的浓度为50~200g/L,反应温度为20~60℃,反应时间为30~240min。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step C, the sodium carbonate solution has a concentration of 50 to 200 g/L, and the reaction temperature is 20 to 60. °C, the reaction time is 30-240min.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤D中,所述氯化锂清液中的钠离子浓度低于1g/L,钾离子浓度低于0.5g/L。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step D, the sodium ion concentration in the lithium chloride supernatant is less than 1 g/L, and the potassium ion The concentration is below 0.5g/L.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤E中,所述钠精制剂为Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3并且所述钠精制剂的加入量为所述氯化锂清液中钠质量的25~30倍。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step E, the sodium fine preparation is Li 1.3 Zr 0.8 Ce 0.4 Si 0.5 Al 0.3 (PO 4 ) 3 and the sodium fine preparation is added in an amount of 25 to 30 times the mass of the sodium in the lithium chloride supernatant.
- 根据权利要求7所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤E中,反应温度为40~95℃,反应时间为2~8h,并且在反应后利用孔径为0.5~1μm的微滤膜进行过滤。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 7, wherein in the step E, the reaction temperature is 40 to 95 ° C, the reaction time is 2 to 8 hours, and the reaction is utilized after the reaction. The microfiltration membrane having a pore diameter of 0.5 to 1 μm was filtered.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤E中,所述高浓度氯化锂溶液中的钠离子浓度低于0.02g/L。The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step E, the sodium ion concentration in the high-concentration lithium chloride solution is less than 0.02 g/L.
- 根据权利要求1所述的利用含锂废液制备无水氯化锂的方法,其特征在于,在步骤F中,将所述高浓度氯化锂溶液置于钛坩埚内并在烘炉内于200~250℃下烘干。 The method for preparing anhydrous lithium chloride by using a lithium-containing waste liquid according to claim 1, wherein in the step F, the high-concentration lithium chloride solution is placed in a titanium crucible and is in an oven. Dry at 200 ~ 250 °C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610257026.3 | 2016-04-22 | ||
CN201610257026.3A CN105836767B (en) | 2016-04-22 | 2016-04-22 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017181759A1 true WO2017181759A1 (en) | 2017-10-26 |
Family
ID=56588969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2017/072970 WO2017181759A1 (en) | 2016-04-22 | 2017-02-06 | Method for manufacturing anhydrous lithium chloride using lithium-containing wastewater |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN105836767B (en) |
WO (1) | WO2017181759A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105836767B (en) * | 2016-04-22 | 2017-10-31 | 天齐锂业股份有限公司 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
CN106565956B (en) * | 2016-10-21 | 2018-09-28 | 天津科技大学 | By-product slurry comprehensive reutilization method in a kind of polyphenylene sulfide production process |
CN108220625B (en) * | 2016-12-21 | 2020-08-14 | 天齐锂业股份有限公司 | Method for recovering lithium from lithium-containing waste liquid |
CN107954455A (en) * | 2017-12-06 | 2018-04-24 | 天齐锂业股份有限公司 | A kind of method for preparing battery-level lithium carbonate using waste liquid containing lithium |
CN108264063B (en) * | 2018-01-13 | 2019-12-24 | 安徽金禾实业股份有限公司 | Method for extracting salt from sewage in maltol production |
CN109574047B (en) * | 2018-10-22 | 2021-03-12 | 天齐锂业(江苏)有限公司 | Method for recovering high-purity efavirenz and lithium chloride from medical lithium-containing waste liquid |
CN110304642B (en) * | 2019-08-15 | 2021-10-29 | 赣州有色冶金研究所有限公司 | Method for removing impurity sodium in lithium chloride and preparation method of battery-grade anhydrous lithium chloride |
CN111017965B (en) * | 2019-11-29 | 2022-06-10 | 湖北金泉新材料有限公司 | Preparation method of industrial-grade lithium chloride |
CN115465932A (en) * | 2022-10-24 | 2022-12-13 | 中化学朗正环保科技有限公司 | Method for removing sulfate ions in calcium salt concentrated solution |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1483673A (en) * | 2003-07-28 | 2004-03-24 | 东北大学 | Process for purifying lithium chloride |
US6921522B2 (en) * | 1998-07-16 | 2005-07-26 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
CN101125667A (en) * | 2007-09-18 | 2008-02-20 | 四川省射洪锂业有限责任公司 | Method for preparing battery-stage anhydrous lithium chloride |
CN102874849A (en) * | 2012-09-11 | 2013-01-16 | 奉新赣锋锂业有限公司 | Method for producing anhydrous lithium chloride special for electrolyzing by using lithium recovered from lithium-containing pharmaceutical waste water |
CN105836767A (en) * | 2016-04-22 | 2016-08-10 | 天齐锂业股份有限公司 | Method for preparing anhydrous lithium chloride by lithium-containing liquid waste |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1781847A (en) * | 2004-11-24 | 2006-06-07 | 中国石化集团巴陵石油化工有限责任公司 | Process for producing lithium chloride using waste liquid containing lithium |
CN103738984B (en) * | 2013-12-26 | 2016-02-24 | 江苏久吾高科技股份有限公司 | A kind of extracting method of bitten lithium chloride and device |
CN105152187A (en) * | 2015-07-23 | 2015-12-16 | 韦海棉 | Method for extracting lithium chloride from high lithium salt lake brine |
-
2016
- 2016-04-22 CN CN201610257026.3A patent/CN105836767B/en active Active
-
2017
- 2017-02-06 WO PCT/CN2017/072970 patent/WO2017181759A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6921522B2 (en) * | 1998-07-16 | 2005-07-26 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
CN1483673A (en) * | 2003-07-28 | 2004-03-24 | 东北大学 | Process for purifying lithium chloride |
CN101125667A (en) * | 2007-09-18 | 2008-02-20 | 四川省射洪锂业有限责任公司 | Method for preparing battery-stage anhydrous lithium chloride |
CN102874849A (en) * | 2012-09-11 | 2013-01-16 | 奉新赣锋锂业有限公司 | Method for producing anhydrous lithium chloride special for electrolyzing by using lithium recovered from lithium-containing pharmaceutical waste water |
CN105836767A (en) * | 2016-04-22 | 2016-08-10 | 天齐锂业股份有限公司 | Method for preparing anhydrous lithium chloride by lithium-containing liquid waste |
Also Published As
Publication number | Publication date |
---|---|
CN105836767B (en) | 2017-10-31 |
CN105836767A (en) | 2016-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017181759A1 (en) | Method for manufacturing anhydrous lithium chloride using lithium-containing wastewater | |
AU2021204689B2 (en) | Methods for treating lithium-containing materials | |
CN106365180B (en) | A kind of technique that industrial grade methanol is extracted in the ore deposit from lithium | |
KR20170088873A (en) | Production of Lithium Hydroxide | |
WO2018072739A1 (en) | Method for comprehensive recycling of by-product slurry during polyphenylene sulfide production | |
CN110550646A (en) | preparation method of cesium sulfate and rubidium sulfate | |
CN103014378A (en) | Vanadium liquid purification method | |
CN109534369B (en) | Membrane integrated lithium chloride preparation equipment and method thereof | |
CN102633293B (en) | Method for refining multistage circulation evaporation-free copper sulfate | |
JP2016056434A (en) | Separation method of nickel from nickel sludge | |
CN102051481A (en) | Method for separating calcium and magnesium in hydrochloric acid soluble salt system | |
CN103012509B (en) | Method of separating and purifying sucrose-6-acetate mother liquor by salt fractionation | |
CN106629809B (en) | Method for purifying coarse scandium oxide | |
CN104447529B (en) | Method for extracting and purifying 3,6-matrigon | |
RU2537626C2 (en) | Method of obtaining potassium alum | |
RU2448175C1 (en) | Method of processing manganese-containing material | |
CN115197101A (en) | Method for preparing urea by recycling vanadium precipitation wastewater | |
CN116283552A (en) | Refining method of oxalic acid | |
CN113044866A (en) | Method for preparing aluminum sulfate from aluminum-containing acid treatment liquid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17785245 Country of ref document: EP Kind code of ref document: A1 |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17785245 Country of ref document: EP Kind code of ref document: A1 |