WO2017181759A1

WO2017181759A1 - Method for manufacturing anhydrous lithium chloride using lithium-containing wastewater

Info

Publication number: WO2017181759A1
Application number: PCT/CN2017/072970
Authority: WO
Inventors: 曹乃珍; 高洁; 肇巍; 樊平; 张炳元; 杜明泽; 赵莉
Original assignee: 天齐锂业股份有限公司
Priority date: 2016-04-22
Filing date: 2017-02-06
Publication date: 2017-10-26
Also published as: CN105836767B; CN105836767A

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

Method for preparing anhydrous lithium chloride by using lithium-containing waste liquid

Technical field

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.

Background technique

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.

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.

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.

Summary of the invention

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.

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, adding hydrogen peroxide to the lithium-containing waste liquid to remove residual organic phase;

B, further adding barium chloride or barium chloride solution and filtering after the reaction to obtain a mother liquor;

C, adding sodium carbonate or sodium carbonate solution to the mother liquor and filtering to obtain a refined mother liquor after the reaction;

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, 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. Drying the high concentration lithium chloride solution to obtain anhydrous lithium chloride.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

detailed description

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.

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.

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.

The method for preparing anhydrous lithium chloride using the lithium-containing waste liquid of the present invention will be described in detail below.

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.

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.

Step A:

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.

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.

Step B:

Further, a solution of ruthenium chloride or ruthenium chloride is added and after the reaction, it is filtered to obtain a mother liquid.

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.

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.

Step C:

A sodium carbonate or sodium carbonate solution is added to the mother liquor and filtered to obtain a refined mother liquor.

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.

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.

Step D:

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;

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.

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.

Step E:

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.

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.

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.

Step F:

Finally, the high concentration lithium chloride solution is dried to obtain anhydrous lithium chloride.

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.

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.

Example 1:

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.

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.

Example 2:

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.

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.

Example 3:

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.

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.

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.

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

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, adding hydrogen peroxide to the lithium-containing waste liquid to remove residual organic phase;

B, further adding barium chloride or barium chloride solution and filtering after the reaction to obtain a mother liquor;

C, adding sodium carbonate or sodium carbonate solution to the mother liquor and filtering to obtain a refined mother liquor after the reaction;

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, 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. Drying the high concentration lithium chloride solution to obtain anhydrous lithium chloride.
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.
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.
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.
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.
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.
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.
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.
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.
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.