CN115198094A - Process method for removing cadmium from cobalt sulfate solution through binary solvent synergistic extraction - Google Patents

Process method for removing cadmium from cobalt sulfate solution through binary solvent synergistic extraction Download PDF

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CN115198094A
CN115198094A CN202210851336.3A CN202210851336A CN115198094A CN 115198094 A CN115198094 A CN 115198094A CN 202210851336 A CN202210851336 A CN 202210851336A CN 115198094 A CN115198094 A CN 115198094A
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cadmium
cobalt sulfate
solution
binary solvent
sulfate solution
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王红忠
曹栋强
龚丽锋
初彦兴
黄飞中
李潮军
仝良玉
罗瑞平
康亮
乔自鹏
邱颖
张璐璐
方聪
罗海川
王海斌
陈子杨
龙彩云
熊绍翔
姜俊彩
刘佳岐
戴春艳
邵蒙阳
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Anhui Gepai Lithium Battery Cycle Technology Co ltd
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Anhui Gepai Lithium Battery Cycle Technology Co ltd
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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
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40Mixtures
    • C22B3/402Mixtures of acyclic or carbocyclic compounds of different types
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00Obtaining cadmium
    • C22B17/04Obtaining cadmium by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • 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

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Abstract

The invention relates to the field of cobalt salt production, in particular to a process method for recovering cadmium from a cobalt sulfate solution by using binary solvent for synergistic extraction. The invention relates to a process for removing cadmium in a cobalt sulfate solution by utilizing binary extraction solvent for synergistic extraction, which comprises the following steps: synthesizing a mixture of different Deep Eutectic Solvents (DES), cadmium-containing cobalt sulfate solution and a proper amount of water, stirring the mixture in a magnetic stirrer with a coating at 50 ℃ and pH =3 at a rotating speed of 1000rpm for 30min to allow cadmium to enter an organic phase, and performing cadmium back extraction by using sulfuric acid at a ratio of 4 on the organic phase at the upper layer of the solution after the cadmium is removed; 1. the invention realizes the separation and recovery of heavy metal ions only by utilizing a binary extractant synergistic extraction system, solves the breakthrough in the aspect of cadmium separation and recovery, and finally realizes the heavy metal in the cobalt sulfate wastewaterAnd separating and recovering metal ions. Compared with the cadmium removal by precipitation, the process does not generate toxic H 2 And S, environmental pollution is reduced.

Description

Process method for removing cadmium from cobalt sulfate solution through binary solvent synergistic extraction
Technical Field
The invention relates to the technical field of impurity removal of a cobalt sulfate solution, in particular to a process method for removing cadmium from the cobalt sulfate solution through synergistic extraction of a binary solvent.
Background
The presence of a small amount of cadmium in the cobalt solution seriously affects the quality of the cobalt solution, so that products produced by using the solution, such as ternary precursors, nickel salt products and cobalt salt products, can not meet the use requirements.
Cadmium is a toxic pollutant, and direct discharge causes great pollution to the environment, so that development of a cadmium removal technology is very important. The related art adopts ion exchange, membrane separation technology, adsorption method, precipitation method and the like. Wherein the ion exchange and membrane separation technology has the defects of complex operation process and high operation cost; adsorption processes have limited adsorption capacity.
Therefore, it is required to develop a method for removing cadmium from a cobalt solution, which has a high cadmium removal rate.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a process method for removing cadmium from a cobalt sulfate solution by using binary solvent for synergistic extraction, the removal rate of cadmium is high, and the specific scheme is as follows:
a process method for removing cadmium from a cobalt sulfate solution by binary solvent synergistic extraction comprises the following steps: mixing and stirring an extracting agent, cadmium-containing cobalt sulfate stock solution and water, and obtaining an upper solution which is a cadmium-containing organic phase; wherein the pH value of the cadmium-containing cobalt sulfate stock solution is 2.8-3; the reaction time is 30min; adjusting the pH =3 of the solution during reaction, wherein the extractant adopts one or the combination of DES1 or DES2, and DES1 is a mixture of choline chloride and lactic acid; the DES2 is a mixture of choline chloride and malonic acid, and the volume ratio of the addition amount of the extracting agent to the cadmium-containing cobalt sulfate stock solution is not less than 1:1.
The extractant adopts DES, DES1, DES2 or combination of DES1 and DES 2.
The mass concentration of cadmium element in the cadmium-containing cobalt sulfate stock solution is less than or equal to 0.1g/L, the mass concentration of nickel element is 0.2g/L-0.5g/L, and the mass concentration of cobalt element is more than or equal to 120g/L. Too high a cobalt content results in a loss of quality during the precipitation.
The volume ratio of the extracting agent to the water is 1:1.
The preparation method of the DES1 comprises the following steps: choline chloride and lactic acid were mixed thoroughly and stirred at 50 ℃ for 8 hours. The mass ratio of choline chloride to lactic acid in DES1 synthesis is 1:2, wherein the choline chloride is 21.773g, and the lactic acid is 28.064g.
The preparation method of the DES2 comprises the following steps: choline chloride and propylene glycol fully mixed at 50 degrees C under stirring for 8 hours. The mass ratio of the synthesized choline chloride and the malonic acid substances of DES2 is 1;1, choline chloride 12.459g and malonic acid 9.295g.
The stirring speed was 1000rpm.
Separating the water phase of the organic phase containing cadmium, further carrying out sulfuric acid back extraction on the organic phase to recover cadmium, wherein the mass ratio of sulfuric acid to the organic phase is 4:1.
The extraction liquid mixture has synergistic effect, liquid-liquid phase balance at low temperature is favorable for separation and extraction, DES1 is a cadmium ion extractant capable of rapidly reacting at low temperature, the extraction efficiency of DES2 is superior to DES1, and the extraction rate at low temperature can be further improved to be close to 100% under the combined action of the DES1 and the DES.
The method utilizes the synergistic reaction of the extractant and cadmium, completely mixes the synthesized binary extractant with the raw material liquid and water, leads the extractant and the cadmium to react and extract into an organic phase, can remove the cadmium in the solution, and has the potential of large-scale application.
The reaction process of the invention has lower requirements on equipment and instruments, the solution preparation and synthesis are simple and efficient, the regulating capability is strong, the maintenance cost is low, and the loss of cobalt element in the cadmium removal process is less; and no toxic gas hydrogen sulfide is generated in the reaction process, so that a tail gas treatment device in the later stage is reduced, and the method is more environment-friendly. The extractant and the stock solution of the cobalt sulfate are in contact reaction fully, and the reaction efficiency is high. Is beneficial to large-scale industrial production.
The invention utilizes the synergistic action of a binary extractant to extract cadmium ions in the raw material liquid, and then cadmium in an organic phase is obtained by back extraction; the method has the advantages of high reaction speed, low cost, easy control and large-scale production potential.
Drawings
FIG. 1 is a schematic flow chart of a method for removing cadmium from a cobalt sulfate solution in example 1 of the present invention;
FIG. 2 is a schematic flow chart of the cadmium removal principle of the resin in comparative example 1 of the present invention.
Detailed Description
The concept and the resulting technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "a specific example," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above-described techniques do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
A preparation stage:
s1, adding a cobalt sulfate solution into a beaker to serve as a stock solution;
s2, measuring the pH value of the stock solution;
s3, adjusting the pH value of the solution;
s4, preparing DES1, and fully mixing choline chloride and lactic acid, and stirring for 8 hours at 50 ℃; the mass ratio of choline chloride to lactic acid in DES1 synthesis is 1:2, wherein choline chloride is 21.773g, and lactic acid is 28.064g;
s5, preparing DES2, and fully mixing choline chloride and malonic acid for 8 hours at 50 ℃; the mass ratio of the synthesized choline chloride and the malonic acid substances of DES2 is 1;1, the choline chloride is 12.459g, and the malonic acid is 9.295g;
s6, controlling the rotating speed to be 1000rpm in the stirring process;
wherein the pH of the solution in step S3 is 3;
the volume ratio of the organic phase to the aqueous phase in step S4 is 1:1;
the embodiment is a process method for removing cadmium from a cobalt sulfate solution by binary solvent synergistic extraction, which comprises the following steps:
s1, selecting a cobalt raw material solution, wherein the mass concentration of each element of the cobalt raw material solution in the embodiment is shown in a table 1;
TABLE 1 Mass concentrations of respective elements of cobalt raw material liquid in this example
Element(s) Co Cd Ni pH
Mass concentration (g/L) 121.01 0.055 0.325 2.97
S2, the reaction schematic diagram of the embodiment is shown in figure 1, and the stock solution, the binary extractant and water are mixed in a beaker and then stirred for reaction; after the reaction is finished, the organic phase and the water phase are separated, and the cadmium can be recovered by further sulfuric acid back extraction of the organic phase (the mass ratio of sulfuric acid to the organic phase is 4:1).
The stock solution had a pH of 2.97 (here the pH was the workshop stock solution cobalt sulphate, which was adjusted to pH 3 during the experiment); the reaction stirring speed is 1000rpm;
the reaction time was 30min.
The mass concentrations of the elements in the cadmium-removing liquid of this example are shown in Table 2.
TABLE 2 Mass concentrations of the elements in the DES1 extractant cadmium-removing solution of this example
Element(s) Co Cd pH Extraction rate
Mass concentration (g/L) 120.42 0.0007 2.82 98.7%
TABLE 3 Mass concentrations of the elements in the DES2 extractant cadmium-removing solution of this example
Element(s) Co Cd pH Extraction rate
Mass concentration (g/L) 120.01 0.0004 2.91 99.1%
TABLE 3 Mass concentrations of the elements in the DES1 and DES2 synergistic extractant cadmium removal solution of this example
Element(s) Co Cd pH Extraction rate
Mass concentration (g/L) 119.84 0.0001 2.92 99.8%
Examples 2-3, which are presented to demonstrate the effect of the ratio of feed to extract, are shown in Table 4
TABLE 4
Figure BDA0003752613410000051
Comparative example 1
The comparative example is a resin method for removing cadmium, and comprises the steps as shown in figure 2:
s1, introducing a cadmium-containing cobalt sulfate solution into a cadmium-removing resin column through a peristaltic pump;
s2, measuring the content of Cd in the cadmium-removed liquid in real time;
s3, the mass concentration of each element in the cadmium-removing liquid of the comparative example is shown in Table 5
TABLE 5
Sample numbering Filtration sample volume (L) Cd content PH
1 1.2 0.0031 1.22
2 2.4 0.0031 1.37
3 3.6 0.0046 2.18
4 4.8 0.0051 2.38
5 6.0 0.0052 2.57
S4, emptying the solution in the resin tank after the resin is saturated, and washing the resin with clear water;
s5, backwashing the resin, and washing the resin with water until the pH value is neutral by using alkali (sodium hydroxide solution) and acid (sulfuric acid solution).
The above-mentioned embodiments are only used for explaining the inventive concept of the present invention, and do not limit the protection of the claims of the present invention, and any insubstantial modifications of the present invention using this concept shall fall within the protection scope of the present invention.

Claims (10)

1. A process method for removing cadmium from a cobalt sulfate solution by binary solvent synergistic extraction is characterized by comprising the following steps: mixing and stirring an extracting agent, cadmium-containing cobalt sulfate stock solution and water, wherein the upper-layer solution is a cadmium-containing organic phase; wherein the pH value of the cadmium-containing cobalt sulfate stock solution is 2.8-3; the reaction time is 30min; the extractant adopts one or the combination of DES1 or DES2, and DES1 is a mixture of choline chloride and lactic acid; the DES2 is a mixture of choline chloride and malonic acid, and the volume ratio of the addition amount of the extracting agent to the cadmium-containing cobalt sulfate stock solution is not less than 1:1.
2. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: the extractant adopts a combination of DES1 and DES 2.
3. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: the mass concentration of cadmium element in the cadmium-containing cobalt sulfate stock solution is less than or equal to 0.1g/L, the mass concentration of nickel element is 0.2g/L-0.5g/L, and the mass concentration of cobalt element is more than or equal to 120g/L.
4. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: the volume ratio of the extracting agent to the water is 1:1.
5. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: the preparation method of the DES1 comprises the following steps: choline chloride and lactic acid were mixed thoroughly and stirred at 50 ℃ for 8 hours.
6. The process of claim 5, wherein the binary solvent is selected from the group consisting of: the mass ratio of choline chloride to lactic acid is 1:2.
7. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: the preparation method of the DES2 comprises the following steps: choline chloride and malonic acid were mixed thoroughly and stirred for 8 hours at 50 ℃.
8. The process of claim 7, wherein the binary solvent is selected from the group consisting of: the mass ratio of choline chloride to malonic acid was 1:1.
9. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: the stirring speed was 1000rpm.
10. The process method for removing cadmium from cobalt sulfate solution by binary solvent synergistic extraction as claimed in claim 1, wherein: separating the water phase of the organic phase containing cadmium, further carrying out sulfuric acid back extraction on the organic phase to recover cadmium, wherein the mass ratio of sulfuric acid to the organic phase is 4:1.
CN202210851336.3A 2022-07-19 2022-07-19 Process method for removing cadmium from cobalt sulfate solution through binary solvent synergistic extraction Pending CN115198094A (en)

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CN115814768A (en) * 2022-12-28 2023-03-21 安徽格派锂电循环科技有限公司 Process method for preparing honeycomb-shaped recyclable magnetic biochar and applying honeycomb-shaped recyclable magnetic biochar to cadmium removal of sewage
CN116814990A (en) * 2023-08-31 2023-09-29 中国科学院过程工程研究所 Method for extracting and separating vanadium in vanadium-arsenic solution by utilizing hydrophobic eutectic solvent

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Application publication date: 20221018