CN113481367A - Method for selectively extracting and separating nickel and lithium - Google Patents

Method for selectively extracting and separating nickel and lithium Download PDF

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CN113481367A
CN113481367A CN202110741741.5A CN202110741741A CN113481367A CN 113481367 A CN113481367 A CN 113481367A CN 202110741741 A CN202110741741 A CN 202110741741A CN 113481367 A CN113481367 A CN 113481367A
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nickel
lithium
organic phase
extraction
compound
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CN113481367B (en
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张贵清
关文娟
陆瑾
曾理
李青刚
曹佐英
巫圣喜
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention discloses a method for selectively extracting and separating nickel and lithium, which comprises the steps of contacting an organic phase containing a synergistic extracting agent with a nickel and lithium mixed solution for extraction, enabling nickel to enter the organic phase, retaining lithium in a water phase, obtaining a lithium salt solution and a nickel-loaded organic phase, carrying out back extraction on the nickel-loaded organic phase by adopting an inorganic acid solution to obtain a nickel salt solution, realizing high-efficiency separation of nickel and lithium, and carrying out saponification treatment on the organic phase after the back extraction and then returning the organic phase to the extraction. The method has the characteristics of good nickel-lithium mutual separation effect, simple operation and easy realization of industrialization.

Description

Method for selectively extracting and separating nickel and lithium
Technical Field
The invention relates to the field of metal ion separation and purification, in particular to a method for selectively extracting and separating nickel and lithium.
Background
With the vigorous development of the new energy power automobile market, the ternary positive electrode material of the lithium ion battery becomes a mainstream product in the power lithium ion battery material market at present due to the characteristics of high energy density, excellent cycle performance and the like, and the market proportion is larger and larger. With the popularization of power automobiles, power batteries gradually enter a batch scrapping stage, and more discarded ternary lithium ion batteries are available in the future. The waste ternary lithium battery contains a large amount of metal resources such as lithium, nickel, cobalt, manganese and the like, and if the metal resources cannot be well recycled and utilized, the waste of the resources is caused, and the environment is also greatly damaged. Therefore, the method has very important significance for environmental protection and resource recycling by recycling valuable metals in the ternary cathode material.
The current main industrial method for recovering valuable metals nickel, cobalt, manganese and lithium from the anode material of the waste ternary battery is to introduce the elements into a solution by a pretreatment-acid leaching method, then to remove impurities from the leachate by precipitation, extraction and other methods, and to separate and obtain compounds of nickel, cobalt, manganese, lithium and the like, thereby realizing high-value utilization of the elements of nickel, cobalt, manganese, lithium and the like. The solvent extraction technology has the characteristics of high selectivity, high reaction speed, good separation effect, easiness in realizing continuous and automatic operation in the process and the like, and is a mainstream industrial production method for separating nickel, cobalt, manganese and lithium from each other and separating the valuable metals from other impurities at present. Since the extraction capacity of common organic phosphorus (phosphonic) acid extractants (such as P507, Cynex272, P204, etc.) to manganese and cobalt is far greater than that to nickel and lithium, the separation of manganese and cobalt from nickel and lithium is realized industrially by adopting the organic phosphorus (phosphonic) acid extractants to preferentially extract manganese and cobalt. For the separation of nickel and lithium, although the organic phosphorus (phosphonic) acid extractant can realize the preferential extraction of nickel and realize the separation of nickel and lithium (CN201811136229.2), the extraction and separation of nickel and lithium by adopting the extractant has the problems of more separation stages and high investment and operation cost because the mutual separation coefficient of nickel and lithium is smaller.
In order to solve the problem of low efficiency of extracting and separating nickel and lithium by using an organic phosphorus (phosphonic) acid extractant, CN201911380735.0 discloses a mixed extractant for separating lithium and nickel, wherein the mixed extractant is a mixture of a mono-substituted alkyl phenoxy carboxylic acid and a di-substituted phenoxy carboxylic acid, the mixed extractant has a high nickel and lithium separation coefficient, and can preferentially extract nickel to realize high-efficiency extraction and separation of nickel and lithium, but both organic matters as metal extractants are not reported to be applied in industry, and whether the extractant can meet industrial requirements needs to be observed.
Disclosure of Invention
The invention aims to overcome the defects of the existing nickel-lithium separation method and provide a high-efficiency synergic extraction separation method for separating nickel and lithium.
In order to solve the problem that the extraction separation coefficient of nickel and lithium is not ideal, the invention provides the following solution scheme through research:
a method for selectively extracting and separating nickel and lithium comprises the steps of mixing an aqueous phase to be separated containing nickel ions and lithium ions with an organic phase containing a combined extracting agent (also called a synergistic extracting agent) for extraction to obtain a nickel-enriched loaded organic phase and a lithium-enriched raffinate;
the combined extracting agent comprises a compound 1 and a compound 2; wherein, the compound 1 is at least one compound with the structural formula of formula 1; compound 2 is at least one compound having the structural formula of formula 2:
Figure BDA0003141685990000021
said R1、R2Independently is C6～12Alkyl or alkoxy of (a); m is H, Na, K, NH4Or Li;
R3is C6～12Alkyl group of (1).
Aiming at the problem of nickel and lithium extraction selectivity, the invention discovers that the nickel and lithium selective separation effect is not ideal by only adopting the compound 1, and the nickel and lithium selective separation effect is not basically possessed by only adopting the compound 2, but the nickel and lithium extraction performance is basically not possessed by the compound 2, but the nickel and the lithium extraction performance can generate a synergistic effect by combining the compound and the compound, the nickel extraction rate can be effectively and positively synergistically improved, the accompanying extraction of the lithium can be inhibited in a counter-synergistic manner, the nickel and lithium separation selectivity can be obviously improved, and the extraction separation coefficients of the nickel and the lithium can be improved.
In the present invention, the aqueous phase to be separated may be a solution containing nickel and lithium from any source, and the concentration of nickel and lithium therein is not required. But the concentration of Ni may be 0.1 to 55g/L for the sake of treatment efficiency and economy; the concentration of Li may be 0.1 to 20 g/L.
In the invention, the combination of the compound 1 and the compound 2 is the key for synergistically improving the extraction separation selectivity and the separation coefficient of the nickel and the lithium.
Preferably, in the formula 2, -COOR3Is located at the 4-position of the pyridine ring. The preferred structural formula is:
Figure BDA0003141685990000022
the research of the invention finds that on the basis of the combined synergy of the compound 1 and the compound 2, the ratio of the compound 1 and the compound 2 and the balance pH value in the extraction process are further controlled, so that the separation selectivity of nickel and lithium can be further synergistically improved.
The research of the invention finds that the compound shown in the formula 2 has no extraction and separation capability on nickel and lithium basically; the compound of formula 1 has certain extraction capacity for both nickel and lithium, and the extraction and separation effect of nickel-lithium is not ideal, however, the combination of formula 2 and formula 1 can unexpectedly produce excellent synergistic effect, and can significantly improve the extraction and separation selectivity of nickel and lithium.
Preferably, the molar ratio of the compound 1 to the compound 2 is 1: 1-1: 6; preferably 1:1 to 1: 4.
In the invention, the concentration of the compound 1 in the organic phase is 0.1-1.0 mol/L; preferably 0.1 to 0.5 mol/L.
In the invention, the organic phase also contains a diluent;
preferably, the diluent is sulfonated kerosene, No. 260 solvent oil, aviation kerosene, Escaid110, C8～13At least one of the higher alcohols of (1).
In the invention, the equilibrium pH value of the extraction process is 1.0-8.0.
In the present invention, the equilibrium pH of the extraction process can be controlled by controlling the pH of the aqueous phase to be separated and the saponification of the organic phase and the degree of saponification.
In the present invention, the organic phase may be unsaponifiable or saponified. When the organic phase is saponified, it may be obtained by mixing previously saponified Compound 1 with other components, or may be obtained by mixing unsaponifiable components and then saponifying them. The alkali liquor adopted in the saponification process is at least one of sodium hydroxide, potassium hydroxide, ammonia water and lithium hydroxide; the concentration of the alkali solution is, for example, 1.0-10.0 mol/L.
In the invention, when the organic phase is a saponified organic phase, the saponification degree is more than 0%, and preferably 10-90%; more preferably 50 to 90%.
In the present invention, the saponification degree of the organic phase means the saponification degree of Compound 1.
Preferably, the pH value of the water phase to be separated is 1.0-8.0; preferably 2.0 to 7.0;
in the invention, the extraction operation can be realized based on the existing means and equipment.
For example, the extraction process has an extraction stage number greater than or equal to 1; preferably 1-10 grades;
preferably, when the extraction stage number is more than or equal to 2 stages, the extraction mode is countercurrent extraction;
preferably, in the extraction process, the volume flow ratio of the organic phase to the aqueous phase feed liquid is 1/10-10/1.
In the present invention, means can be used to recover lithium from the raffinate and nickel from the loaded organic phase.
For example, stripping the loaded organic phase enriched with nickel with acid solution to obtain a stripping solution enriched with nickel;
preferably, the acid solution is an aqueous solution of at least one inorganic acid selected from sulfuric acid, nitric acid and hydrochloric acid;
preferably, H in the acid liquor+The concentration of (a) is 0.1-3.0 mol/L; more preferably 0.2 to 3M.
In the invention, the stripping stage number of the stripping process is more than or equal to 1 stage; preferably 1-10 grades.
Preferably, when the number of stripping stages is greater than or equal to 2, the stripping mode is preferably countercurrent stripping;
preferably, the volume flow ratio of the organic phase to the aqueous phase feed liquid in the back extraction process is 1/1-15/1.
According to the preferable scheme of the invention, before back extraction, the loaded organic phase can be washed in advance; the washing liquid for washing treatment is water or a low acid aqueous solution. Further preferably, the H of the aqueous solution of a low acid is H during washing+Molar amount of less than or equal to Li in the loaded organic phase+The molar amount of (c).
The invention discloses a preferable method for selectively extracting and separating nickel and lithium from a nickel and lithium mixed solution, which comprises the following steps:
first-step saponification: mixing an organic phase containing a synergistic extraction agent with an inorganic alkali aqueous solution to obtain a saponified organic phase;
the organic phase consists of a synergistic extractant and a diluent, the synergistic extractant is formed by compounding a compound shown in a formula 1-A and a compound shown in a formula 2-A, and the ratio of the total mole number of the compound shown in the formula 1-A to the total mole number of the compound shown in the formula 2-A is 1: 1-6.
Figure BDA0003141685990000041
The second step of extraction: and (3) contacting the saponified organic phase obtained in the first step with mixed feed liquid containing nickel and lithium ions to perform single-stage extraction or multi-stage countercurrent extraction, wherein nickel is preferentially extracted into the organic phase to obtain a nickel-negative organic phase and a lithium salt aqueous solution, so that the separation of nickel and lithium is realized.
The third step is back extraction: and washing the organic phase loaded with the nickel ions, mixing the washed organic phase with an inorganic acid aqueous solution, and performing single-stage or multi-stage countercurrent back extraction to obtain a nickel salt solution. After the reaction, the organic phase returns to the first saponification procedure for repeated use.
It should be noted that the negative nickel organic phase obtained in the second extraction step can be washed and then fed to the stripping step. The effect of the washing is to remove entrained lithium as well as co-extracted lithium from the loaded organic phase. The detergent is pure water or dilute inorganic acid solution, and the pure water mainly removes physically-carried lithium; the dilute acid removes both physically entrained lithium and co-extracted lithium. The aqueous phase produced by the washing can be incorporated into the extract liquor or can be treated separately. Where the aqueous phase resulting from the washing is incorporated into the extract liquor, the countercurrent extraction and washing may be referred to collectively as fractional extraction.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the synergistic extraction agent adopted by the invention has a large separation coefficient on nickel and lithium, can realize high-efficiency separation of nickel and lithium, greatly reduces the number of extraction separation stages compared with the conventional method, and reduces the investment cost;
(2) the components of the synergistic extractant adopted by the invention are all conventional mature extractants sold in the market, so that the stability is good, the production cost is low, and the use cost of the extractant is favorably reduced;
(3) other reagents used in the method are common inorganic acid and alkali, the consumption is low, and the reagent cost is low;
(4) the method has the advantages of simple and convenient operation, short flow, low cost and easy industrial realization.
Detailed Description
In order that the invention may be better understood, the invention will now be further described by way of specific embodiments, which are not intended to limit the scope of the invention.
Example 1
The aqueous feed contained 13.00g/L, Li 2.95.2.95 g/L, pH Ni of 5.10. 1#The organic phase is 0.25mol/L formula 1-1+ sulfonated kerosene; 2#The organic phase is 0.5mol/L sulfonated kerosene with the formula of 2-1 +; 3#The organic phase is 0.25mol/L formula 1-1+0.5mol/L formula 2-1+ sulfonated kerosene.
Figure BDA0003141685990000051
Saponifying 3 organic phases with 1mol/LNaOH as saponifier, 1#The organic phase saponification rate (based on formula 1-1) was 80%, 2#Organic phaseThe saponification rate (based on formula 1-1) is 0%, 3#The organic phase saponification rate (based on formula 1-1) was 80%.
The 3 organic phases are respectively contacted with the aqueous phase feed liquid for single-stage extraction, the contact time is 15min compared with O/A (2/1), the temperature is 25 ℃, and the experimental results are shown in table 1.
TABLE 1 synergistic Effect of formulas 1-1 and 2-1 on the extraction separation of Nickel and lithium
Experiment number 1 2 3
Kind of organic phase 1# 2# 3#
Formula 1-1 concentration (mol/L) 0.25 0 0.25
Formula 2-1 concentration (mol/L) 0 0.5 0.5
Extraction ratio of Nickel (%) 46.5 0.21 99.73
Extraction ratio of lithium (%) 17.0 0.36 3.29
DNi 0.44 0.13 184.69
DLi 0.10 0.28 0.017
DXie, Ni / / 324.02
The combination of the step D and the step D,Li / / 0.045
βNi/Li 4.24 0.58 10857.69
as can be seen from Table 1, the extraction efficiencies of nickel and lithium were 46.5% and 17.0%, respectively, and the separation coefficient β in the case of the extraction of the above-mentioned formula 1-1 aloneNi/LiIs 4.24; independent formula 21, the extraction rate of nickel and lithium is less than 1.0%, and the separation coefficient betaNi/LiIs 0.58; when the mixed organic phase of the formula 1-1 and the formula 2-1 is used for extraction, the extraction rate of nickel reaches 99.73 percent, the extraction rate of lithium is only 3.29 percent, and the separation coefficient beta isNi/LiUp to 10857.69. The mixed extractant of the formula 1-1 and the formula 2-1 shows obvious positive synergistic effect on nickel and a synergistic extraction coefficient DXie, Ni324.02, has obvious anti-synergistic effect on lithium and synergistic coefficient DXie, Li0.045. The mixed extraction system composed of the formula 1-1 and the formula 2-1 can effectively separate nickel and lithium from sulfuric acid leaching solution.
Example 2
Compared with the example 1, the difference is mainly that the components of the extracting agent are changed, and the steps are mainly as follows:
the aqueous feed contained Ni 15.00g/L, Li 3.12.12 g/L, pH value 4.95.
The organic phase is 0.25mol/L formula 1-1+0.5mol/L formula 2-2+ sulfonated kerosene.
Figure BDA0003141685990000061
By controlling different saponification rates, the equilibrium pH value in the extraction process can be controlled. The organic phase was saponified with 10mol/L NaOH as a saponifying agent, and the saponification rates (based on the formula 1-1) were controlled to be 0%, 20%, 40%, 60%, 80% and 100%, respectively.
The organic phases with different saponification rates are respectively contacted with the aqueous phase feed liquid for single-stage extraction, the contact time is 15min compared with that of O/A (2/1), the temperature is 20 ℃, and the experimental results are shown in Table 2.
TABLE 2 influence of saponification rate and equilibrium pH on the separation effect of nickel-lithium extraction
Experiment number 1 2 3 4 5 6
Saponification ratio (%) 0 20 40 60 80 100
Equilibrium pH value 1.64 1.83 2.39 3.37 5.00 6.29
Extraction ratio of Nickel (%) 42.30 51.37 66.09 87.07 99.73 99.90
Extraction ratio of lithium (%) 1.56 0.83 1.84 2.23 3.29 5.01
DNi 0.37 0.53 0.97 3.37 184.69 499.50
DLi 0.0079 0.0042 0.0094 0.0114 0.0170 0.0264
βNi/Li 46.26 126.21 103.97 295.24 10857.69 18941.12
As can be seen from Table 2, the equilibrium pH increased with the increase in the saponification rate, the saponification rate increased from 0% to 100%, and the equilibrium pH increased from 1.64 to 6.29. Within the experimental range, the combined extracting agent shows certain nickel-lithium separation effect and separation coefficient betaNi/LiThe separation coefficient is between 46.26 and 18941.12In the case of the individual use, and the higher the saponification rate, the higher the equilibrium pH, the separation factor betaNi/LiThe larger the Ni extraction rate, the more the co-extracted lithium increases.
Example 3
The aqueous feed solution had a Ni 0.1g/L, Li 10g/L, pH value of 8.0.
The organic phase is 0.1mol/L solvent oil with the formula of 1-1+0.6mol/L No. 2-3+ 260.
Figure BDA0003141685990000071
The operation is as follows: the organic phase was saponified before extraction with a saponifying agent of 1mol/LNaOH solution and a saponification rate (based on formula 1-1) of 10%. And (3) carrying out 5-stage countercurrent extraction on the saponified organic phase and the water phase feed liquid under the condition of a flow ratio O/A (oxygen/oxygen) of 1/10, carrying out single-stage back extraction on the loaded organic phase by adopting 3.0mol/L hydrochloric acid as a back extractant under the condition of a flow ratio O/A (oxygen/oxygen) of 15/1, and carrying out saponification on the back organic phase and returning to the extraction.
After the above saponification-extraction-back extraction operation reached a steady state, the following results were obtained: the raffinate contained Ni 0.001g/L and Li 9.98g/L, and the strip liquor contained Ni 14.70g/L and Li 3.59 g/L.
Example 4
Compared with the example 3, the difference is that the stripping is carried out after the loaded organic phase loaded with nickel is washed, and the difference is that:
the aqueous feed solution had a Ni 0.1g/L, Li 10g/L, pH value of 8.0.
The organic phase is 0.1mol/L solvent oil with the formula of 1-1+0.6mol/L No. 2-3+ 260.
The operation is as follows: the organic phase was saponified before extraction with a saponifying agent of 1mol/LNaOH solution and a saponification rate (based on formula 1-1) of 10%. After saponification, the organic phase and the aqueous phase are subjected to 5-stage countercurrent extraction under the condition of a flow ratio O/A of 1/10, and 3-stage countercurrent washing is performed under the condition of a flow ratio O/A of 10/1 to remove lithium entrained in the loaded organic phase and co-extracted lithium, and the washing agent is 0.05mol/L hydrochloric acid. The aqueous phase resulting from the washing is incorporated into the extract liquor (also known as fractional extraction). And 3.0mol/L hydrochloric acid is adopted as a stripping agent for the washed organic phase, single-stage stripping is carried out under the condition that the flow ratio O/A is 15/1, and the organic phase after the stripping is saponified and then returned for extraction.
After the above saponification-extraction-back extraction operation reached a steady state, the following results were obtained: the raffinate contains 0.0050g/L of Ni and 9.90g/L of Li, and the strip liquor contains 14.18g/L of Ni and 0.60g/L of Li.
Example 5
Compared with the example 3, the differences mainly lie in that the concentrations of Ni and Li in the feed liquid of the water phase and the initial pH value of the water phase are changed, the proportion and the concentration of the synergic extractant are changed, and the composition of the back extractant and the back extraction stage number are changed, and the main points are that:
the aqueous feed had a Ni 55g/L, Li 0.1g/L, pH value of 1.0.
The organic phase is 1.0mol/L of formula 1-1+1.0mol/L of formula 2-1+ Escaid 110.
The operation is as follows: the organic phase was saponified before extraction with a saponifying agent of 10mol/LKOH solution and a saponification rate (based on formula 1-1) of 100%. And (3) carrying out 10-grade countercurrent extraction on the saponified organic phase and the water phase feed liquid under the condition that the flow ratio O/A is 10/1, carrying out 10-grade countercurrent back extraction on the loaded organic phase by adopting 3.0mol/L nitric acid as a back extractant under the condition that the flow ratio O/A is 15/1, and carrying out saponification on the back organic phase and then returning to the extraction.
After the above saponification-extraction-back extraction operation reached a steady state, the following results were obtained: the raffinate contained Ni 0.055g/L and Li 0.095 g/L. The stripping solution contains 81.92g/L Ni and 0.0075g/L Li.
Example 6
Compared with the example 3, the differences mainly lie in that the concentrations of Ni and Li in the feed liquid of the water phase and the initial pH value of the water phase are changed, the proportion and the concentration of the synergistic extractant are changed, the components of the diluent are changed, the components of the saponifying agent and the saponification rate are changed, the extraction flow ratio and the stage number are changed, and the back extraction flow ratio and the stage number are changed, and the differences mainly lie in that:
the aqueous feed had a Ni 21.2g/L, Li 3.98.98 g/L, pH value of 4.01.
The organic phase is 0.6mol/L of aviation kerosene with the formula of 1-1+1.8mol/L of aviation kerosene with the formula of 2-1 +.
The operation is as follows: saponifying the organic phase before extraction with a saponifying agent of 5mol/LNH4OH solution, saponification ratio (based on formula 1-1) was 60%. Organic phase after saponificationAnd carrying out 8-stage countercurrent extraction with the aqueous phase feed liquid under the condition that the flow ratio O/A is 2.5/1, carrying out 5-stage countercurrent back extraction on the loaded organic phase under the condition that the flow ratio O/A is 5/1 by adopting 0.8mol/L sulfuric acid as a back extractant, and saponifying the organic phase after the back extraction and returning the organic phase to the extraction.
After the above saponification-extraction-back extraction operation reached a steady state, the following results were obtained: the raffinate contains Ni 0.0170g/L and Li 3.97g/L, and the strip liquor contains Ni 42.32g/L and Li 0.0103 g/L.
Example 7
Compared with the example 3, the differences mainly lie in that the concentrations of Ni and Li in the aqueous phase feed liquid and the initial pH value of the aqueous phase are changed, the components and the proportion of the synergistic extractant are changed, the components and the saponification rate of the saponifying agent are changed, the extraction flow ratio and the stage number are changed, and the back extraction flow ratio and the stage number are changed, and the main points are that:
the aqueous feed had a Ni 15.0g/L, Li 20g/L, pH value of 2.06.
The organic phase is 0.3mol/L of sulfonated kerosene with the formula of 1-2+1.2mol/L of sulfonated kerosene with the formula of 2-1 +.
Figure BDA0003141685990000081
The operation is as follows: the organic phase was saponified before extraction with a saponifying agent of 1mol/L LiOH solution and a saponification rate (based on formula 1-2) of 60%. After saponification, the organic phase and the aqueous phase feed liquid are subjected to 4-stage countercurrent extraction under the condition that the flow ratio O/A is 3/1. In order to remove the lithium entrained in the loaded organic phase and the co-extracted lithium, 2-stage countercurrent washing was carried out at a flow ratio O/a of 10/1, the washing agent was 0.1mol/L hydrochloric acid, and the aqueous phase resulting from the washing was incorporated into the feed liquid (also referred to as fractional extraction). And the loaded organic phase adopts 0.6mol/L sulfuric acid as a stripping agent, countercurrent back extraction is carried out under the condition that the flow ratio O/A is 7/1, and the organic phase after the reaction is saponified and then returned to the extraction.
After the above saponification-extraction-back extraction operation reached a steady state, the following results were obtained: the raffinate contains Ni 0.09g/L and Li 23.77g/L, and the strip liquor contains Ni 34.76g/L and Li 0.014 g/L.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims (10)

1. A method for selectively extracting and separating nickel and lithium is characterized in that a water phase to be separated containing nickel ions and lithium ions and an organic phase containing a combined extracting agent are mixed for extraction to obtain a loaded organic phase enriched with nickel and a raffinate enriched with lithium;
the combined extracting agent comprises a compound 1 and a compound 2; wherein, the compound 1 is at least one compound with the structural formula of formula 1; compound 2 is at least one compound having the structural formula of formula 2:
Figure FDA0003141685980000011
said R1、R2Independently is C6～12Alkyl or alkoxy of (a); m is H, Na, K, NH4Or Li;
R3is C6～12Alkyl group of (1).
2. The method for selective extraction separation of nickel and lithium according to claim 1, wherein the pH of the aqueous phase to be separated is 1-8; preferably 2.0 to 7.0;
preferably, the concentration of Ni in the water phase to be separated is 0.1-55 g/L; the concentration of Li is 0.1-20 g/L.
3. The process for selective extractive separation of nickel lithium as claimed in claim 1, wherein in formula 2, -COOR3Is located at the 4-position of the pyridine ring.
4. The method for selective extraction separation of nickel lithium as claimed in claim 1, wherein the molar ratio of the compound 1 to the compound 2 is 1:1 to 1: 6; preferably 1:1 to 1: 4.
5. The method for selective extraction separation of nickel and lithium according to claim 1, wherein the concentration of the compound 1 in the organic phase is 0.1-1.0 mol/L; preferably 0.1 to 0.5 mol/L.
6. The method for selective extraction separation of nickel lithium as claimed in claim 1, wherein the organic phase further comprises a diluent;
preferably, the diluent is sulfonated kerosene, No. 260 solvent oil, aviation kerosene, Escaid110, C8～13At least one of the higher alcohols of (1).
7. The method for selective extraction separation of nickel lithium as claimed in claim 1, wherein the organic phase is unsaponifiable organic phase or saponified organic phase, and when the organic phase is saponified, the alkali solution used in the saponification process is at least one of sodium hydroxide, potassium hydroxide, ammonia water and lithium hydroxide; the saponification degree of the resin is more than 0 percent, and preferably 10 to 90 percent; more preferably 50 to 90%.
8. The selective extraction separation method of nickel and lithium according to claim 1, wherein the extraction stage number is greater than or equal to 1; preferably 1-10 grades;
preferably, when the extraction stage number is more than or equal to 2 stages, the extraction mode is countercurrent extraction;
preferably, in the extraction process, the volume flow ratio of the organic phase to the aqueous phase feed liquid is 1/10-10/1.
9. The method for selective extraction separation of nickel and lithium as claimed in any one of claims 1 to 8, characterized in that the loaded organic phase enriched with nickel is subjected to stripping with an acid solution to obtain a stripping solution enriched with nickel;
preferably, the acid solution is an aqueous solution of at least one inorganic acid selected from sulfuric acid, nitric acid and hydrochloric acid;
preferably, H in the acid liquor+The concentration of (a) is 0.1-3.0 mol/L;
preferably, in strippingFirstly, washing the loaded organic phase in advance; the washing liquid for washing treatment is water or low acid water solution; further preferably, the H of the aqueous solution of a low acid is H during washing+The molar amount is less than or equal to the molar amount of Li + in the loaded organic phase.
10. The method for selective extraction separation of nickel and lithium according to claim 9, wherein the stripping process has a stripping stage number greater than or equal to 1; preferably 1-10 grades;
preferably, when the back extraction stage number is more than or equal to 2 stages, the back extraction mode is counter-current back extraction;
preferably, in the back extraction process, the volume flow ratio of the loaded organic phase to the acid liquor is 1/1-15/1.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103421952A (en) * 2013-08-01 2013-12-04 中南大学 Synergic extraction agent and method for selectively extracting nickel in acidic nickeliferous solution through synergic extraction agent
CN107815542A (en) * 2017-10-17 2018-03-20 中南大学 A kind of synergic reagent and method for being used for nickel selective extraction in acid solution
CN111041203A (en) * 2019-12-27 2020-04-21 厦门钨业股份有限公司 Mixed extracting agent for nickel-lithium separation and separation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103421952A (en) * 2013-08-01 2013-12-04 中南大学 Synergic extraction agent and method for selectively extracting nickel in acidic nickeliferous solution through synergic extraction agent
CN107815542A (en) * 2017-10-17 2018-03-20 中南大学 A kind of synergic reagent and method for being used for nickel selective extraction in acid solution
CN111041203A (en) * 2019-12-27 2020-04-21 厦门钨业股份有限公司 Mixed extracting agent for nickel-lithium separation and separation method

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