CN113801159B - Amino phosphonate compound and application thereof in lithium ion-containing alkaline solution extraction of lithium - Google Patents
Amino phosphonate compound and application thereof in lithium ion-containing alkaline solution extraction of lithium Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
- C07F9/4009—Esters containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
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Abstract
The invention provides an aminophosphonate compound and application thereof in lithium ion-containing alkaline solution extraction, and relates to the technical field of metal ion extraction. The structure of the aminophosphonate compound is shown as the following formula (I), wherein in the formula (I), R1 is C1-C20 straight chain or branched chain alkyl, C1-C20 straight chain or branched chain alkoxy, or C6-C10 aryl; r2 and R3 are respectively and independently hydrogen, C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C6-C10 aryl; r4 and R5 are respectively and independently C1-C10 straight-chain or branched-chain, saturated or unsaturated, substituted or unsubstituted alkyl or C6-C10 aryl; n is an integer of 1 to 4. The amino phosphonate compound can be widely applied to extraction of lithium ions in an alkaline solution containing the lithium ions.
Description
Technical Field
The invention relates to the technical field of metal ion extraction, in particular to an aminophosphonate compound and application thereof in extracting lithium from an alkaline solution containing lithium ions.
Background
Lithium is the lightest metal in nature, has extremely strong electrochemical activity, and the metal and the compound thereof are widely applied to the industries and the fields of glass, ceramic aluminum smelting, organic chemical industry, aerospace, nuclear fusion and the like as the explosive of thermonuclear fusion (hydrogen bomb), the high-performance propelling fuel of airplanes, rockets and missiles and the shielding material of nuclear reactors.
The current effective method for extracting lithium from salt lake brine comprises a solvent extraction method, and FeCl is inevitably adopted in the solvent extraction method 3 As the co-extractant, the density of the extracted organic phase is increased, the density difference of the two phases is reduced, the requirement on extraction and separation equipment is higher, the traditional mixer-settler is difficult to meet the process requirement, and high-efficiency centrifugation is adoptedThe cost of equipment for extraction is high; at the same time, feCl is introduced 3 Then, the difficulty is high when the extractant is regenerated by alkali, and very accurate flow control is needed, otherwise, the problems of extraction rate reduction or extractant emulsification failure and the like can be caused. In addition, the organic phase contains FeCl as a synergist 3 The extraction liquid (brine) is required to be weakly acidic, otherwise, fe hydrolysis is caused, the brine entering an extraction working section is required to be acidified, lithium and boron in salt lakes in Qinghai-Tibet regions of China commonly exist in an associated mode, boric acid is inevitably separated out in the acidification process, and filtration treatment is required, so that the extraction method is not applicable to extraction of lithium in an alkaline system. Most of the current extracting agents for lithium can only realize lithium-magnesium separation, and have poor extraction effect on an alkali metal system. In conclusion, feCl was the synergist 3 The existing method has the disadvantages of complex process flow, great difficulty in process control and great equipment investment.
Therefore, there is an urgent need to develop a method for extracting and separating organic compounds with high efficiency and without FeCl 3 A process suitable for extracting lithium from an alkaline solution containing lithium ions as a synergist has become necessary and desirable.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an aminophosphonate compound which can be widely applied to the extraction of lithium ions from an alkaline solution containing lithium ions.
The second purpose of the invention is to provide a method for extracting lithium from an alkaline solution containing lithium ions, wherein the extraction method takes the aminophosphonate compound as an extracting agent, has the advantages of high extraction efficiency and good separation effect in the process of extracting lithium from the alkaline solution containing lithium ions, and can effectively avoid using FeCl 3 A series of post-treatment problems brought about as co-extractants.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an aminophosphonate compound, which has a structure shown in the following formula (I):
in the formula (I), R1 is C1-C20 linear chain or branched chain alkyl, C1-C20 linear chain or branched chain alkoxy, or C6-C10 aromatic group;
r2 and R3 are respectively and independently hydrogen, C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C6-C10 aryl;
r4 and R5 are respectively and independently C1-C10 straight-chain or branched-chain, saturated or unsaturated, substituted or unsubstituted alkyl or C6-C10 aryl;
n is an integer of 1 to 4.
Further, the C6-C10 aryl group comprises one of phenyl, benzyl, o-dimethylbenzene, naphthalene, m-dimethylbenzene and p-dimethylbenzene.
Further, the aminophosphonate compound is 2-ethylhexyl (2- (2-ethylhexyl amino)) methyl phosphonate monoester;
the structure of the 2-ethylhexyl (2- (2-ethylhexyl amino)) methyl phosphonate monoester is shown as the following formula (II):
the invention provides application of the amino phosphonate compound in lithium ion-containing alkaline solution extraction.
Further, the pH value of the alkaline solution containing lithium ions is 7.5-14, and Li in the solution + The mass concentration of the lithium ion battery is 0.01-20 g/L, and the total concentration of other metals except lithium ions is less than or equal to 90g/L;
preferably, the alkaline solution containing lithium ions comprises at least one of lithium-containing brine, tail liquor obtained after cobalt and nickel are extracted from waste ternary batteries, a solution selectively leached from waste lithium iron phosphate power batteries or a filtrate obtained after lithium precipitation.
The invention provides a method for extracting lithium from an alkaline solution containing lithium ions, which comprises the following steps:
(a) Adding the aminophosphonate compound into the diluent, uniformly mixing, and then adding alkali liquor for saponification to obtain an extracted organic phase;
(b) Taking an alkaline solution containing lithium ions to be extracted as an extraction water phase, uniformly mixing an extraction organic phase and the extraction water phase, and then carrying out countercurrent extraction to obtain a raffinate and a loaded organic phase;
(c) Washing the extracted loaded organic phase to obtain a washing residual liquid and a washing organic phase;
(d) And performing back extraction on the lithium-loaded washing organic phase by adopting a back extraction solution to obtain a blank organic phase and a lithium back extraction solution with higher purity.
Further, the diluent in the step (a) comprises at least one of C6-C16 alkane, C6-C10 aromatic hydrocarbon, aviation kerosene and sulfonated kerosene, and preferably sulfonated kerosene;
preferably, the C6-C16 alkane is one of hexane, heptane and octane;
preferably, the C6-C10 aromatic hydrocarbon is one of toluene or xylene;
preferably, the concentration of the aminophosphonate compound in the step (a) is 0.01-0.3 mol/L;
preferably, the volume ratio of the mixed extraction organic phase and the mixed extraction aqueous phase in the step (b) is 1-30: 1 to 10;
more preferably, the countercurrent extraction is a multistage countercurrent extraction.
Further, the washing in the step (c) is multi-stage countercurrent washing or multi-stage cross-flow washing;
preferably, the washing solution in the step (c) is a solution of 0.01-3 mol/L hydrochloric acid, sulfuric acid and nitric acid;
more preferably, the volume ratio of the loaded organic phase to the washing liquid in the step (c) is 1 to 40:1.
further, the back extraction in the step (d) is multi-stage counter-current back extraction or multi-stage cross-flow back extraction;
preferably, the stripping solution in the step (d) is hydrochloric acid solution with the concentration of 0.01 mol/L-6 mol/L
More preferably, the volume ratio of the washing organic phase to the stripping solution in the step (d) is 1-80: 1.
further, the method for extracting lithium from the alkaline solution containing lithium ions further comprises the step (e) of regenerating the stripped blank organic phase.
Further, the steps of extraction and stripping are performed in a separatory funnel, a mixed clarification extraction tank or a centrifuge.
Further, the method for extracting lithium is carried out by adopting a solid-liquid extraction method, and comprises the steps of loading the aminophosphonate compound with the general formula I on resin, porous silica spheres or diatomite to prepare a solid separation material, and using the prepared solid separation material for separating lithium in an alkaline solution to further obtain a lithium-containing solid separation material and a lithium extraction residual liquid.
Compared with the prior art, the invention has the beneficial effects that:
the structure of the aminophosphonate compound provided by the invention is shown as the following formula (I), wherein in the formula (I), R1 is C1-C20 straight chain or branched chain alkyl, C1-C20 alkoxy or C6-C10 aryl; r2 and R3 are respectively and independently hydrogen, C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C6-C10 aryl; r4 and R5 are respectively independent C1-C10 straight-chain or branched-chain alkyl or C6-C10 aryl; n is an integer of 1 to 4. The amino phosphonate compound can be widely applied to extraction of lithium ions in an alkaline solution containing the lithium ions.
The invention provides a method for extracting lithium from an alkaline solution containing lithium ions, which comprises the steps of firstly adding an aminophosphonate compound into a diluent for uniformly mixing, and then adding alkali liquor for saponification to obtain an extracted organic phase; then evenly mixing the alkaline solution serving as a water phase and to be extracted and containing lithium ions, and then carrying out countercurrent extraction to obtain raffinate and a loaded organic phase; and washing and back-extracting the loaded organic phase in sequence to obtain a blank organic phase and a high-purity lithium back-extraction solution. The extraction method takes the aminophosphonate compound as the extracting agent, and the extraction of lithium from the alkaline solution containing lithium ions has the advantages of high extraction efficiency and good separation effect, and can effectively avoid a series of post-treatment problems caused by the use of ferric trichloride as the co-extracting agent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph of the change in extraction rate with acidity provided in example 4 of the present invention;
FIG. 2 is a diagram illustrating the variation of hydrogen ion concentration and stripping rate in the stripping process provided in example 4 of the present invention;
FIG. 3 is a graph of the saturated capacity cycle of metal ions in an organic phase provided in example 4 of the present invention;
FIG. 4 is a graph showing the extraction rate of metal ions as a function of time, which is provided in example 4 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention, an aminophosphonate compound is provided, wherein the structure of the aminophosphonate compound is shown in formula (I):
in the formula (I), R1 is C1-C20 linear chain or branched chain alkyl, C1-C20 linear chain or branched chain alkoxy, or C6-C10 aromatic group;
r2 and R3 are respectively and independently hydrogen, C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C6-C10 aryl;
r4 and R5 are respectively independent C1-C10 straight chain or branched chain, saturated or unsaturated, substituted or unsubstituted alkyl or C6-C10 aryl;
n is an integer of 1 to 4.
In a preferred embodiment of the present invention, the C6 to C10 aryl group includes one of phenyl, benzyl, o-xylene, naphthalene, m-xylene, and p-xylene.
In a preferred embodiment of the present invention, the aminophosphonate compound is 2-ethylhexyl (2- (2-ethylhexylamino)) methylphosphonate monoester;
the structure of the 2-ethylhexyl (2- (2-ethylhexyl amino)) methyl phosphonate monoester is shown as the following formula (II):
according to one aspect of the invention, the application of the aminophosphonate compound in the extraction of lithium from an alkaline solution containing lithium ions is provided.
The amino phosphonate compound provided by the invention can be widely applied to extracting lithium from an alkaline solution containing lithium ions.
The extraction principle of the aminophosphonate compound is as follows:
in a preferred embodiment of the present invention, the pH of the alkaline solution containing lithium ions is 7.5 to 14, and Li in the solution + The mass concentration of (3) is 0.01-20 g/L, except lithiumThe total concentration of other metal ions except ions is less than or equal to 90g/L;
in the above preferred embodiment, the alkaline solution containing lithium ions includes at least one of lithium-containing brine, a tail solution obtained after cobalt and nickel are extracted from a waste ternary battery, a solution selectively leached from a waste lithium iron phosphate power battery, or a filtrate obtained after lithium precipitation.
According to one aspect of the invention, a method of extracting lithium in a basic solution containing lithium ions comprises the steps of:
(a) Adding the aminophosphonate compound into the diluent, uniformly mixing, and then adding alkali liquor for saponification to obtain an extracted organic phase;
(b) Taking an alkaline solution containing lithium ions to be extracted as an extraction water phase, uniformly mixing an extraction organic phase and the extraction water phase, and then carrying out countercurrent extraction to obtain a raffinate and a loaded organic phase;
(c) Washing the extracted loaded organic phase to obtain a washing residual liquid and a washing organic phase;
(d) And carrying out back extraction on the lithium-loaded washing organic phase by adopting a back extraction solution to obtain a blank organic phase and a lithium back extraction solution with higher purity.
The invention provides a method for extracting lithium from an alkaline solution containing lithium ions, which comprises the steps of firstly adding an aminophosphonate compound into a diluent for uniformly mixing, and then adding alkali liquor for saponification to obtain an extracted organic phase; then evenly mixing the alkaline solution serving as a water phase and to be extracted and containing lithium ions, and then carrying out countercurrent extraction to obtain raffinate and a loaded organic phase; and washing and back-extracting the loaded organic phase in sequence to obtain a blank organic phase and a high-purity lithium back-extraction solution. The extraction method takes the aminophosphonate compound as the extracting agent, and the extraction of lithium from the alkaline solution containing lithium ions has the advantages of high extraction efficiency and good separation effect, and can effectively avoid a series of post-treatment problems caused by the use of ferric trichloride as the co-extracting agent.
In a preferred embodiment of the present invention, the diluent in the step (a) comprises at least one of C6-C16 alkane, C6-C10 aromatic hydrocarbon, aviation kerosene and sulfonated kerosene, preferably sulfonated kerosene;
preferably, the C6-C16 alkane is one of hexane, heptane and octane;
preferably, the C6-C10 aromatic hydrocarbon is one of toluene or xylene;
in the above preferred embodiment, the concentration of the aminophosphonate ester compound in step (a) is 0.01 to 3.0mol/L;
in a preferred embodiment, the concentration of the aminophosphonate ester compound is 0.2 to 2mol/L.
In the above preferred embodiment, the volume ratio of the extraction organic phase and the extraction aqueous phase mixed in step (b) is 1 to 30:1 to 10;
in a preferred embodiment, the volume ratio of the organic extraction phase to the aqueous extraction phase is 1 to 10:1 to 20.
More preferably, the countercurrent extraction is a multistage countercurrent extraction.
In a preferred embodiment of the present invention, the washing of step (c) is a multistage countercurrent washing or a multistage cross-flow washing;
in the above preferred embodiment, the washing solution in the step (c) is a solution of 0.01 to 3mol/L hydrochloric acid, sulfuric acid or nitric acid;
more preferably, the volume ratio of the loaded organic phase to the washing liquid in the step (c) is 1 to 40:1.
in a preferred embodiment of the present invention, the back extraction of step (d) is a multi-stage counter-current back extraction or a multi-stage cross-flow back extraction;
in the above preferred embodiment, the stripping solution in the step (d) is hydrochloric acid solution with a concentration of 0.01mol/L to 6 mol/L;
preferably, the volume ratio of the washing organic phase to the stripping solution in the step (d) is 1-80: 1.
as a preferred embodiment, the stripping step can realize the stripping of the lithium-loaded washing organic phase only by using acid with lower concentration, and has better economical efficiency and production safety.
In a preferred embodiment of the present invention, the method for extracting lithium from a basic solution containing lithium ions further comprises the step of (e) regenerating the stripped blank organic phase.
Preferably, the method for extracting lithium in an alkaline solution containing lithium ions comprises the following steps:
(1) Providing an extraction aqueous phase: taking an alkaline solution containing lithium ions as an extraction water phase; wherein the pH of the alkaline solution containing lithium ions is 7.5 to 14, and Li is contained in the alkaline solution containing lithium ions + The mass concentration of the lithium ion battery is 0.01 g/L-20 g/L, and the total concentration of other metals except lithium is not more than 90g/L;
(2) Providing an extracted organic phase: the diluent is sulfonated kerosene, and the mass concentration of the extractant is 0.3 mol/L-0.01 mol/L.
Preferably, the extractant can be prepared by reacting formula 1:
firstly, amino phosphonate ester compound (II) is obtained through aminomethylation reaction, and then amino phosphonate monoester compound (I) is obtained through hydrolysis reaction and acidification
Reaction formula 1;
preparation of an organic phase: 0.3 to 2mol of extractant is dissolved in sulfonated kerosene to obtain an organic phase, and a saponifying agent (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water and the like) aqueous solution is added into the organic phase to carry out saponification, wherein the preferable saponification degree is 20 to 40 percent. A saponified organic phase is obtained.
Degree of saponification% = molar amount of base/molar amount of extractant × 100.
(3) And an extraction step: mixing the extraction organic phase and the extraction water phase according to the volume ratio of 1-30 to 1-10, performing 2-10-stage countercurrent extraction, and after extraction balance, performing phase splitting to obtain raffinate and a loaded organic phase;
(4) And a washing step: carrying out 2-10-level countercurrent washing or 2-10-level cross-flow washing on the loaded organic phase by taking 0.01-3 mol/L hydrochloric acid solution as a washing solution, and carrying out phase separation to obtain a washing residual solution and a washing organic phase;
wherein the volume ratio of the loaded organic phase to the washing solution is 1-40;
(5) And a back extraction step: carrying out 2-10-level counter-current back extraction or 2-10-level cross-current back extraction on the washed organic phase by taking 0.01-6 mol/L hydrochloric acid solution as back extraction solution, and after the back extraction is balanced, carrying out phase separation to obtain a lithium chloride solution (high-purity lithium back extraction solution) and a blank organic phase;
wherein the volume ratio of the washing organic phase to the stripping solution is 1-80;
(6) And a regeneration step: water or alkaline solution is used as regeneration liquid to carry out 2-5 level countercurrent regeneration or 2-5 level cross flow regeneration on the empty organic phase, and phase splitting is carried out to obtain regeneration residual liquid and regeneration organic phase;
wherein the volume ratio of the empty organic phase to the regeneration liquid is 1-20.
The applicant further describes the technical scheme of the present invention with reference to examples using 2-ethylhexyl (2- (2-ethylhexylamino)) methylphosphonate as an example.
The nuclear magnetic data of the 2-ethylhexyl (2- (2-ethylhexyl amino)) methylphosphonate monoester are: 1 H NMR 600MHz,(CDCl 3) ,ppm:0.92,0.87(t,18H,CH 3 ),1.27(s,12H,CH 2 ),1.55(m,18H,CH 2 ),3.54(s,2H,PCH 2 N),3.84(m,6H,NCH 2 CH). 31 P NMR600MHz,(CDCl 3) ppm:7.35. Mass spectrometry data: m/z 448.3[ m ] +H] + 。
Note: the extractant used in the examples of this application was 2-ethylhexyl (2- (2-ethylhexylamino)) methylphosphonate monoester.
Example 1
A method of extracting lithium in a basic solution containing lithium ions, the method comprising the steps of:
1. preparation of an organic phase: 0.2mol of extractant is mixed with 1.0L of sulfonated kerosene, and then sodium hydroxide solution with the saponification degree of 30% is added for saponification to obtain an extracted organic phase.
2. The original feed liquid is a filtrate obtained after lithium precipitation in a salt lake, the pH is =10.33, and the ion concentrations are shown in the table
| Ion(s) | Li | Na | Mg | Ca | K |
| g/L | 1.85 | 73.17 | 0.32 | 0.039 | 0.14 |
3. The washing liquid is 0.01mol/L hydrochloric acid solution;
4. the stripping agent is 0.5mol/L hydrochloric acid solution;
5. organic phase regeneration liquid: 1mol/L sodium carbonate;
6. and (3) mixing the organic phase and the feed liquid according to the volume ratio of 8: performing 3-stage countercurrent extraction according to the proportion of 1 to obtain an extracted organic phase containing lithium and an extracted water phase, and then performing volume ratio of the organic phase containing lithium to a washing solution of 10:1 mixing and washing. And then, mixing the lithium-containing extraction organic phase and a stripping agent according to a volume ratio of 5:1, performing 3-stage countercurrent back extraction and phase separation to obtain an enriched lithium chloride aqueous solution and a blank organic phase;
7. mixing the organic phase with the regeneration liquid according to the volume ratio of 5. Regenerating the organic phase for extracting the organic phase in the next period;
8. elemental analysis of the obtained lithium-containing aqueous solution was carried out (analytical instrument: ICP-OES, model: thermo iCAP 6500), and the result showed that the relative purity of the lithium chloride solution was 94.9%.
Example 2
A method of extracting lithium in a basic solution containing lithium ions, the method comprising the steps of:
1. preparation of an organic phase: 0.2mol of extractant is mixed with 1.0L of sulfonated kerosene, and then sodium hydroxide solution with the saponification degree of 30% is added for saponification to obtain an extracted organic phase.
2. The experimental feed liquid is tail liquid obtained after cobalt and nickel are extracted from waste ternary batteries, sodium hydroxide solution is added, the pH of the feed liquid is adjusted to 9.8, and the concentration of each ion is shown as the following table:
| ion(s) | Li | Na | Ni | Co | Mg | Ca |
| g/L | 1.87 | 32 | 0.028 | 0.005 | 0.002 | 0.005 |
3. The washing liquid is 0.01mol/L hydrochloric acid solution;
4. the stripping agent is 0.5mol/L hydrochloric acid solution;
5. organic phase regeneration liquid: 1mol/L sodium carbonate;
6. and (3) mixing the organic phase and the feed liquid according to the volume ratio of 8: performing 4-stage countercurrent extraction according to the proportion of 1 to obtain an extracted organic phase containing lithium and an extracted water phase, and then performing volume ratio of the organic phase containing lithium to a washing solution of 10:1 mix and 7 stages of counter current washing. Then, mixing the lithium-containing extraction liquid and a stripping agent according to the volume ratio of 5:1, performing 3-stage countercurrent back extraction, and performing phase separation to obtain an enriched lithium chloride aqueous solution and a blank organic phase.
7. Mixing the organic phase with a regeneration liquid according to the volume ratio of 5. The organic phase is regenerated for the next cycle of extraction.
8. Elemental analysis is carried out on the obtained lithium-containing aqueous solution, (an analytical instrument: ICP-OES, model: thermo iCAP 6500), and the result shows that the back extraction rate of lithium can reach 94%, the relative purity of the lithium solution obtained after back extraction is more than 93%, and the lithium solution can be used for preparing other related products of lithium.
Example 3
A method of extracting lithium in a basic solution containing lithium ions, the method comprising the steps of:
1. preparation of an organic phase: 0.3mol of extractant is mixed with 1.0L of sulfonated kerosene, and then sodium hydroxide solution with the saponification degree of 30% is added for saponification to obtain an extracted organic phase.
2. The feed liquid is a solution selectively leached by the waste lithium iron phosphate power battery: the concentration of lithium ions is 3.95g/L, the concentration of iron ions is 0.24g/L, and the pH value of the solution is 4.58. Adjusting pH to above 8 with sodium hydroxide, and filtering.
3. The washing liquid is 0.01mol/L hydrochloric acid solution;
4. the stripping agent is 0.5mol/L hydrochloric acid solution;
5. organic phase regeneration liquid: 1mol/L sodium carbonate;
6. and (3) mixing the organic phase and the feed liquid according to the volume ratio of 10: performing 6-stage countercurrent extraction according to the proportion of 1 to obtain an extracted organic phase containing lithium and an extracted water phase, and then performing volume ratio of the organic phase containing lithium to a washing solution of 10:1 mixing and washing. Then, mixing the lithium-containing extraction liquid and a stripping agent according to the volume ratio of 5:1, performing 2-stage countercurrent back extraction, and performing phase separation to obtain an enriched lithium chloride aqueous solution and a blank organic phase.
7. Mixing the organic phase with a regeneration liquid according to the volume ratio of 5. The organic phase is regenerated for the next cycle of extraction.
8. Elemental analysis is carried out on the obtained lithium-containing aqueous solution, (an analytical instrument is ICP-OES, the model is Thermo iCAP 6500), the result shows that the back extraction rate of the lithium can reach 94%, the relative purity of the lithium solution obtained after back extraction is more than 92%, and the lithium solution can be used for preparing lithium related products.
Example 4
A method of extracting lithium in a basic solution containing lithium ions, the method comprising the steps of:
1. preparation of an organic phase: 0.2mol of extractant is mixed with 1.0L of sulfonated kerosene, and then sodium hydroxide solution with the saponification degree of 30% is added for saponification to obtain an extracted organic phase.
2. Lithium solution with the concentration of lithium ions being 0.21g/L, and adjusting the pH value of the feed liquid to 9.28;
3. the washing liquid is 0.01mol/L hydrochloric acid solution;
4. the stripping agent is 0.5mol/L hydrochloric acid solution;
5. organic phase regeneration liquid: 1mol/L sodium carbonate;
6. and (3) mixing the organic phase and the feed liquid according to the volume ratio of 1: performing 4-stage countercurrent extraction at a ratio of 1, obtaining an extracted organic phase containing lithium and an extracted aqueous phase after the extraction with an equilibrium pH =7.82, and then mixing the organic phase containing lithium with a washing solution according to a volume ratio of 10:1 mixing and washing. Then, mixing the lithium-containing extraction liquid and a stripping agent according to the volume ratio of 5:1, performing 2-stage countercurrent back extraction, and performing phase separation to obtain an enriched lithium chloride aqueous solution and a blank organic phase.
FIG. 1 is a graph showing the change of extraction rate with acidity according to the present example;
FIG. 2 is a graph showing the variation of hydrogen ion concentration and stripping rate in the stripping process of this embodiment;
FIG. 3 is a graph showing the cycle of the saturation capacity of metal ions in the organic phase according to the present example;
FIG. 4 is a graph showing the time-dependent change in the metal ion extraction rate of this example.
7. Mixing the organic phase with a regeneration liquid according to the volume ratio of 5. The organic phase is regenerated for the next cycle of extraction.
8. The obtained lithium-containing aqueous solution is subjected to element analysis (an analytical instrument: ICP-OES, model: thermo iCAP 6500), and the result shows that the back extraction rate of lithium can reach 92%, and the lithium-containing aqueous solution can be used for preparing related products of lithium.
Example 5
1. Preparing extraction leaching resin: 60ml of 2-ethylhexyl (2- (2-ethylhexyl amino)) methyl phosphonate monoester is mixed with 60ml of styrene-divinylbenzene to prepare an oil phase, wherein the volume ratio of the styrene to the divinylbenzene is 2:1. taking 600ml of deionized water, adding 18g of gelatin and 3g of ammonium thiocyanate, heating to 50 ℃, slowly adding an oil phase after the gelatin is completely dissolved, stirring for half an hour, heating to 80 ℃, reacting for 6 hours, then heating to 90 ℃, and curing for half an hour. The filtered resin was taken out, washed with water and air-dried to obtain 90g of levextrel resin.
2. Extraction experiment: 60g of the extraction resin is put into a separation column, lithium-containing feed liquid (0.6 g/L, acidity pH = 10) is added, the flow rate of the feed liquid is 2ml/min, and sampling and monitoring are carried out at intervals of 5 minutes. And stopping feeding when the content of lithium in the lithium extraction tail liquid is more than 0.01 g/L. The lithium-containing extraction resin was washed by adding a washing solution (hydrochloric acid solution with pH = 4) at a flow rate of 2 ml/min. Then, the back extract (1 mol/L hydrochloric acid solution) was added at a flow rate of 2 ml/min. When the concentration of lithium in the stripping solution is lower than 0.01g/L, the stripping is finished.
3. The obtained lithium-containing aqueous solution is subjected to element analysis (an analytical instrument: ICP-OES, model: thermo iCAP 6500), and the result shows that the back extraction rate of lithium can reach 95%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for extracting lithium from a basic solution containing lithium ions, the method comprising the steps of:
(a) Adding the aminophosphonate compound into the diluent, uniformly mixing, and then adding alkali liquor for saponification to obtain an extracted organic phase;
(b) Taking an alkaline solution containing lithium ions to be extracted as an extraction water phase, uniformly mixing an extraction organic phase and the extraction water phase, and then carrying out countercurrent extraction to obtain a raffinate and a loaded organic phase;
(c) Washing the extracted loaded organic phase to obtain a washing residual liquid and a washing organic phase;
(d) Carrying out back extraction on the lithium-loaded washing organic phase by adopting a back extraction solution to obtain a blank organic phase and a lithium back extraction solution with higher purity;
the structure of the aminophosphonate compound is shown as the following formula (I):
in the formula (I), R1 is C1-C20 linear chain or branched chain alkyl, C1-C20 linear chain or branched chain alkoxy, or C6-C10 aromatic group;
r2 and R3 are respectively and independently hydrogen, C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C6-C10 aryl;
r4 and R5 are respectively and independently C1-C10 straight-chain or branched-chain, saturated or unsaturated, substituted or unsubstituted alkyl or C6-C10 aryl;
n is an integer of 1 to 4;
the pH value of the alkaline solution containing the lithium ions is 7.5-14, and Li in the solution + The mass concentration of the lithium ion battery is 0.01-20 g/L, and the total concentration of other metals except lithium ions is less than or equal to 90g/L.
2. The method of claim 1, wherein the aryl group having 6 to 10 carbon atoms in the aminophosphonate compound comprises one of phenyl, benzyl, o-xylene, naphthalene, m-xylene, and p-xylene.
3. The method for extracting lithium from a basic solution containing lithium ions according to claim 1, wherein the aminophosphonate compound is 2-ethylhexyl (2- (2-ethylhexylamino)) methylphosphonate monoester;
the structure of the 2-ethylhexyl (di- (2-ethylhexyl amino)) methyl phosphonate monoester is shown as the following formula (II):
4. the method of claim 1, wherein the alkaline solution containing lithium ions comprises at least one of lithium-containing brine, tail liquid obtained by extracting cobalt and nickel from waste ternary batteries, solution obtained by selectively leaching waste lithium iron phosphate power batteries, or filtrate obtained by precipitating lithium.
5. The method of claim 1, wherein the diluent in step (a) comprises at least one of a C6-C16 alkane, a C6-C10 aromatic hydrocarbon, aviation kerosene, sulfonated kerosene;
the C6-C16 alkane is one of hexane, heptane and octane;
the C6-C10 aromatic hydrocarbon is one of toluene or xylene;
the concentration of the aminophosphonate compound in the step (a) is 0.01-3 mol/L;
the volume ratio of the extraction organic phase to the extraction aqueous phase in the step (b) is 1-30: 1 to 10;
the countercurrent extraction in the step (b) is multi-stage countercurrent extraction.
6. The method for extracting lithium from a basic solution containing lithium ions according to claim 1, wherein the washing in step (c) is a multi-stage counter-current washing or a multi-stage cross-current washing;
and/or, the washing liquid in the step (c) is a hydrochloric acid, sulfuric acid or nitric acid solution with the concentration of 0.01-3 mol/L;
and/or the volume ratio of the loaded organic phase to the washing liquid in the step (c) is 1-40: 1.
7. the method of claim 1, wherein the step (d) comprises a multi-stage counter-current back-extraction or a multi-stage cross-current back-extraction;
and/or, the back extraction solution in the step (d) is hydrochloric acid solution with the concentration of 0.01-6 mol/L;
and/or the volume ratio of the washing organic phase to the stripping solution in the step (d) is 1-80: 1.
8. the method of claim 1, further comprising the step of (e) regenerating the stripped blank organic phase.
9. The method of claim 1, wherein the steps of extracting and stripping are performed in a separatory funnel, a mixed-clarification extraction tank, or a centrifuge.
10. The method for extracting lithium from an alkaline solution containing lithium ions according to claim 1, wherein the method for extracting lithium is performed by a solid-liquid extraction method, and comprises the steps of loading the aminophosphonate compound of the general formula I on resin, porous silica spheres or diatomite to prepare a solid separation material, and using the prepared solid separation material for separating lithium from the alkaline solution to obtain a lithium-containing solid separation material and a lithium extraction residual solution.
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