CN115786735A - Lithium extractant and extraction method thereof - Google Patents
Lithium extractant and extraction method thereof Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- 150000002576 ketones Chemical class 0.000 claims abstract description 33
- 239000003607 modifier Substances 0.000 claims abstract description 28
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 26
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 21
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims description 77
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 102220012898 rs397516346 Human genes 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 22
- 238000000638 solvent extraction Methods 0.000 abstract description 7
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 38
- 238000002156 mixing Methods 0.000 description 24
- 239000008346 aqueous phase Substances 0.000 description 22
- 238000005191 phase separation Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- BQGIRHZHJCKMQF-UHFFFAOYSA-N 8-methyl-1-phenylnonane-1,3-dione Chemical group CC(C)CCCCC(=O)CC(=O)C1=CC=CC=C1 BQGIRHZHJCKMQF-UHFFFAOYSA-N 0.000 description 12
- 238000000819 phase cycle Methods 0.000 description 11
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- DYQAZJQDLPPHNB-UHFFFAOYSA-N 1-phenyl-2-hexanone Chemical compound CCCCC(=O)CC1=CC=CC=C1 DYQAZJQDLPPHNB-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal group Chemical group C(C)C(C=O)CCCC LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 4
- BHQNLESEZHPANI-UHFFFAOYSA-N 1-(4-methylphenyl)butan-2-one Chemical group CCC(=O)CC1=CC=C(C)C=C1 BHQNLESEZHPANI-UHFFFAOYSA-N 0.000 description 3
- LRAWMVLQUISSNR-UHFFFAOYSA-N 10,10-dioctyloctadecan-1-amine Chemical group C(CCCCCCC)C(CCCCCCCCCN)(CCCCCCCC)CCCCCCCC LRAWMVLQUISSNR-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical group CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 229940093609 tricaprylin Drugs 0.000 description 3
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QBDCOUHKEVYWLO-UHFFFAOYSA-N Decanoyl acetaldehyde Chemical group CCCCCCCCCC(=O)CC=O QBDCOUHKEVYWLO-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of lithium extraction, and particularly relates to a lithium extraction agent and an extraction method thereof, wherein the lithium extraction agent comprises beta-diketone and a modifier, the modifier comprises one or more of a tertiary amine extraction agent, aldehyde, ketone and fatty alcohol, the carbon atom number of the fatty alcohol is 8-20, the chemical structure of the aldehyde and the ketone contains groups R1-R5, the chemical structure of the tertiary amine extraction agent contains groups R6-R8, R1-R3 and R5 are respectively selected from H, ar and C n H 2n+1 (n = 1-10), ar contains groups R19 to R23, and R19 to R23 are H or CH 3 ，R4＝C n H 2n+1 (n = 1-15), R6 to R8 are C n H 2n+1 (n = 5-20). The invention avoids using expensive trialkyl phosphine oxide, and effectively reduces the cost of the extracting agent. The lithium extraction method provided by the invention uses the extractant, is simple and efficient, and fully exerts the advantage of lithium extraction by a solvent extraction technology.
Description
Technical Field
The invention belongs to the technical field of lithium extraction, and particularly relates to a lithium extracting agent and an extracting method thereof.
Background
With the rapid development and application of lithium batteries, lithium and compounds thereof are increasingly widely applied in the industrial fields of chemical industry, medicine, electronics and the like. Under the large background of the rapid rise of lithium salt demand, the lithium extraction technology is changing day by day and emerges endlessly. The solvent extraction technology is mature, the process is simple and reliable, and the lithium extraction cost can be greatly reduced, so that the lithium extraction technology has obvious advantages in the comprehensive utilization of lithium resources.
Beta-diketones are common lithium extractants, beta-diketones without trifluoromethyl group (e.g. Mextral 54) have a pH above 10 for lithium extraction and require trialkylphosphine oxide (TRPO) as a co-extractant. The price of TRPO is very expensive, and if the synergistic extraction system of beta-diketone and TRPO is adopted for lithium extraction, the price of an extractant can cause the lithium extraction scheme of a solvent extraction technology to lose advantages. In contrast, tributyl phosphate, although inexpensive, is easily degraded under high pH conditions, with potential risks as a co-extractant instead of TRPO. In addition, because the raffinate is more or less entrained with the components of the extractant, the organophosphorus compound in the extractant not only increases the level of environmental pollution, but also increases the difficulty of three-waste treatment, thereby indirectly increasing the cost of lithium extraction.
Disclosure of Invention
The invention aims to provide a lithium extraction agent and an extraction method thereof, and aims to solve the problem of high lithium extraction cost in a solvent extraction technology.
In order to achieve the purpose, the scheme of the invention is as follows: a lithium extractant comprises beta-diketone and a modifier, wherein the modifier comprises one or more of a tertiary amine extractant, aldehyde, ketone and fatty alcohol, the carbon atom number of the fatty alcohol is 8-20, the aldehyde and ketone have the structure shown in a formula (I), and the tertiary amine extractant has the structure shown in a formula (II);
in the formula (I), R1, R2, R3 and R5 are respectively and independently selected from the following groups：H、Ar、C n H 2n+1 ，C n H 2n+1 N =1-10, R4= C n H 2n+1 ，n＝1-15；
In the formula (II), R6, R7 and R8 are respectively C independently n H 2n+1 ，n＝6-20；
Wherein, the structure of Ar is shown as formula (III) or formula (IV);
in the formulas (III) and (IV), R19, R20, R21, R22 and R23 are each independently H or CH 3 。
Alternatively, the beta-diketone has a structure shown in formula (V);
in the formula (V), R9, R10, R11 and R12 are each independently H or CH 3 ，R13＝C n H 2n+1 ，n＝5-15。
Optionally, in the chemical structure of the aldehyde, R5= H, R1, R2, R3 are each independently H or a straight chain alkyl group of 1-3 carbon atoms, and the sum of the carbon atoms of R1, R2, R3, and R4 is between 4 and 15.
Optionally, in the chemical structure of the ketone, R5 is phenyl, R1, R2, and R3 are each independently H or a straight-chain alkyl group having 1 to 3 carbon atoms, and the total number of carbon atoms of R1, R2, R3, and R4 is between 3 and 10.
Alternatively, in formula (II), the sum of the carbon atoms of R6, R7 and R8 is between 20 and 30.
Optionally, in formula (V), R9, R10, R11 and R12 are all H, and R13 has 5-10 carbon atoms.
Optionally, in the modifier, the ratio of the sum of the masses of aldehyde and ketone to the mass of beta-diketone is 0.5 to 2.5; or the mass ratio of the ketone to the beta-diketone is 0.5-2.5.
Optionally, in the modifier, the mass ratio of aldehyde to ketone is 0 to 1.5.
Optionally, in the modifier, the mass ratio of the tertiary amine extractant to the beta-diketone is 1-2:1.
Optionally, in the modifier, the mass ratio of the fatty alcohol to the beta-diketone is 1-3:1.
The scheme also provides a lithium extraction method, which comprises the step of extracting the lithium-containing solution by adopting the extraction organic phase containing the lithium extracting agent.
The working principle and the beneficial effects of the scheme are as follows: the lithium extracting agent in the scheme does not use organic phosphorus compound trialkyl phosphine oxide, so that the cost of the extracting agent is reduced, the lithium extracting cost of the solvent extraction technology is directly reduced, the level of environmental pollution is reduced, the three-waste treatment cost is reduced, and the lithium extracting cost is indirectly reduced, therefore, the scheme can fully exert the advantage of the lithium extracting by the solvent extraction technology. In addition, the extraction rate of the lithium-containing solution can reach 97.6%, and the extraction rate is high.
Drawings
Fig. 1 is a process flow diagram of a lithium extraction method according to an embodiment of the present invention.
Detailed Description
The following is further detailed by way of specific embodiments:
the invention provides a lithium extractant which comprises beta-diketone and a modifier, wherein the modifier comprises one or more than two of tertiary amine extractant, aldehyde, ketone and fatty alcohol. In the modifier, the mass ratio of the sum of the aldehyde and the ketone or the mass ratio of the ketone to the beta-diketone is 0.5-2.5, and the mass ratio of the aldehyde to the ketone is 0-1.5; the mass ratio of the tertiary amine extractant to the beta-diketone is 1-2:1; the mass ratio of the fatty alcohol to the beta-diketone is 1-3:1.
The carbon atom number of the aliphatic alcohol is 8-20, the structures of aldehyde and ketone are shown as formula (I), and the structure of the tertiary amine extractant is shown as formula (II);
in the formula (I), R1, R2, R3,Each R5 is independently selected from the following groups: H. ar, C n H 2n+1 ，C n H 2n+1 N =1-10, R4= C n H 2n+1 ，n＝1-15；
In the formula (II), R6, R7 and R8 are respectively C independently n H 2n+1 N =6-20; preferably, the sum of the number of carbon atoms of R6, R7 and R8 is between 20 and 30.
Wherein, the structure of Ar is shown as formula (III) or formula (IV);
in the formulas (III) and (IV), R19, R20, R21, R22 and R23 are each independently H or CH 3 。
In the chemical structure of the aldehyde, R5= H, R1, R2 and R3 are respectively independent H or straight-chain alkyl with 1-3 carbon atoms, and the sum of the carbon atoms of R1, R2, R3 and R4 is between 4 and 15.
In the chemical structure of the ketone, R5 is phenyl, R1, R2 and R3 are respectively H or straight-chain alkyl with 1-3 carbon atoms, and the sum of the carbon atoms of R1, R2, R3 and R4 is between 3 and 10.
The structure of the beta-diketone is shown as the formula (V);
in the formula (V), R9, R10, R11 and R12 are each independently H or CH 3 Preferably, R9, R10, R11 and R12 are all H, R13= C n H 2n+1 N =5-15, preferably n =5-10.
The invention also provides a lithium extraction method, which comprises the step of extracting the lithium-containing solution by using the extraction organic phase containing the lithium extracting agent.
Example 1
In this embodiment, the modifiers include tertiary amine extractants, ketones, and fatty alcohols.
In this example, the fatty alcohol is isotridecyl alcohol; the ketone being phenylcyclohexaneKetones, i.e. R1, R2, R3 are all H, R4 is C 3 H 7 R5 is Ar, the structure of which is shown as the formula (III), and R19, R20, R21, R22 and R23 are all H; the tertiary amine extractant is trioctyl decylamine, namely R6 and R7 are both C 8 C 17 R8 is C 10 H 21 (ii) a The beta-diketone is 1-phenyl-3-isoheptyl-1,3-propanedione, namely R9, R10, R11 and R12 are all H, and R13 is C 7 H 15 。
In this example, the mass ratio of ketone (phenylhexanone) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 2.06, the mass ratio of tertiary amine extractant (tricaprylin) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1.45, and the mass ratio of fatty alcohol (isotridecanol) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1.89.
The embodiment also provides a lithium extraction method, which comprises the following steps:
1. preparation step
Step one, preparing an extraction organic phase: according to the mass ratio of the phenylhexanone to the trioctyl decylamine to the isotridecyl alcohol to the 1-phenyl-3-isoheptyl-1,3-propanedione = 2.06. The extractant concentration in the organic phase of the extraction was 55.5% (v/v).
Step two, initial extraction (E0): 300mL of the lithium-containing feed solution was mixed with 450mL of the organic phase for 5min, and then 10mL of a 30% (w/w) aqueous solution of sodium hydroxide was added within the initial 30 seconds of the mixing, and the mixing temperature was 35 ℃. Stirring was then stopped and phase separation was complete in 2.5 minutes. The organic phase (org 0) is separated off into E1 of the first organic phase circuit and the aqueous phase (aq 0) is separated off into E2 of the first organic phase circuit. The pH of the aqueous phase aq0 was found to be 12.57. The components of the lithium-containing feed liquid are shown in table 1.
TABLE 1 ingredients of lithium-containing feed solutions
| Composition (I) | Li | Na | Ca | Mg | pH(H + ) |
| Content (wt.) | 1.52g/L | 59.04g/L | 0.49ppm | 2.48ppm | 12.9 |
2. The first cycle of organic phase circulation (organic phase circulation according to the process flow shown in FIG. 1)
Step one, first extraction (E1): 300mL of the lithium-containing feed liquid was mixed with the organic phase org0 for 5min, and then, within the initial 30 seconds of mixing, 10mL of a 30% (w/w) aqueous solution of sodium hydroxide was added, and the mixing temperature was 35 ℃. Stirring was then stopped and phase separation was complete in 2.5 minutes. The organic phase (orgE 1) is separated off for the first washing (W1) and the aqueous phase (aqE) is separated off into the next round of E2. The pH of aqueous phase aqE was measured to be 12.65.
Step two, washing for the first time W1: 150mL of purified water was taken, mixed with the organic phase orgE1 for 5min, and 2mL of 9mol/L sulfuric acid (H2 SO 4) was added during the initial 30 seconds of mixing at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase (orgW 1) and the aqueous phase (aqW) are separated. The pH of aqW1 was found to be 11.5.aqW1 enters E1 of the next round of organic phase circulation. OrgW1 goes into W2.
Step three, washing W2 for the second time: 150mL of purified water was taken, mixed with the organic phase orgW1 for 5min, and 0.5mL of 9mol/L sulfuric acid was added within the initial 30 seconds of mixing at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete for 3 minutes. The organic phase (orgW 2) and the aqueous phase (aqW) are separated. The pH of aqW2 was found to be 11.3.aqW2 enters W1 of the next round of organic phase circulation. OrgW2 goes to S1.
Step four, carrying out first back extraction S1: 150mL of purified water was taken, mixed with the organic phase orgW2 for 5min, and 3mL of 9mol/L sulfuric acid was added within the initial 30 seconds of mixing at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase (orgS 1) and the aqueous phase (aqS) are separated. The pH of aqS1 was found to be 9.8. The next organic phase cycle of S1 is still stripped with aqS 1. orgS1 proceeds to S2.
Step five: and (3) performing secondary back extraction S2: 150mL of purified water was taken, mixed with the organic phase orgS1 for 5min, and 0.5mL of 9mol/L sulfuric acid was added within the initial 30 seconds of mixing at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase (orgS 2) and the aqueous phase (aqS) are separated. The pH of aqS2 was found to be 9.5. The next round of organic phase recycled S2 was still stripped with aqS 2. OrgS2 goes to E2.
Step six: second extraction E2: 300mL of the aqueous phase aq0 were mixed with the organic phase orgS2 for 5min at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete for 3 minutes. The organic phase (orgE 2) is separated off. The water phase is the raffinate of the organic phase cycle. The organic phase orgE2 enters E1 of the next organic phase cycle. The raffinate pH was measured to be 12.55.
3. The second cycle of organic phase circulation (organic phase circulation according to the process flow shown in FIG. 1)
Step one, first extraction (E1): 300mL of lithium-containing feed liquid is taken and added into 150mL of aqueous phase aqW1 circulated in the previous circle of organic phase, and the total amount is 450mL. Mix with the last round of organic phase circulating orgE2 for 5min, add 10mL of 30% (w/w) aqueous sodium hydroxide solution during the initial 30 seconds of mixing, at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 2.5 minutes. The organic phase (orgE 1) is separated off for the first washing (W1) and the aqueous phase (aqE) is separated off into the next round of E2. The pH of aqueous phase aqE was measured to be 12.57.
Step two, washing for the first time W1: 150mL of the aqueous phase aqW2 from the previous cycle of the organic phase was mixed with the organic phase orgE1 for 5min, and during the initial 30 seconds of mixing, 2mL of 9mol/L sulfuric acid was added, the mixing temperature being 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase (orgW 1) and the aqueous phase (aqW) are separated. The pH of aqW1 was found to be 11.5.aqW1 enters E1 of the next round of organic phase circulation. OrgW1 goes into W2.
Step three, washing W2 for the second time: 150mL of purified water was taken, mixed with the organic phase orgW1 for 5min, and 0.5mL of 9mol/L sulfuric acid was added within the initial 30 seconds of mixing at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete for 3 minutes. The organic phase (orgW 2) and the aqueous phase (aqW) are separated. The pH of aqW2 was found to be 11.3.aqW2 enters W1 of the next round of organic phase circulation. OrgW2 goes to S1.
Step four, carrying out first back extraction S1: 150mL of the aqueous phase aqS1 from the previous cycle of the organic phase was mixed with the organic phase orgW2 for 5min, and 3mL of 9mol/L sulfuric acid was added during the initial 30 seconds of mixing, at a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase (orgS 1) and the aqueous phase (aqS) are separated. The pH of aqS was measured to be 9.8. The next organic phase cycle of S1 is still stripped with aqS 1. orgS1 proceeds to S2.
Step five: and (3) performing secondary back extraction S2: 150mL of the aqueous phase aqS2 from the previous cycle of the organic phase was mixed with the organic phase orgS1 for 5min, and during the initial 30 seconds of mixing, 0.5mL of 9mol/L sulfuric acid was added, with a mixing temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase (orgS 2) and the aqueous phase (aqS) are separated. The pH of aqS2 was found to be 9.5. The next round of organic phase recycled S2 was still stripped with aqS 2. OrgS2 goes to E2.
Step six: second extraction E2: the aqueous phase aqE1 from the previous cycle of organic phase was mixed with the organic phase orgS2 for 5min at a temperature of 35 ℃. Stirring was then stopped and phase separation was complete in 3 minutes. The organic phase is separated off (orgE 2). The water phase is the raffinate of the organic phase cycle. The organic phase orgE2 enters E1 of the next organic phase cycle. The raffinate pH was measured to be 12.55.
The organic phase circulation was repeated for 8 cycles according to the process shown in FIG. 1, the extraction organic phase and the aqueous phase were mixed for 5min, 30% (w/w) aqueous sodium hydroxide solution or 9mol/L sulfuric acid was added during the mixing to adjust the pH, and the pH of the sodium hydroxide, sulfuric acid and extraction equilibrium consumed in each cycle of the extraction organic phase are shown in Table 2.
TABLE 2 sodium hydroxide and sulfuric acid consumption and extraction equilibrium pH
| Extraction unit | E1 | E2 | W1 | W2 | S1 | S2 |
| Acid/base consumption | 8-10mL | - | 2mL | 0.5mL | 3mL | 0.5mL |
| Equilibrium pH | 12.3-12.8 | 12.3-12.8 | 11.3-11.6 | 11.0-11.5 | 9.7-10.3 | 9.5-10.0 |
In this example, the raffinate from the 8 th organic phase cycle had a lithium concentration of 69ppm and an extraction rate of 95.5%. The concentrations of lithium and sodium in the back extraction aqueous phase aqS1 are respectively 17.6g/L and 0.74g/L, and the method can be used for preparing lithium carbonate.
Example 2
This embodiment is different from embodiment 1 in that: the modifier for the extractant in this example is different from the modifier for the extractant in example 1. Modifiers for the extractant in this example include tertiary amine extractants, aldehydes, ketones, and fatty alcohols.
In this example, the aldehyde is 2-ethylhexanal, i.e., R2, R3, R5 are H, and R1 is C 2 H 5 R4 is C 3 H 7 . The tertiary amine extractant, ketone and fatty alcohol were the same as in example 1.
In this example, the mass ratio of aldehyde (2-ethylhexanal) to ketone (phenylhexanone) was 36, the mass ratio of the sum of aldehyde and ketone (sum of mass of 2-ethylhexanal + phenylhexanone) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1:1, the mass ratio of tertiary amine extractant (tricaprylin) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1.45, the mass ratio of fatty alcohol (isotridecanol) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1.89.
Compared with the lithium extraction method provided in example 1, the lithium extraction method provided in this example has the following differences, and the remaining steps are the same:
1. preparing an extraction organic phase: according to the mass ratio of 2-ethylhexanal, phenylhexanone, tricaprylin, isotridecanol, 1-phenyl-3-isoheptyl-1,3-propanedione =0.36, 1.89. The extractant concentration in the organic phase of the extraction was 46.7% (v/v).
2. The sodium hydroxide, sulfuric acid and the extraction equilibrium pH consumed for each cycle of the extraction organic phase are shown in table 3.
TABLE 3 sodium hydroxide and sulfuric acid consumption and extraction equilibrium pH
| Extraction unit | E1 | E2 | W1 | W2 | S1 | S2 |
| Acid/base consumption | 7-8mL | - | 1.5-2mL | 0.5mL | 3mL | 0.5mL |
| Equilibrium pH | 12.3-12.8 | 12.3-12.8 | 11.3-11.6 | 11.0-11.5 | 9.7-10.3 | 9.5-10.0 |
In this example, the lithium concentration in the raffinate from the 8 th organic phase cycle was 37ppm, and the extraction rate was 97.6%. 5363 the concentrations of lithium and sodium in aqS1 are 19.8g/L and 0.55g/L, respectively, and can be used for preparing lithium carbonate.
Example 3
This embodiment is different from embodiment 1 in that: the modifier for the extractant in this example is different from the modifier for the extractant in example 1. The modifier of the extractant in this example comprises only the tertiary amine extractant and the ketone. The tertiary amine extractant and beta-diketone were the same as in example 1. The ketone is benzononanone, i.e. R1, R2 and R3 are all H, and R4 is C 6 H 13 R5 is Ar, the structure of Ar is shown in a formula (III), and R19, R20, R21, R22 and R23 are all H.
In this example, the mass ratio of ketone (benzononanone) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1.8, and the mass ratio of tertiary amine extractant (trioctydecylamine) to β -diketone (1-phenyl-3-isoheptyl-1,3-propanedione) was 1.4.
Compared with the lithium extraction method provided in example 1, the lithium extraction method provided in this example has the following differences, and the remaining steps are the same:
1. preparing an extraction organic phase: preparing an extracting agent according to the mass ratio of benzononanone to trioctyl decylamine to 1-phenyl-3-isoheptyl-1,3-propanedione = 1.8. The extractant concentration in the organic phase was 50.0% (v/v).
2. The sodium hydroxide, sulfuric acid and the extraction equilibrium pH consumed for each cycle of the extraction organic phase are shown in table 4.
Table 4 sodium hydroxide and sulfuric acid consumption and extraction equilibrium pH
| Extraction unit | E1 | E2 | W1 | W2 | S1 | S2 |
| Acid/base consumption | 9mL | - | 2mL | 0.5mL | 3mL | 0.5mL |
| Equilibrium pH | 12.3-12.8 | 12.3-12.8 | 11.3-11.6 | 11.0-11.5 | 9.7-10.3 | 9.5-10.0 |
In this example, the lithium concentration in the raffinate from the 8 th organic phase cycle was 46ppm, and the extraction rate was 97.0%. 5363 the concentrations of lithium and sodium in aqS1 are respectively 18.4g/L and 0.62g/L, and can be used for preparing lithium carbonate.
Example 4
This embodiment is different from embodiment 1 in that: the modifier of the extractant in this example is different from the modifier of the extractant in example 1, and the structure of the beta-diketone in this example is different from that of the beta-diketone in example 1. The modifying agent is mainly characterized in that the tertiary amine extracting agent and the ketone have different structures, the ketone in the embodiment is p-methyl phenyl butanone, that is, R1, R2 and R3 are all H, and R4 is CH 3 R5 is Ar, and the structure of Ar is shown as the formula (III), R19R20, R22 and R23 are all H, R21 is CH 3 (ii) a The tertiary amine extractant in this example is trioctylamine, i.e., R6, R7, and R8 are all C 8 C 17 (ii) a The beta-diketone in this example is 1- (2,5-dimethyl) phenyl-3-isoheptyl-1,3-propanedione, i.e., R10 and R11 are both H, and R9 and R12 are both CH 3 (ii) a R13 is C 7 H 15 。
In this example, the mass ratio of ketone (p-methyl phenyl butanone) to β -diketone (1- (2,5-dimethyl) phenyl-3-isoheptyl-1,3-propanedione) was 1.6, the mass ratio of tertiary amine extractant (trioctylamine) to β -diketone (1- (2,5-dimethyl) phenyl-3-isoheptyl-1,3-propanedione) was 1.2, and the mass ratio of fatty alcohol (isotridecyl alcohol) to β -diketone (1- (2,5-dimethyl) phenyl-3-isoheptyl-1,3-propanedione) was 1.7.
Compared with the lithium extraction method provided in example 1, the lithium extraction method provided in this example has the following differences, and the remaining steps are the same:
1. preparing an extraction organic phase: according to the mass ratio of p-methyl phenylbutanone to trioctylamine to isotridecanol to 1- (2,5-dimethyl) phenyl-3-isoheptyl-1,3-propanedione =1.6, preparing an extracting agent, and then taking 230mL of the extracting agent, diluting the extracting agent to 450mL by using hydrogenated kerosene to obtain an extracted organic phase. The extractant concentration in the organic phase of the extraction was 51.1% (v/v).
2. The sodium hydroxide, sulfuric acid and the extraction equilibrium pH consumed for each cycle of the extraction organic phase are shown in table 5.
TABLE 5 sodium hydroxide and sulfuric acid consumption and extraction equilibrium pH
| Extraction unit | E1 | E2 | W1 | W2 | S1 | S2 |
| Acid/base consumption | 10-11mL | - | 2.2mL | 0.5mL | 3mL | 0.5mL |
| Equilibrium pH | 12.3-12.8 | 12.3-12.8 | 11.3-11.6 | 11.0-11.5 | 9.7-10.3 | 9.5-10.0 |
In this example, the raffinate from the 8 th organic phase cycle had a lithium concentration of 52ppm and an extraction rate of 96.6%. 5363 the concentrations of lithium and sodium in aqS are 19.1g/L and 0.58g/L, respectively, and can be used for preparing lithium carbonate.
Example 5
This embodiment is different from embodiment 1 in that: the modifier of the extractant in this example is different from the modifier of the extractant in example 1, and the structure of the beta-diketone in this example is different from that of the beta-diketone in example 1. In this example, the modifier contained only a tertiary amine extractant and a fatty alcohol, and the tertiary amine extractant and the fatty alcohol were the same as in example 1. The beta-diketone in this example was 1- (2,5-dimethyl) phenyl-3-tert-nonylThe radical-1,3-propanedione is R10 and R11 are both H, R9 and R12 are both CH 3 (ii) a R13 is C 9 H 19 。
In this example, the mass ratio of tertiary amine extractant (trioctydecylamine) to β -diketone (1- (2,5-dimethyl) phenyl-3-tert-nonyl-1,3-propanedione) was 1.2, and the mass ratio of fatty alcohol (isotridecanol) to β -diketone (1- (2,5-dimethyl) phenyl-3-isoheptyl-1,3-propanedione) was 1.2.
Compared with the lithium extraction method provided in example 1, the lithium extraction method provided in this example has the following differences, and the remaining steps are the same:
1. preparing an extraction organic phase: preparing an extracting agent according to the mass ratio of 1- (2,5-dimethyl) phenyl-3-tertiary nonyl-1,3-propanedione = 1.2. The extractant concentration in the organic phase of the extraction was 55.5% (v/v).
2. The sodium hydroxide, sulfuric acid and the extraction equilibrium pH consumed for each cycle of the extraction organic phase are shown in table 6.
TABLE 6 sodium hydroxide and sulfuric acid consumption and extraction equilibrium pH
| Extraction unit | E1 | E2 | W1 | W2 | S1 | S2 |
| Acid/base consumption | 10-11mL | - | 2.3mL | 0.5mL | 3mL | 0.5mL |
| Equilibrium pH | 12.3-12.8 | 12.3-12.8 | 11.3-11.6 | 11.0-11.5 | 9.7-10.3 | 9.5-10.0 |
In this example, the raffinate from the 8 th organic phase cycle had a lithium concentration of 61ppm and an extraction rate of 96.0%. 5363 the concentrations of lithium and sodium in aqS are 19.5g/L and 0.63g/L, respectively, and can be used for preparing lithium carbonate.
In summary, the lithium extraction agent of the present invention can effectively extract lithium element from the lithium-containing solution, and according to the lithium extraction method of the present invention, the extraction rate of lithium can be as high as 97.6%. Moreover, the lithium extracting agent does not use an organic phosphorus compound trialkyl phosphine oxide, so that the cost of the extracting agent is reduced, and the pollution level to the environment is reduced, so that the three-waste treatment cost is reduced, the cost for extracting lithium by a solvent extraction technology can be directly and indirectly reduced, and the lithium extracting agent has a very excellent industrial application prospect.
The above are merely examples of the present invention, and the present invention is not limited to the field related to this embodiment, and the common general knowledge of the known specific structures and characteristics in the schemes is not described herein too much, and those skilled in the art can know all the common technical knowledge in the technical field before the application date or the priority date, can know all the prior art in this field, and have the ability to apply the conventional experimental means before this date, and those skilled in the art can combine their own ability to perfect and implement the scheme, and some typical known structures or known methods should not become barriers to the implementation of the present invention by those skilled in the art in light of the teaching provided in the present application. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the present invention. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. A lithium extractant, characterized by: the modifier comprises one or more of tertiary amine extractant, aldehyde, ketone and fatty alcohol, wherein the carbon atom number of the fatty alcohol is 8-20, the aldehyde and ketone have a structure shown in a formula (I), and the tertiary amine extractant has a structure shown in a formula (II);
in the formula (I), R1, R2, R3 and R5 are respectively and independently selected from the following groups: H. ar, C n H 2n+1 ，C n H 2n+1 N =1-10, R4= C n H 2n+1 ，n＝1-15；
In the formula (II), R6, R7 and R8 are respectively C n H 2n+1 ，n＝6-20；
Wherein, the structure of Ar is shown as formula (III) or formula (IV);
in the formulas (III) and (IV), R19, R20, R21, R22 and R23 are each independently H or CH 3 。
2. The lithium extractant of claim 1, characterized in that: the structure of the beta-diketone is shown as a formula (V);
in the formula (V), R9, R10, R11 and R12 are each independently H or CH 3 ，R13＝C n H 2n+1 ，n＝5-15。
3. The lithium extractant of claim 1, characterized in that: in the chemical structure of the aldehyde, R5= H, R1, R2 and R3 are respectively independent H or straight-chain alkyl with 1-3 carbon atoms, and the sum of the carbon atoms of R1, R2, R3 and R4 is between 4 and 15.
4. The lithium extractant of claim 1, characterized in that: in the chemical structure of the ketone, R5 is phenyl, R1, R2 and R3 are respectively H or straight-chain alkyl with 1-3 carbon atoms, and the sum of the carbon atoms of R1, R2, R3 and R4 is between 3 and 10.
5. The lithium extractant of claim 1, characterized in that: in the formula (II), the total number of carbon atoms of R6, R7 and R8 is between 20 and 30.
6. The lithium extractant of claim 2, characterized in that: in the formula (V), R9, R10, R11 and R12 are all H, and the carbon number of R13 is between 5 and 10.
7. The lithium extractant of claim 1, characterized in that: in the modifier, the mass ratio of the sum of the aldehyde and ketone to the beta-diketone is 0.5-2.5; or the mass ratio of the ketone to the beta-diketone is 0.5-2.5.
8. The lithium extractant of claim 1, characterized in that: in the modifier, the mass ratio of aldehyde to ketone is 0-1.5.
9. The lithium extractant of claim 1, characterized in that: in the modifier, the mass ratio of the tertiary amine extractant to the beta-diketone is 1-2:1;
and/or in the modifier, the mass ratio of the fatty alcohol to the beta-diketone is 1-3:1.
10. A lithium extraction method, characterized in that: comprising extracting a lithium-containing solution with an extraction organic phase comprising a lithium extractant as defined in any of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3479147A (en) * | 1966-11-22 | 1969-11-18 | Atomic Energy Commission | Extraction of lithium values |
| JP2009161794A (en) * | 2007-12-28 | 2009-07-23 | Kumamoto Technology & Industry Foundation | Method for recovering lithium, and lithium recovering apparatus using the method |
| CN110240183A (en) * | 2019-08-02 | 2019-09-17 | 青岛华友恒新能源材料技术研究院有限公司 | A kind of preparation method of lithium carbonate |
| US20220205064A1 (en) * | 2020-12-31 | 2022-06-30 | Cytec Industries Inc. | Recovering mixed-metal ions from aqueous solutions |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3479147A (en) * | 1966-11-22 | 1969-11-18 | Atomic Energy Commission | Extraction of lithium values |
| JP2009161794A (en) * | 2007-12-28 | 2009-07-23 | Kumamoto Technology & Industry Foundation | Method for recovering lithium, and lithium recovering apparatus using the method |
| CN110240183A (en) * | 2019-08-02 | 2019-09-17 | 青岛华友恒新能源材料技术研究院有限公司 | A kind of preparation method of lithium carbonate |
| US20220205064A1 (en) * | 2020-12-31 | 2022-06-30 | Cytec Industries Inc. | Recovering mixed-metal ions from aqueous solutions |
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