CN116983964B - Lithium-sodium separation material and preparation method and application method thereof - Google Patents
Lithium-sodium separation material and preparation method and application method thereof Download PDFInfo
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- CN116983964B CN116983964B CN202311122511.6A CN202311122511A CN116983964B CN 116983964 B CN116983964 B CN 116983964B CN 202311122511 A CN202311122511 A CN 202311122511A CN 116983964 B CN116983964 B CN 116983964B
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- 238000000926 separation method Methods 0.000 title claims abstract description 55
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000012267 brine Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 10
- 239000013522 chelant Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 230000008961 swelling Effects 0.000 claims abstract description 6
- 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 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/42—Selective adsorption, e.g. chromatography characterised by the development mode, e.g. by displacement or by elution
- B01D15/424—Elution mode
- B01D15/426—Specific type of solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- 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
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a lithium-sodium separation material, a preparation method and an application method thereof, wherein the preparation method comprises the following steps: s1, synthesizing polyamino resin: swelling macroporous resin in polyamine for 12-24 h, heating to 110-120 ℃, carrying out reflux reaction for 15-24 h, and washing the reacted resin with pure water to obtain polyamino resin; s2, synthesizing polyamino phosphonic acid chelate resin: mixing the polyamino resin obtained in the step S1 with phosphorous acid, concentrated hydrochloric acid and deionized water, heating to 50-70 ℃, slowly adding aldehyde compounds, heating to 60-100 ℃ and carrying out reflux reaction for 8-16 h; s3, purifying: and (3) purifying and drying the material obtained in the step (S2) to obtain a lithium-sodium separation material, wherein the lithium-sodium separation material can effectively separate lithium from sodium by a chromatographic column separation-like method. The polyaminophosphonic acid chelate resin prepared by the invention has excellent performance of lithium-sodium separation, and is suitable for lithium-sodium separation in high-concentration brine.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a lithium-sodium separation material, a preparation method and an application method thereof.
Background
The rapid development of new energy industry causes the increasing demand for lithium resources, and further, the continuous exploitation and consumption of ore lithium resources brings a series of problems of high cost, high consumption, high pollution and the like, thereby limiting the further expansion and development of the lithium extraction mode. In comparison, the salt lake brine has rich lithium content, and along with the continuous development of the mining technology, the salt lake brine has great development potential for extracting lithium. And with the sudden increase in the trade volume of lithium resources, how to recover high-quality lithium salts from low-quality salt lake brine is a key issue of research.
At present, the main methods for extracting lithium from brine include an evaporation crystallization method, a precipitation method, a calcination leaching method, a membrane separation method and a solvent extraction method. The extraction method is a method for separating metal ions in wide industrial application, and the Chinese patent application (CN 109628758B) discloses an extraction solvent for lithium elements and an extraction method thereof, wherein the extraction solvent containing phosphate groups is used for extracting the lithium elements in mixed feed liquid, but the extraction method inevitably generates a large amount of wastewater, and the possibility that an organic phase and an aqueous phase are mixed to generate a third phase exists, so that the COD of water is increased, and the treatment cost is increased. Compared with an extraction method, the ion exchange method solves the problem, wherein aminophosphonic acid is used as a functional group containing double active centers, can generate stronger coordination with metal elements, and is widely used as a chelating group in the fields of wastewater treatment, metal element enrichment, mineral flotation and the like. Currently, researchers have used aminophosphonic acid materials for lithium-sodium separation, wherein chinese patent application (CN 108421539B) discloses a material for lithium-sodium separation, focusing on the key role of N-N bond (hydrazine) in lithium-sodium separation, but the use of hydrazine in synthesis is at a certain risk, and hydrazine is easily oxidized and unstable. The phosphoramidate group is widely used on chelating resin at present, but the exchange capacity of single phosphate group on functional monomer is limited, so that it is necessary to develop a stable, high ion exchange amount phosphoramidate material for lithium-sodium separation.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a lithium-sodium separation material, a preparation method and an application method thereof, wherein the invention generates polyamino phosphoric acid chelate resin containing a plurality of phosphoric acid groups on a monomer through Mannich reaction, the polyamino phosphoric acid chelate resin has excellent performance of lithium-sodium separation, and the separation technology is improved by using a chromatographic column separation-like principle to achieve the effect of lithium-sodium separation, the lithium-sodium separation material is suitable for brine lithium-sodium separation, the mass ratio of lithium to sodium is 0.008-1, and the high-concentration brine only contains Li and Na ions and does not contain other metal ions.
The technical scheme of the invention is as follows:
The invention relates to a preparation method of a lithium-sodium separation material, which comprises the following steps:
S1, synthesizing polyamino resin: swelling macroporous resin in polyamine for 12-24 h, heating to 110-120 ℃, carrying out reflux reaction for 15-24 h, and washing the reacted resin with pure water to obtain polyamino resin;
s2, synthesizing polyamino phosphonic acid chelate resin: mixing the polyamino resin obtained in the step S1 with phosphorous acid, concentrated hydrochloric acid and deionized water, heating to 50-70 ℃, slowly adding aldehyde compounds, heating to 60-100 ℃ and carrying out reflux reaction for 8-16 h;
S3, purifying: and (3) purifying and drying the material obtained in the step (S2) to obtain the lithium-sodium separation material.
Preferably, in step S1, the polyamine is one or more of diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine; the macroporous resin is styrene series chlorine balls or methyl acrylate series macroporous resin.
Preferably, in step S1, the mixing mass ratio of the macroporous resin to the polyamine is 1: (3-6).
Preferably, in the step S2, the aldehyde compound is one or a mixture of several of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde; further preferably, formaldehyde is added in the form of a formaldehyde solution, and the mass concentration of the formaldehyde solution is 37-44%.
Preferably, in step S2, the polyamino resin: phosphorous acid: the mass ratio of the aldehyde compounds is 1: (0.5-0.9): (0.2 to 0.5); the mass concentration of the concentrated hydrochloric acid is 35-37%, and the polyamino resin: concentrated hydrochloric acid: the mass ratio of deionized water is 1: (2-5): (2-5).
Preferably, in step S3, the purification is performed by washing with ethanol, water or recovering the solvent by distillation; the temperature condition of the drying is 40-60 ℃.
The invention also relates to a lithium-sodium separation material prepared by the preparation method.
The invention also relates to a lithium-sodium separation method by utilizing the lithium-sodium separation material, which comprises the following steps:
(1) Filling a chromatographic column: filling a lithium-sodium separation material into a chromatographic column with the height-diameter ratio of 8-20;
(2) Adsorption: pretreating resin by using acid liquor before adsorption, then injecting an adsorption water sample from one end of a chromatographic column, wherein the volume of the adsorption water sample is 0.5-2.5 BV, and the adsorption flow rate is 1-5 BV/h;
(3) Analysis: resolving by using 5-15% acid liquor, wherein the acid liquor has a volume of 3-6 BV, an adsorption flow rate of 1-5 BV/h, and resolving liquor is reserved every 0.5-1 BV;
(4) And (5) applying qualified liquid mechanically: repeating the steps S2-S3 to concentrate and retain the analysis liquid.
Preferably, the acid solution in steps (2) and (3) is one or more of hydrochloric acid, sulfuric acid, nitric acid.
Preferably, the adsorption water sample in the step (2) is brine, the mass ratio of lithium to sodium (Li/Na) is 0.008-1, and the brine only contains Li and Na ions and does not contain other metal ions.
The beneficial effects of the invention are as follows:
1) The polyamino phosphonic acid type chelate resin synthesized by the method has excellent lithium-sodium separation performance, the selectivity of phosphate groups to lithium is stronger than that of sodium, the selection effect is amplified by using the polyphosphate groups, and the lithium-sodium separation is carried out by matching with the ion separation principle of a chromatographic column, so that the method has industrial application prospect;
2) The preparation method is simple to operate, the reagent cost is low, and the reaction conditions are mild; and reduces the use of toxic reagents and dangerous surface treatment means.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is an infrared spectrum of a lithium-sodium separation material prepared in example 1;
FIG. 2 is a schematic diagram showing the relationship between the concentration of Li and Na ions in the analytical solution and the amount of the analytical solution in example 1.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
In addition, styrene-based chlorine balls (containing 15 to 18wt percent of chlorine and having a granularity of 0.03 to 0.06 cm) and acrylic methyl ester balls (containing 16 to 20wt percent of methyl ester and having a granularity of 0.03 to 0.06 cm) involved in the synthesis of the lithium-sodium separation material of the present invention are all purchased from Shanghai resin factories.
Example 1
Synthesis of lithium sodium separation material
S1, synthesizing polyamino resin: swelling styrene-series chlorine ball macroporous resin in diethylenetriamine for 12 hours, wherein the mass ratio of the macroporous resin to the diethylenetriamine is 1:5, heating to 110 ℃ at a speed of 2 ℃/min, carrying out reflux reaction for 16 hours, and washing the reacted resin with pure water to obtain polyamino resin;
s2, synthesizing polyamino phosphonic acid chelate resin: mixing polyamino resin with phosphorous acid, concentrated hydrochloric acid and deionized water, heating to 60 ℃, slowly adding formaldehyde solution (Wt 37%), and heating to 100 ℃ for reflux reaction for 8h; wherein, the mass ratio of the polyamino resin to the phosphorous acid to the aldehyde compound is 1:0.5:0.3, concentrated hydrochloric acid with a mass concentration of 37%, wherein the polyamino resin: concentrated hydrochloric acid: the mass ratio of deionized water is 1:5:5, a step of;
s3, purifying: and (3) recovering the solvent from the material obtained in the step (S2) in a distillation mode, and drying at 60 ℃ to obtain the product lithium-sodium separation material.
The lithium-sodium separation material prepared by the embodiment is used for lithium-sodium separation, and the specific application method is as follows:
(1) Filling a chromatographic column: loading 10mL of lithium-sodium separation material into a chromatographic column with the height-diameter ratio of 10;
(2) Adsorption: pretreating by using hydrochloric acid with the mass concentration of 5% before adsorption, then injecting an adsorption water sample from one end of a chromatographic column, wherein the volume of the adsorption water sample is 1BV, and the adsorption flow rate is 2BV/h;
(3) Analysis: resolving by using hydrochloric acid solution with the mass concentration of 10%, wherein the acid solution has the volume of 5BV and the adsorption flow rate of 2BV/h, and resolving solution is reserved every 0.5 BV;
(4) And (5) applying qualified liquid mechanically: repeating the steps S2-S3 on the qualified liquid with the lithium-sodium ratio being more than 1, and concentrating and retaining the analysis liquid.
The infrared spectrograms of the lithium-sodium separation material prepared in the embodiment are shown in fig. 1, absorption peaks at 3377cm -1 and 3120cm -1 represent that the composite material with the amino functional group on the surface is successfully synthesized, and characteristic peaks at 1162cm -1 and vibration peaks at 1062cm -1 represent that the composite material with the phosphate group is successfully synthesized.
Example 2
Synthesis of lithium sodium separation material
S1, synthesizing polyamino resin: swelling methyl acrylate macroporous resin in diethylenetriamine for 12 hours, wherein the mixing mass ratio of the macroporous resin to the diethylenetriamine is 1:5, heating to 110 ℃ at a speed of 2 ℃/min, carrying out reflux reaction for 16 hours, and washing the reacted resin with pure water to obtain polyamino resin;
S2, synthesizing polyamino phosphonic acid chelate resin: mixing polyamino resin with phosphorous acid, concentrated hydrochloric acid and deionized water, heating to 60 ℃, slowly adding formaldehyde solution (Wt 37%), and heating to 100 ℃ for reflux reaction for 8h; wherein, the mass ratio of the polyamino resin to the phosphorous acid to the aldehyde compound is 1:0.5:0.4, concentrated hydrochloric acid with a mass concentration of 37%, polyamino resin: concentrated hydrochloric acid: the mass ratio of deionized water is 1:5:5, a step of;
s3, purifying: and (3) recovering the solvent from the material obtained in the step (S2) in a distillation mode, and drying at 60 ℃ to obtain the product lithium-sodium separation material.
The lithium-sodium separation material prepared by the embodiment is used for lithium-sodium separation, and the specific application method is as follows:
(1) Filling a chromatographic column: loading 10mL of lithium-sodium separation material into a chromatographic column with the height-diameter ratio of 10;
(2) Adsorption: before adsorption, hydrochloric acid with the mass concentration of 5% is used for pretreatment of the resin, then an adsorption water sample is injected from one end of the chromatographic column, the volume of the adsorption water sample is 1BV, and the adsorption flow rate is 2BV/h;
(3) Analysis: resolving by using hydrochloric acid solution with the mass concentration of 10%, wherein the acid solution has the volume of 5BV and the adsorption flow rate of 2BV/h, and resolving solution is reserved every 0.5 BV;
(4) And (5) applying qualified liquid mechanically: repeating the steps S2-S3 to concentrate and retain the analysis liquid.
Example 3
Synthesis of lithium sodium separation material
S1, synthesizing polyamino resin: swelling styrene chlorball macroporous resin in tetraethylenepentamine for 12 hours, wherein the mass ratio of the macroporous resin to the tetraethylenepentamine is 1:5, heating to 110 ℃ at a speed of 2 ℃/min, carrying out reflux reaction for 16 hours, and washing the reacted resin with pure water to obtain polyamino resin;
S2, synthesizing polyamino phosphonic acid chelate resin: mixing polyamino resin with phosphorous acid, concentrated hydrochloric acid and deionized water, heating to 60 ℃, slowly adding formaldehyde solution (Wt 37%), and heating to 100 ℃ for reflux reaction for 8h; wherein, the mass ratio of the polyamino resin to the phosphorous acid to the aldehyde compound is 1:0.6:0.3, concentrated hydrochloric acid with a mass concentration of 37%, polyamino resin: concentrated hydrochloric acid: the mass ratio of deionized water is 1:5:5, a step of;
s3, purifying: and (3) recovering the solvent from the material obtained in the step (S2) in a distillation mode, and drying at 60 ℃ to obtain the product lithium-sodium separation material.
The lithium-sodium separation material prepared by the embodiment is used for lithium-sodium separation, and the specific application method is as follows:
(1) Filling a chromatographic column: loading 10mL of lithium-sodium separation material into a chromatographic column with the height-diameter ratio of 10;
(2) Adsorption: before adsorption, hydrochloric acid with the mass concentration of 5% is used for pretreatment of the resin, then an adsorption water sample is injected from one end of the chromatographic column, and the volume of the adsorption water sample is 2BV; the adsorption flow rate is 2BV/h;
(3) Analysis: resolving by using hydrochloric acid solution with the mass concentration of 10%, wherein the acid solution has the volume of 5BV and the adsorption flow rate of 2BV/h, and resolving solution is reserved every 0.5 BV;
(4) And (5) applying qualified liquid mechanically: repeating the steps S2-S3 to concentrate and retain the analysis liquid.
Lithium-sodium separation was performed on the products obtained in examples 1 to 3, and the adsorption fraction data are shown in Table 1 below:
Table 1 effect of lithium sodium separation material on adsorption of salt lake brine
As is apparent from table 1 above, the polyaminophosphonic acid resin synthesized by the present invention is excellent in lithium adsorption performance.
The desorption test was performed according to the desorption process, and the data thereof are shown in the following table 2:
Table 2 effect of lithium sodium separation material on desorption of salt lake brine
As can be seen from the data in Table 2, at 2.5-5 BV, the lithium-sodium ratio of the effluent is greater than 1, and the effluent is qualified liquid and can be used for further concentration treatment.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (9)
1. The preparation method of the lithium-sodium separation material is characterized by comprising the following steps of:
s1, synthesizing polyamino resin: swelling macroporous resin in polyamine for 12-24 h, heating to 110-120 ℃, carrying out reflux reaction for 15-24 h, and washing the reacted resin with pure water to obtain polyamino resin; wherein the polyamine is one or a mixture of more of diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine; the macroporous resin is styrene series chlorine balls or methyl acrylate series macroporous resin;
s2, synthesizing polyamino phosphonic acid chelate resin: mixing the polyamino resin obtained in the step S1 with phosphorous acid, concentrated hydrochloric acid and deionized water, heating to 50-70 ℃, slowly adding aldehyde compounds, heating to 60-100 ℃ and carrying out reflux reaction for 8-16 h;
S3, purifying: and (3) purifying and drying the material obtained in the step (S2) to obtain the lithium-sodium separation material.
2. The preparation method according to claim 1, wherein in step S1, the mixing mass ratio of the macroporous resin to the polyamine is 1: (3-6).
3. The preparation method according to claim 1, wherein in the step S2, the aldehyde compound is one or a mixture of several of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde.
4. The method according to claim 1, wherein in step S2, the polyamino resin: phosphorous acid: the mass ratio of the aldehyde compounds is 1: (0.5-0.9): (0.2 to 0.5); the mass concentration of the concentrated hydrochloric acid is 35-37%, and the polyamino resin: concentrated hydrochloric acid: the mass ratio of deionized water is 1: (2-5): (2-5).
5. The method of claim 1, wherein in step S3, the purification is performed by washing with ethanol, water or by recovering the solvent by distillation; the temperature condition of the drying is 40-60 ℃.
6. A lithium-sodium separation material, characterized by being produced by the production method according to any one of claims 1 to 5.
7. A lithium-sodium separation method using the lithium-sodium separation material according to claim 6, comprising the steps of:
(1) Filling a chromatographic column: filling a lithium-sodium separation material into a chromatographic column with the height-diameter ratio of 8-20;
(2) Adsorption: pretreating resin by using acid liquor before adsorption, then injecting an adsorption water sample from one end of a chromatographic column, wherein the volume of the adsorption water sample is 0.5-2.5 BV, and the adsorption flow rate is 1-5 BV/h;
(3) Analysis: resolving by using 5-15% acid liquor, wherein the acid liquor has a volume of 3-6 BV, an adsorption flow rate of 1-5 BV/h, and resolving liquor is reserved every 0.5-1 BV;
(4) And (5) applying qualified liquid mechanically: repeating the steps S2-S3 to concentrate and retain the analysis liquid.
8. The method of claim 7, wherein the acid solution in steps (2) and (3) is one or more of hydrochloric acid, sulfuric acid, and nitric acid.
9. The method of claim 7, wherein the adsorbed water sample in the step (2) is brine, the mass ratio of lithium to sodium is 0.008-1, and the brine only contains Li and Na ions and does not contain other metal ions.
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