CN114134327A - Process and device for preparing lithium carbonate from carbonic acid type brine - Google Patents
Process and device for preparing lithium carbonate from carbonic acid type brine Download PDFInfo
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- CN114134327A CN114134327A CN202111065343.2A CN202111065343A CN114134327A CN 114134327 A CN114134327 A CN 114134327A CN 202111065343 A CN202111065343 A CN 202111065343A CN 114134327 A CN114134327 A CN 114134327A
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- 239000012267 brine Substances 0.000 title claims abstract description 90
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 89
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 44
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims description 15
- 238000000034 method Methods 0.000 title abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 86
- 238000001556 precipitation Methods 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000003463 adsorbent Substances 0.000 claims abstract description 45
- 239000012528 membrane Substances 0.000 claims abstract description 42
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 37
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 37
- 238000003795 desorption Methods 0.000 claims description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000004458 analytical method Methods 0.000 claims description 13
- 238000000909 electrodialysis Methods 0.000 claims description 13
- -1 hydrogen ions Chemical class 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229920001429 chelating resin Polymers 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 238000009292 forward osmosis Methods 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000013014 purified material Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 150000005323 carbonate salts Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a technology for extracting lithium from salt lake brine, in particular to a technology for extracting lithium carbonate from carbonate type salt lake brine. The carbonate brine is treated in the invention, contains more carbonate ions, fully utilizes and adsorbs carbonate in tail brine, and serves as a carbon source in the preparation process of lithium carbonate without adding sodium carbonate for reaction; in the process of the lithium precipitation reaction, the bipolar membrane technology is utilized to treat the lithium precipitation mother liquor to obtain acid and alkali, the acid is used for resolving the adsorbent, and the alkali is used for the lithium precipitation reaction and adsorption, so that a closed cycle of the previous and subsequent processes is formed, the raw material cost is saved, and the lithium recovery rate is improved.
Description
Technical Field
The invention relates to a technology for extracting lithium from salt lake brine, in particular to a technology for extracting lithium carbonate from carbonate type salt lake brine.
Background
Lithium is an important strategic resource substance and is an indispensable important raw material of modern high-tech products. With the wide application of lithium and lithium salt and the continuous development of high and new technology, especially the rapid development of lithium battery industry in recent years, the demand of the market for lithium is rapidly increased. At present, lithium salt is mostly extracted from the ore in China, but with the continuous reduction of high-grade lithium ore and the continuous improvement of the cost of extracting lithium from the ore, and because the salt lake is rich in a large amount of lithium elements, the lithium extraction from the salt lake gradually draws attention of people.
China has huge lithium resource reserves, is second to Vivia only and is located in the second position in the world. The Tibet of China has rich lithium resources in the hydrochloride salt lakes, and the famous carbonate salt lakes comprise Bangkong, Dangzongiao, Zabuye tea card, Guogaline and the like, wherein the Zabuye salt lake is the first and third salt lakes in China, and the lithium carbonate reserve is about 184 ten thousand tons. Carbonate type lithium salt lake due to CO existing in large amount in brine3 2-Limit Ca2+、Mg2+The concentration range of the salt lake exists in the brine, so that the small magnesium-lithium ratio of the brine is created, and the carbonate salt lake is a high-quality resource for extracting lithium from the brine.
At present, a gradient solar cell process is adopted for extracting lithium from a carbonate salt lake, and patent CN1398786A provides a method for extracting lithium carbonate from carbonate salt lake brine by crystallizing and separating out the lithium carbonate from the carbonate salt lake brine by using solar energy and taking an solar cell as a crystallization cell. The method has the advantages of simple operation and low cost, but has the problems of low lithium yield, need of constructing a salt field, long lithium extraction period, low product purity, difficulty in quickly expanding the productivity and the like.
Disclosure of Invention
The invention aims to provide a process and a device for preparing lithium carbonate from carbonate type salt lake brine.
A process for preparing lithium carbonate from carbonic acid type brine comprises the following steps:
and 3, mixing the analysis solution with tail halogen, and performing precipitation reaction of lithium carbonate to obtain lithium carbonate.
In one embodiment, the desorption solution is mixed with tail halide after membrane concentration and/or resin purification.
In one embodiment, the concentrations of lithium ion, calcium ion and magnesium ion are 5-40g/L, 0.0001-0.1g/L and 0.0001-0.1g/L respectively after membrane concentration and resin purification treatment.
The membrane concentration is selected from reverse osmosis concentration, forward osmosis concentration or electrodialysis concentration.
The resin purification adopts chelating resin or ion exchange resin.
In one embodiment, the concentrations of lithium, sodium, magnesium, boron, carbonate, and chloride ions in the carbonated brine are 0.1-15g/L, 10-150g/L, 0.01-1g/L, 0.1-4g/L, 14-60g/L, and 15-154g/L, respectively.
In one embodiment, the lithium extraction adsorbent is selected from a titanium-based or manganese-based adsorbent.
In one embodiment, the desorption treatment uses an acid for desorption; the acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid or acetic acid solution, wherein the concentration of hydrogen ions is 0.01-1 mol/L.
In one embodiment, the tail halide has a lithium ion concentration of 0.05 to 1g/L and a carbonate concentration of 14 to 60 g/L.
In one embodiment, the reaction temperature in the precipitation reaction is 45-95 ℃, and the pH is adjusted to 9-14 by adding alkali liquor in the reaction process.
In one embodiment, solid-liquid separation is performed on lithium carbonate obtained after the precipitation reaction, and the obtained mother liquor is subjected to bipolar membrane electrodialysis treatment to obtain an acid solution and an alkali solution.
In one embodiment, the concentration of hydrogen ions in the acid solution is 1.0-2.5 mol/L, and the acid solution is recycled for desorption of a lithium extraction adsorbent or for removal of redundant carbonate ions in a mother solution.
In one embodiment, the concentration of hydroxide ions in the alkali liquor is 1.0-2.5 mol/L, and the alkali liquor is recycled for pH adjustment in a precipitation reaction or pH adjustment before a carbonic acid type brine is used for adsorption of a lithium extraction adsorbent.
An apparatus for preparing lithium carbonate from carbonated brine, comprising:
the adsorbent tank is used for carrying out lithium adsorption treatment on the carbonate brine;
the tail brine storage tank is connected to the adsorbent tank and is used for collecting the residual brine after lithium adsorption;
the desorption liquid tank is used for adding desorption liquid into the adsorbent tank to obtain eluent containing lithium ions;
and the precipitation reaction tank is respectively connected with the analysis solution outlet of the adsorbent tank and the tail brine storage tank and is used for carrying out precipitation reaction of the lithium carbonate.
Further comprising: and the solid-liquid separation equipment is connected to the precipitation reaction tank and is used for separating the lithium carbonate in the material after the precipitation reaction.
The solid-liquid separation equipment is selected from one or a combination of a plurality of centrifuges, filters or settlers.
Further comprising: and the bipolar membrane electrodialyzer is connected to the mother liquor side of the solid-liquid separation equipment and is used for performing bipolar membrane electrodialysis treatment on the mother liquor.
Further comprising: and the acid liquid tank and the alkali liquid tank are respectively connected with the acid liquid side and the alkali liquid side of the bipolar membrane electrodialyzer and used for storing the acid liquid and the alkali liquid.
The acid solution tank is connected with the desorption solution tank and is used for supplying the acid solution to the desorption solution tank.
The alkali liquor tank is connected with the precipitation reaction tank and/or the adsorbent tank and is used for respectively supplying alkali liquor into the precipitation reaction tank or the adsorbent tank.
Further comprising: and the membrane concentrator is connected with the analytic solution outlet of the adsorbent tank and is used for concentrating the analytic solution and supplying the concentrated solution to the precipitation reaction tank.
The membrane concentrator is selected from one or a combination of a reverse osmosis concentrator, a forward osmosis concentrator or an electrodialysis concentrator.
Further comprising: and the resin tower is connected to the concentration side of the membrane concentrator and is used for purifying the concentrated solution obtained by the membrane concentrator to cations and feeding the purified material into the precipitation reaction tank.
The resin tower is filled with chelating resin or ion exchange resin.
Advantageous effects
(1) The method does not need to construct a salt pan for brine drying, not only shortens the lithium extraction period, but also avoids the problem of low lithium yield caused by the problem that brine infiltrates or lithium salt is carried in salt crystallization in the brine drying process. In addition, the invention can realize continuous automatic production and is easy to expand the capacity.
(2) The carbonate brine is treated in the invention, contains more carbonate ions, fully utilizes and adsorbs carbonate in tail brine, and serves as a carbon source in the preparation process of lithium carbonate without adding sodium carbonate for reaction; in the process of the lithium precipitation reaction, the bipolar membrane technology is utilized to treat the lithium precipitation mother liquor to obtain acid and alkali, the acid is used for resolving the adsorbent, and the alkali is used for the lithium precipitation reaction and adsorption, so that a closed cycle of the previous and subsequent processes is formed, the raw material cost is saved, and the lithium recovery rate is improved.
(3) The preparation process is simple to operate, low in cost, free of chemical consumption and environment hazards, and suitable for extracting lithium from carbonate salt lakes in Tibet and abroad.
Drawings
Fig. 1 is a flow chart of a process for preparing lithium carbonate from carbonate lake brine in example 1.FIG. 2 shows this patent The apparatus of (1).
Wherein, 1, an adsorbent tank; 2. a tail bittern storage tank; 3. a desorption liquid tank; 4. a membrane concentrator; 5. a resin tower; 6. a precipitation reaction tank; 7. a solid-liquid separation device; 8. bipolar membrane electrodialysers; 9. an acid liquor tank; 10. and a lye tank.
Detailed Description
The invention provides a process method for preparing lithium carbonate from carbonate type salt lake brine, which comprises the following steps:
(1) absorbing carbonic acid type brine by adopting a lithium extraction adsorbent, and performing acid analysis to obtain two streams of brine, namely tail brine containing a large amount of carbonate after absorption and a lithium-containing analysis solution; in some typical implementations, the concentrations of lithium, sodium, magnesium, boron, carbonate, and chloride ions in the carbonated brine are 0.1-15g/L, 10-150g/L, 0.01-1g/L, 0.1-4g/L, 14-60g/L, and 15-154g/L, respectively; the adsorbent used herein is not particularly limited, and lithium adsorbent known in the art may be used to adsorb lithium in brine, and for example, titanium-based or manganese-based adsorbents; after adsorption treatment, most of lithium in the brine can be adsorbed by an adsorbent, and then is eluted by deionized water or dilute acid to obtain a lithium-containing analysis solution, wherein the acid in the acid analysis process is at least one of hydrochloric acid, sulfuric acid, nitric acid or acetic acid solution, and the concentration of hydrogen ions is 0.01-1 mol/L; after lithium in the fed brine is adsorbed, the proportion of carbonate to other ions is remarkably increased, the concentration of lithium ions in tail brine after adsorption is 0.05-1g/L, and the concentration of carbonate is 14-60 g/L.
(2) Concentrating the lithium-containing analysis solution by adopting a membrane, purifying the solution by using resin, and enriching to obtain lithium-rich brine; for the analytic solution, lithium ions can be mainly contained, and small amount of other ions (such as sodium ions and other divalent ions) can also be contained, when the analytic solution is subjected to membrane concentration treatment, the concentration of the lithium ions can be increased, and meanwhile, the analytic solution is subjected to treatment by some ion exchange resins, some other cations in the analytic solution can be adsorbed and replaced by the sodium ions, so that impurity precipitation in subsequent lithium precipitation reaction is avoided, and the resin purification can be one or more of chelating resin or ion exchange resin; the membrane concentration can be one or more of reverse osmosis concentration, forward osmosis concentration and electrodialysis concentration; the concentrations of lithium ion, calcium ion and magnesium ion in the lithium-rich brine are respectively 5-40g/L, 0.0001-0.1g/L and 0.0001-0.1 g/L;
(3) mixing the lithium-rich brine and the tail brine after adsorption to perform a lithium precipitation reaction to obtain a lithium carbonate product; carbonate ions can be added in the lithium precipitation reaction to react with lithium, in the process, tail water after adsorption treatment is particularly adopted, wherein the tail water contains a large proportion of carbonate ions, and lithium carbonate precipitation is obtained after the tail water reacts with the lithium; mixing the lithium-rich brine and the tail brine after adsorption to precipitate lithium, wherein the reaction temperature is 45-95 ℃, and adding alkali liquor to adjust the pH value to 9-14 in the reaction process;
(4) and preparing acid and alkali from the lithium precipitation mother liquor by adopting bipolar membrane electrodialysis, wherein the acid is used for extracting a lithium adsorbent to analyze and remove redundant carbonate in the lithium precipitation mother liquor, and the alkali is used for lithium carbonate precipitation reaction to adjust alkali and is mixed into brine to enter an adsorption device. In the step, lithium carbonate is generated through the reaction of carbonate ions and lithium ions in the lithium precipitation process, sodium chloride is generated through the reaction in the mother liquor after the sodium carbonate is introduced, and a NaOH solution and an HCl solution can be obtained after the bipolar membrane electrodialysis treatment; the concentration of hydrogen ions in the acid solution prepared by the bipolar membrane is 1.0-2.5 mol/L, and the concentration of hydroxide ions in the alkali solution is 1.0-2.5 mol/L;
the whole process of the invention does not need to supplement sodium carbonate raw material and acid and alkali additionally.
Based on the above method, the apparatus provided in this patent, as shown in fig. 2, includes:
an adsorbent tank 1 for adsorbing lithium to carbonate brine;
a tail brine storage tank 2 connected to the adsorbent tank 1 and used for collecting the residual brine after lithium adsorption;
a desorption liquid tank 3 for adding a desorption liquid into the adsorbent tank 1 to obtain an eluent containing lithium ions;
and the precipitation reaction tank 6 is respectively connected with the analysis solution outlet of the adsorbent tank 1 and the tail brine storage tank 2 and is used for carrying out precipitation reaction of lithium carbonate.
Further comprising: and the solid-liquid separation equipment 7 is connected to the precipitation reaction tank 6 and is used for separating lithium carbonate in the materials after the precipitation reaction.
The solid-liquid separation equipment 7 is one or a combination of a plurality of centrifuges, filters or settlers.
Further comprising: and the bipolar membrane electrodialyzer 8 is connected to the mother liquor side of the solid-liquid separation equipment 7 and is used for performing bipolar membrane electrodialysis treatment on the mother liquor.
Further comprising: and the acid liquid tank 9 and the alkali liquid tank 10 are respectively connected with the acid liquid side and the alkali liquid side of the bipolar membrane electrodialyzer and used for storing acid liquid and alkali liquid.
The acid liquor tank 9 is connected with the desorption liquor tank 3 and is used for supplying acid liquor to the desorption liquor tank 3.
The lye tank 10 is connected with the precipitation reaction tank 6 and/or the adsorbent tank 1 and is used for respectively supplying lye into the precipitation reaction tank 6 or the adsorbent tank 1.
Further comprising: and a membrane concentrator 4 connected to the desorption solution outlet of the adsorbent tank 1, for concentrating the desorption solution and supplying the concentrated solution to the precipitation reaction tank 6.
The membrane concentrator 4 is selected from one or a combination of a reverse osmosis concentrator, a forward osmosis concentrator or an electrodialysis concentrator.
Further comprising: and a resin column 5 connected to the concentration side of the membrane concentrator 4 for purifying the cation of the concentrated solution obtained by the membrane concentrator 4 and supplying the purified material to the precipitation reaction tank 6.
The resin tower 5 is filled with chelating resin or ion exchange resin.
Example 1
The embodiment provides a process method for preparing lithium carbonate from carbonate lake brine, wherein the brine used is carbonate lake brine from a salt lake in Tibet, the concentrations of main ions, namely lithium ions, sodium ions, magnesium ions, boron elements and carbonate ions in the original brine are respectively 0.30g/L, 44.0g/L, 0.08g/L, 0.6g/L and 18.9g/L, and the process of the embodiment is shown in FIG. 1, and the method of the embodiment comprises the following steps:
and (3) feeding the carbonate type salt lake brine into a pretreatment multi-medium filter to filter and remove part of mechanical impurities such as silt and the like to obtain pretreated brine.
Sending the pretreated brine into a device filled with a titanium adsorbent, and after adsorption, carrying out desorption by using 0.3mol/L sulfuric acid to obtain adsorption tail brine and a lithium-containing desorption solution, wherein the concentration of lithium ions in the adsorption tail solution is 0.05g/L, the concentration of carbonate is 18.06g/L, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements and carbonate in the lithium-containing desorption solution are 1.2g/L, 1.4g/L, 0.08g/L, 0.01g/L and 0g/L respectively.
Concentrating the lithium-containing analysis solution by a reverse osmosis system at an operating pressure of 3.8MPa to obtain a lithium ion concentrate of 3.2g/L, then carrying out evaporation concentration by MVR to obtain a lithium ion concentrate of 15g/L, and then entering a chelating resin system to carry out deep calcium and magnesium removal to obtain the lithium-rich brine.
And (3) carrying out lithium deposition reaction on the lithium-rich brine and the adsorption tail brine according to a ratio, wherein the reaction temperature is 85 ℃, the reaction time is 45 minutes, and centrifuging to obtain a lithium carbonate product, wherein the purity of the lithium carbonate reaches 99.5%.
And (3) adjusting the pH value of the lithium precipitation mother liquor to about 4 by using 2mol/L sulfuric acid, removing carbonate in the lithium precipitation mother liquor, converting the lithium precipitation mother liquor into a mixed solution of sodium sulfate and lithium sulfate, and then feeding the mixed solution into a bipolar membrane device for electrolysis to obtain 2mol/L sulfuric acid and 1.8mol/L sodium hydroxide and lithium hydroxide mixed alkali.
Example 2
The embodiment provides a process method for preparing lithium carbonate from carbonate type salt lake brine, wherein the brine used is carbonate type brine of a certain salt lake from Tibet, the concentrations of main ions, namely lithium ions, sodium ions, magnesium ions, boron elements and carbonate ions in the original brine are respectively 0.81g/L, 142g/L, 0.1g/L, 3g/L and 28.9g/L, and the process of the embodiment is shown in fig. 1, and the method of the embodiment comprises the following steps:
and (3) feeding the carbonate type salt lake brine into a pretreatment multi-medium filter to filter and remove part of mechanical impurities such as silt and the like to obtain pretreated brine.
Sending the pretreated brine into a device filled with a titanium adsorbent, and after adsorption, carrying out desorption by using 0.4mol/L sulfuric acid to obtain adsorption tail brine and a lithium-containing desorption solution, wherein the concentration of lithium ions in the adsorption tail solution is 0.1g/L, the concentration of carbonate is 28.03g/L, and the concentrations of lithium ions, sodium ions, magnesium ions, boron elements and carbonate in the lithium-containing desorption solution are 1.1g/L, 1.3g/L, 0.04g/L, 0.02g/L and 0g/L respectively.
Concentrating the lithium-containing analysis solution by a sea-fresh reverse osmosis system at an operating pressure of 3.6MPa, concentrating lithium ions to 2.9g/L, then performing deep concentration by high-pressure reverse osmosis at an operating pressure of 10MPa, concentrating the lithium ions to 10g/L, then entering a chelating resin system, and performing deep calcium and magnesium removal to obtain the purified lithium-rich brine.
And (3) carrying out lithium precipitation reaction on the lithium-rich brine and the adsorption tail brine according to a ratio to obtain a lithium carbonate product, wherein the purity of the lithium carbonate reaches 99.8%.
Preparing 1.8mol/L sulfuric acid by using a bipolar membrane, adjusting the pH value of lithium precipitation mother liquor to about 5, removing carbonate in the lithium precipitation mother liquor, converting the lithium precipitation mother liquor into a mixed solution of sodium sulfate and lithium sulfate, and then feeding the mixed solution into a bipolar membrane device for electrolysis to obtain 1.8mol/L sulfuric acid and 2.1mol/L sodium hydroxide and lithium hydroxide mixed alkali.
Example 3
The brine used in this example is a lithium precipitation mother liquor of a certain salt lake, the concentrations of main lithium ions, sodium ions and carbonate ions in the mother liquor are 1.81g/L, 32.5g/L and 18.9g/L, respectively, the process shown in fig. 1 is the flow of this example, and other conditions are completely the same as those in example 2, so that the purity of the obtained lithium carbonate product reaches 99.5%.
Claims (10)
1. A process for preparing lithium carbonate from carbonic acid type brine is characterized by comprising the following steps:
step 1, absorbing carbonic acid type brine by adopting a lithium extraction adsorbent to obtain tail brine;
step 2, carrying out desorption treatment on the lithium extraction adsorbent to obtain an analytic solution;
and 3, mixing the analysis solution with tail halogen, and performing precipitation reaction of lithium carbonate to obtain lithium carbonate.
2. The process for preparing lithium carbonate from carbonic acid brine according to claim 1, wherein the desorption solution is mixed with tail brine after membrane concentration and/or resin purification treatment;
after the analysis solution is subjected to membrane concentration and resin purification, the concentrations of lithium ions, calcium ions and magnesium ions are respectively 5-40g/L, 0.0001-0.1g/L and 0.0001-0.1 g/L.
3. The process for preparing lithium carbonate from carbonated brine as claimed in claim 1, wherein said membrane concentration is selected from reverse osmosis concentration, forward osmosis concentration or electrodialysis concentration;
the resin purification adopts chelating resin or ion exchange resin.
4. The process for preparing lithium carbonate from carbonic brine according to claim 1, wherein the concentrations of lithium ions, sodium ions, magnesium ions, boron, carbonate and chloride ions in the carbonic brine are 0.1-15g/L, 10-150g/L, 0.01-1g/L, 0.1-4g/L, 14-60g/L and 15-154g/L, respectively;
the lithium extraction adsorbent is selected from a titanium adsorbent or a manganese adsorbent;
in the desorption treatment, acid is adopted for desorption; the acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid or acetic acid solution, wherein the concentration of hydrogen ions is 0.01-1 mol/L.
5. The process for preparing lithium carbonate from the carbonated brine as claimed in claim 1, wherein the concentration of lithium ions in the tail halide is 0.05-1g/L, and the concentration of carbonate is 14-60 g/L;
the reaction temperature in the precipitation reaction is 45-95 ℃, and alkali liquor is added in the reaction process to adjust the pH value to 9-14.
6. The process for preparing lithium carbonate from carbonic acid brine according to claim 1, wherein the lithium carbonate obtained after the precipitation reaction is subjected to solid-liquid separation, and the obtained mother liquor is subjected to bipolar membrane electrodialysis treatment to obtain an acid solution and an alkali solution;
the concentration of hydrogen ions in the acid solution is 1.0-2.5 mol/L, and the hydrogen ions are recycled for desorption of a lithium extraction adsorbent or for removal of redundant carbonate ions in the mother solution;
the concentration of hydroxide ions in the alkali liquor is 1.0-2.5 mol/L, and the alkali liquor is recycled for pH adjustment in a precipitation reaction or pH adjustment before a carbonic acid type brine is used for a lithium extraction adsorbent for adsorption.
7. The utility model provides a device of carbonic acid type brine preparation lithium carbonate which characterized in that includes:
an adsorbent tank (1) for adsorbing lithium to carbonate brine;
the tail brine storage tank (2) is connected to the adsorbent tank (1) and is used for collecting the residual brine after lithium adsorption;
the desorption liquid tank (3) is used for adding desorption liquid into the adsorbent tank (1) to obtain eluent containing lithium ions;
and the precipitation reaction tank (6) is respectively connected with the analysis solution outlet of the adsorbent tank (1) and the tail brine storage tank (2) and is used for carrying out precipitation reaction of lithium carbonate.
8. The apparatus of claim 7, further comprising: the solid-liquid separation equipment (7) is connected to the precipitation reaction tank (6) and is used for separating lithium carbonate in the materials after the precipitation reaction;
the solid-liquid separation equipment (7) is selected from one or a combination of a plurality of centrifuges, filters or settlers.
9. The apparatus of claim 7, further comprising: the bipolar membrane electrodialyzer (8) is connected to the mother liquor side of the solid-liquid separation equipment (7) and is used for performing bipolar membrane electrodialysis treatment on the mother liquor; further comprising: the acid liquid tank (9) and the alkali liquid tank (10) are respectively connected with the acid liquid side and the alkali liquid side of the bipolar membrane electrodialyzer and used for storing acid liquid and alkali liquid; the acid liquor tank (9) is connected with the desorption liquor tank (3) and is used for supplying acid liquor into the desorption liquor tank (3); the alkali liquor tank (10) is connected with the precipitation reaction tank (6) and/or the adsorbent tank (1) and is used for respectively supplying alkali liquor into the precipitation reaction tank (6) or the adsorbent tank (1).
10. The apparatus of claim 7, further comprising: a membrane concentrator (4) connected to the desorption solution outlet of the adsorbent tank (1) for concentrating the desorption solution and supplying the concentrated solution to the precipitation reaction tank (6);
the membrane concentrator (4) is selected from one or a combination of a plurality of reverse osmosis concentrators, forward osmosis concentrators or electrodialysis concentrators;
further comprising: and a resin tower (5) connected to the concentration side of the membrane concentrator (4) for purifying the concentrated solution obtained by the membrane concentrator (4) for cations and feeding the purified material to the precipitation reaction tank (6).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159550A (en) * | 2022-08-26 | 2022-10-11 | 江苏特丰新材料科技有限公司 | Process and device for circularly extracting lithium from salt lake brine |
| CN116443901A (en) * | 2023-03-22 | 2023-07-18 | 礼思(上海)材料科技有限公司 | Method for preparing lithium carbonate by using lithium-rich liquid obtained by lithium ion sieve adsorption method |
| CN116445732A (en) * | 2023-01-19 | 2023-07-18 | 礼思(上海)材料科技有限公司 | Method for preparing lithium product by utilizing lithium precipitation mother liquor based on adsorption method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310446A (en) * | 2014-10-17 | 2015-01-28 | 江苏久吾高科技股份有限公司 | Process and device for extracting battery grade lithium from brine |
| CN111252788A (en) * | 2020-04-03 | 2020-06-09 | 启迪清源（北京）科技有限公司 | Method for preparing high-purity lithium carbonate by using fractional crystallization technology |
| CN112593094A (en) * | 2020-07-23 | 2021-04-02 | 江苏久吾高科技股份有限公司 | Process and device for extracting lithium from salt lake |
| CN112624160A (en) * | 2020-12-17 | 2021-04-09 | 宝武水务科技有限公司 | Method for extracting lithium carbonate from carbonate type salt lake brine |
| CN112661321A (en) * | 2020-12-07 | 2021-04-16 | 浙江开创环保科技股份有限公司 | Salt lake lithium extraction system and method based on membrane separation |
| CN216427370U (en) * | 2021-09-12 | 2022-05-03 | 江苏久吾高科技股份有限公司 | Device of carbonic acid type brine preparation lithium carbonate |
-
2021
- 2021-09-12 CN CN202111065343.2A patent/CN114134327A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310446A (en) * | 2014-10-17 | 2015-01-28 | 江苏久吾高科技股份有限公司 | Process and device for extracting battery grade lithium from brine |
| CN111252788A (en) * | 2020-04-03 | 2020-06-09 | 启迪清源（北京）科技有限公司 | Method for preparing high-purity lithium carbonate by using fractional crystallization technology |
| CN112593094A (en) * | 2020-07-23 | 2021-04-02 | 江苏久吾高科技股份有限公司 | Process and device for extracting lithium from salt lake |
| CN112661321A (en) * | 2020-12-07 | 2021-04-16 | 浙江开创环保科技股份有限公司 | Salt lake lithium extraction system and method based on membrane separation |
| CN112624160A (en) * | 2020-12-17 | 2021-04-09 | 宝武水务科技有限公司 | Method for extracting lithium carbonate from carbonate type salt lake brine |
| CN216427370U (en) * | 2021-09-12 | 2022-05-03 | 江苏久吾高科技股份有限公司 | Device of carbonic acid type brine preparation lithium carbonate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159550A (en) * | 2022-08-26 | 2022-10-11 | 江苏特丰新材料科技有限公司 | Process and device for circularly extracting lithium from salt lake brine |
| CN115159550B (en) * | 2022-08-26 | 2024-05-24 | 江苏特丰新材料科技有限公司 | Process and device for circularly extracting lithium from salt lake brine |
| CN116445732A (en) * | 2023-01-19 | 2023-07-18 | 礼思(上海)材料科技有限公司 | Method for preparing lithium product by utilizing lithium precipitation mother liquor based on adsorption method |
| CN116443901A (en) * | 2023-03-22 | 2023-07-18 | 礼思(上海)材料科技有限公司 | Method for preparing lithium carbonate by using lithium-rich liquid obtained by lithium ion sieve adsorption method |
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