CN118221142A - Method and system for preparing lithium carbonate by extracting lithium from lithium-containing brine - Google Patents
Method and system for preparing lithium carbonate by extracting lithium from lithium-containing brine Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 218
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000012267 brine Substances 0.000 title claims abstract description 148
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 76
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 47
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 claims abstract description 349
- 239000007788 liquid Substances 0.000 claims abstract description 231
- 238000003795 desorption Methods 0.000 claims abstract description 169
- 239000003463 adsorbent Substances 0.000 claims abstract description 74
- 238000001556 precipitation Methods 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010979 pH adjustment Methods 0.000 claims abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 53
- 239000012535 impurity Substances 0.000 claims description 44
- 239000012452 mother liquor Substances 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 33
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- 230000001105 regulatory effect Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000029219 regulation of pH Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000000909 electrodialysis Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 3
- 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 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910014235 MyOz Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- -1 boron ion Chemical class 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000012797 qualification Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 6
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- 239000002245 particle Substances 0.000 description 7
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- 239000007791 liquid phase Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
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Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of lithium extraction in salt lakes and discloses a method and a system for preparing lithium carbonate by extracting lithium from lithium-containing brine. The method comprises the following steps: (1) Carrying out first pH adjustment on lithium-containing brine to obtain pretreated brine with pH of 5-12; (2) Carrying out one-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1; (3) Adjusting the second pH value of the adsorption tail liquid 1 to 5-12, and then performing secondary adsorption; (4) Carrying out desorption treatment on the saturated adsorbent generated after the first-stage adsorption and the second-stage adsorption are respectively completed, and carrying out lithium precipitation reaction on the obtained desorption qualified liquid to obtain lithium carbonate; wherein the concentration of lithium ions in the lithium-containing brine is more than 0.8g/L. The method greatly reduces the dissolution loss of the adsorbent while improving the recovery rate of lithium, prolongs the service life of the adsorbent and avoids the environmental protection problem caused by the dissolution loss.
Description
Technical Field
The invention relates to the technical field of lithium extraction in salt lakes, in particular to a method and a system for preparing lithium carbonate by extracting lithium from lithium-containing brine.
Background
Lithium is known as "white petroleum" and "industrial monosodium glutamate" and has important applications in a variety of industrial production fields, including battery, ceramic, glass, lubricant, metallurgy, and other industries. In recent years, the rapid development of new energy automobiles promotes the rapid increase of the demand of lithium batteries, and lithium becomes a scarcity resource for competing. The global lithium resources are mainly reserved in salt lake brine, hard rock lithium ores and lithium clay, wherein the lithium resources of the salt lake brine type account for about 58% of the total amount, and the single resource scale of the salt lake project is generally larger than that of the hard rock lithium ores, so that the lithium extraction of the salt lake is the center of gravity of the future lithium resource development from the aspects of economy, sustainability and environmental protection.
Among the numerous salt lake lithium extraction process methods, the adsorption method is a recent research hot spot due to the high efficiency and environmental protection characteristics. The basic process of extracting lithium from salt lake by adsorption method includes pretreatment of brine, adsorption and desorption (adsorption section) of lithium, impurity removal and concentration of qualified liquid of desorption liquid, and final lithium precipitation section to produce lithium carbonate product. The most critical and most research and development efforts are the development of efficient lithium ion adsorbents and the optimization of the technological process of the adsorption section. At present, patent reports are reported on technical research and development related to various aspects of the technology for extracting lithium from salt lakes by an adsorption method, including synthesis of novel adsorption materials, granulation of adsorbents, production processes of adsorption sections, industrial equipment of the adsorption sections and the like, and mature adsorbents (molecular sieve type lithium adsorbents and ion sieve type lithium adsorbents) and adaptive adsorption processes (such as continuous ion exchange processes and the like) have been developed. However, for the operation process of extracting lithium from salt lakes by using ion sieve type adsorbents, particularly, the process of extracting lithium from brine with high lithium concentration by using ion sieve type lithium adsorbents has been studied and reported. In the production practice of extracting lithium from high-lithium-concentration brine by using an ion sieve type lithium adsorbent, the concentration of lithium ions in the brine is high, and the concentration of lithium ions is greatly reduced in the adsorption process, so that the traditional adsorption method is difficult to realize high lithium recovery rate, and the phenomenon of dissolution loss of the adsorbent in the adsorption section can occur; in order to improve the lithium desorption rate, the desorption process adopts acid liquor with higher concentration, so that the dissolution loss phenomenon of the adsorbent is aggravated, and the problems of low adsorption efficiency, serious dissolution loss of the adsorbent, lower total lithium yield and the like can occur. How to solve the above problems is the key whether the ion sieve type lithium adsorbent can be industrially applied.
Disclosure of Invention
The invention aims to solve the problems of low adsorption efficiency, serious solvent loss of an adsorbent, low total lithium yield and the like in the lithium extraction process of lithium-containing brine in the prior art, and provides a method and a system for preparing lithium carbonate by extracting lithium from lithium-containing brine.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing lithium carbonate by extracting lithium from lithium-containing brine, comprising the following steps:
(1) Carrying out first pH adjustment on lithium-containing brine to obtain pretreated brine with pH of 5-12;
(2) Carrying out one-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1;
(3) Adjusting the second pH value of the adsorption tail liquid 1 to 5-12, and then performing secondary adsorption;
(4) Carrying out desorption treatment on the saturated adsorbent generated after the first-stage adsorption and the second-stage adsorption are respectively completed, and carrying out lithium precipitation reaction on the obtained desorption qualified liquid to obtain lithium carbonate;
wherein the concentration of lithium ions in the lithium-containing brine is more than 0.8g/L.
The second aspect of the invention provides a system for preparing lithium carbonate by extracting lithium from high-lithium-concentration brine, wherein the system comprises: the lithium carbonate lithium ion battery pack comprises a pretreatment unit, a first-stage adsorption unit, a second pH regulation unit, a second-stage adsorption unit, a concentration impurity removal unit and a lithium precipitation reaction unit, wherein the pretreatment unit is used for regulating the pH value of lithium-containing brine to be 5-12, the first-stage adsorption unit is used for carrying out first-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1, the second pH regulation unit is used for regulating the second pH value of the adsorption tail liquid 1 to be 5-12 to obtain adsorption tail liquid 1 regulated by the second pH value, the second-stage adsorption unit is used for carrying out second-stage adsorption on the adsorption tail liquid 1 regulated by the pH value to obtain adsorption tail liquid 2, the first-stage adsorption unit and the second-stage adsorption unit are also used for carrying out desorption treatment on saturated adsorbents generated after the first-stage adsorption and the second-stage adsorption are respectively completed to obtain desorption qualified liquid, the concentration impurity removal unit is used for carrying out impurity removal and concentration on the qualified liquid to obtain concentration qualified liquid, and the lithium precipitation reaction unit is used for carrying out lithium precipitation reaction on the concentration qualified liquid to obtain lithium carbonate.
Through the technical scheme, the method and the system for preparing the lithium carbonate by extracting the lithium from the high-lithium-concentration brine have the following beneficial effects:
(1) The lithium-containing brine is firstly pretreated, the pH value of the brine is adjusted to an interval which is most beneficial to production, and suspended matters and solid impurities which possibly exist or are generated are removed, so that the subsequent adsorption efficiency is ensured to be maximized, and the influence of the solid impurities on the adsorbent is eliminated.
(2) The adsorption section is set as a two-section adsorption process, brine is subjected to one-section adsorption at a certain flow rate, the obtained adsorption tail liquid enters the two-section adsorption after alkali adjustment, and the desorption qualified liquid obtained by the two-section adsorption is combined into the total desorption liquid of the adsorption section, so that the lithium recovery rate of the brine with high lithium concentration can reach more than 90%.
(3) The process greatly reduces the dissolution loss of the adsorbent while improving the recovery rate of lithium, prolongs the service life of the adsorbent and avoids the environmental protection problem caused by dissolution loss.
Drawings
Fig. 1 is a flow chart for extracting lithium from lithium-containing brine to prepare lithium carbonate.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for preparing lithium carbonate by extracting lithium from lithium-containing brine, which comprises the following steps:
(1) Carrying out first pH adjustment on lithium-containing brine to obtain pretreated brine with pH of 5-12;
(2) Carrying out one-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1;
(3) Adjusting the second pH value of the adsorption tail liquid 1 to 5-12, and then performing secondary adsorption;
(4) Carrying out desorption treatment on the saturated adsorbent generated after the first-stage adsorption and the second-stage adsorption are respectively completed, and carrying out lithium precipitation reaction on the obtained desorption qualified liquid to obtain lithium carbonate;
wherein the concentration of lithium ions in the lithium-containing brine is more than 0.8g/L.
In the invention, the lithium-containing brine can be lithium-containing natural brine, the concentration of the lithium-containing brine is more than 0.8g/L, and other components including but not limited to sodium, potassium, calcium, magnesium, boron, iron, manganese, aluminum and the like are contained, wherein the concentration range of each main component is 10-150g/L, 0.01-1g/L, 0.1-4g/L, 5-50g/L and 20-150g/L respectively.
Compared with the traditional adsorption method lithium-containing brine extraction process, the method has the advantages that the first pH adjustment is carried out on the lithium-containing brine, and the universality of the process is improved by uniformly adjusting the pH values of different lithium-containing brines to the designated interval; and the dissolution loss of the adsorbent caused by excessive reduction of the pH value in the adsorption process is improved through the second pH adjustment, and meanwhile, the Li recovery rate can be improved.
In some embodiments of the present invention, the adsorbent used in the one-stage or two-stage adsorption is an ion sieve type lithium adsorbent.
In some embodiments of the invention, the adsorbent is of the general formula Li xMyOz, where M is selected from aluminum, manganese, iron, or titanium, 1.ltoreq.x.ltoreq.4, 1.ltoreq.y.ltoreq.5, 3.ltoreq.z.ltoreq.12. Where M represents a metal, including but not limited to metals such as aluminum, manganese, iron, titanium, and the like. The material can be synthesized by mixing lithium salt and corresponding metal salt in a certain proportion through a high-temperature solid-phase method or a liquid-phase method, and can also be directly purchased into a mature commercial material. The industry uses certain binders to granulate to form the adsorbent resins by specific processes, which can be referred to in patent CN108722341 and CN102631897.
In some embodiments of the invention, the first pH adjustment is performed by adding an alkaline substance selected from the group consisting of sodium hydroxide, potassium hydroxide, quicklime, solutions or suspensions of slaked lime, and the like, at a concentration of 0.5-5mol/L. Mixing a certain amount of solution or suspension with lithium-containing brine, and fully reacting until the pH value of the brine is stable. This step is not required if the pH of the lithium-containing brine itself meets the subsequent operating requirements.
In some embodiments of the present invention, step (1) further includes filtering the liquid obtained after the first pH adjustment to obtain pretreated brine. Solid impurities in the brine are removed through a cartridge filter, and the solid impurities possibly generated in the alkali adjusting process are removed. The exploitation of natural brine is often accompanied by sediment, floating dust and other kinds of solid impurities, and because certain brine contains certain specific components such as calcium, magnesium and aluminum with higher concentration, solid precipitation can be generated in the process of alkali adjustment, the brine needs to be removed by a security filter to avoid the influence of the brine on subsequent processes. The cartridge filter can be selected from a filter screen, a grid, a plate frame, a medium filter or a membrane filter, and the filtering precision is 0.1-10 mu m.
In some embodiments of the invention, in step (1), the pH is 7-9. The first-stage adsorption tail liquid 1 is collected for second-stage adsorption to maximize the lithium adsorption rate, and the pH value of the adsorption tail liquid 1 is low at this time, so that the further adsorption is difficult, the pH of the first-stage adsorption tail liquid is adjusted, alkaline substances are needed to be added to adjust the first pH value of the tail liquid to 5-12, preferably 7-9, and the second-stage adsorption can be realized to maximize the lithium adsorption rate. The alkaline substance is one or more selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, quicklime and lithium precipitation mother liquor. Preferably lithium precipitation mother liquor or 0.5-3mol/L sodium hydroxide solution and potassium hydroxide solution.
In some embodiments of the invention, in step (3), the pH is 7-9.
In some embodiments of the invention, the one-stage adsorption comprises loading a certain amount of adsorbent resin into a resin tower, and flowing the filtered pretreated brine through the adsorbent by a pump and a pipeline for one-stage adsorption, wherein the flow rate of the pretreated brine is 0.1-20BV/h, preferably 1-10BV/h. In the adsorption process, H + on the adsorption resin can be replaced with Li + in brine, H + is transferred from a solid phase to a liquid phase, and Li + is transferred from the liquid phase to the solid phase, so that the pH value of the adsorption tail liquid 1 is reduced relative to that of the original brine, and the absorption rate and the performance of the adsorbent can be influenced by the reduced pH value. Therefore, the pH value of the adsorption tail liquid 1 needs to be monitored in the adsorption process, and the flow rate of the brine is adjusted to be kept above 1.0BV/h, preferably above 2.5 BV/h. The total amount of the feed brine is 0.1BV-20BV, preferably 1-5BV, the residual lithium content of the adsorption tail liquid 1 is kept to be 20% -80% of that of the raw brine, preferably 30% -60%, and the adsorption tail liquid 1 needs to be collected for secondary adsorption.
In some embodiments of the present invention, the saturated adsorbent generated after the first-stage adsorption and the second-stage adsorption are respectively completed refers to an adsorbent for adsorbing lithium ions obtained by the first-stage adsorption and the second-stage adsorption, and the adsorbent has completely adsorbed lithium ions to reach a saturated state.
In some embodiments of the present invention, in step (4), before the desorption treatment, the method further includes: eluting the saturated adsorbent by using eluent, and desorbing the obtained leached adsorbent by using desorption liquid to obtain desorption qualified liquid. And after the first-stage adsorption and the second-stage adsorption are respectively finished, draining the brine in the resin tower, and leaching the generated saturated adsorbent to clear the brine remained on the saturated adsorbent so as to prevent impurity ions carried in the brine from entering the rear stage and affecting the purity of the final product.
In some embodiments of the present invention, after leaching is completed, the leaching solution in the resin tower is drained, the obtained leaching adsorbent is desorbed by using a desorption solution to obtain a desorption qualified solution, and desorption is performed to make the adsorbed lithium reenter the liquid phase, namely the desorption qualified solution. In contrast to the adsorption process, li + on the resin is replaced with H + in the brine in the desorption process, li + is transferred from the solid phase to the liquid phase, and H + is transferred from the liquid phase to the solid phase, so that the pH of the desorption qualified liquid rises relative to the desorption liquid, the desorption tends to be completed with the progress of desorption, the rising degree is weakened, and the pH of the desorption qualified liquid decreases. Too low a pH may lead to dissolution loss of the adsorbent and thus to an impossible decrease in adsorption efficiency, and the desorption qualification liquid obtained by the desorption is subjected to pH monitoring of more than 1, preferably more than 1.5. When the pH falls to this value, the desorption process stops. And collecting the desorption qualified liquid for subsequent lithium carbonate production.
In some embodiments of the present invention, after the desorption is completed in step (4), the desorption adsorbent is rinsed 2 with a rinsing solution. After the desorption is completed, the desorption liquid in the resin tower is drained, and the desorption adsorbent is leached 2 to clearly remain on the adsorbent so as not to influence the subsequent adsorption process.
In some embodiments of the invention, in step (4), the desorption qualified liquid obtained by the desorption is subjected to pH monitoring of more than 1, preferably more than 1.5. Too low a pH may lead to dissolution loss of the adsorbent, thereby causing impossible reduction of adsorption efficiency.
In some embodiments of the present invention, in step (4), the desorption solution is one or more selected from a hydrochloric acid solution, a sulfuric acid solution, a phosphoric acid solution, an acetic acid solution and a nitric acid solution.
In some embodiments of the invention, in step (4), the flow rate of the desorption liquid is 0.1-20BV/h, preferably 2-7BV/h.
In some embodiments of the present invention, in the step (4), the leaching solution is selected from one or more of water, 0.1-50wt% nacl aqueous solution, and 0.1-50wt% sodium hydroxide solution, preferably water.
In some embodiments of the invention, in step (4), the flow rate of the eluent is between 0.1 and 20BV/h, preferably between 3 and 10BV/h.
In some embodiments of the present invention, the second stage adsorption comprises that the first stage adsorption tail liquid 1 with the adjusted pH value is adsorbed by a fresh or desorbed adsorbent flowing through a pipeline through a pump, and the flow rate of the adsorption tail liquid 1 is 0.1-20BV/h, preferably 1-10BV/h. In the adsorption process, the pH value of the adsorption tail liquid 2 needs to be monitored, and the flow rate of brine is kept above 1.0, preferably above 2.5, so that the dissolution loss of the adsorbent caused by the severe drop of the pH value of the adsorption tail liquid is avoided. The total amount of the halogen entering of the adsorption tail liquid 1 in the two-stage adsorption is between 0.1BV and 20BV, and is preferably between 1BV and 5BV.
In the invention, the adsorption section comprises two sections of adsorption, and the recovery rate of the adsorbed lithium in the first section is accurately controlled by controlling the flow rate and the total amount of brine and detecting the pH value of the adsorption tail liquid, so that the dissolution loss of the adsorbent caused by the severe drop of the pH value of the adsorption tail liquid is avoided; the second pH value of the first-stage adsorption tail liquid is adjusted, the second-stage adsorption is carried out, lithium in the brine can be adsorbed to the greatest extent by finely controlling the flow rate and the total amount of the brine, the lithium content of the adsorption tail liquid is reduced, the maximum adsorption efficiency is realized, and the lithium recovery rate of the brine with high lithium concentration can reach more than 90%; in the two-stage adsorption process, the desorption step of each stage uses acid with lower concentration as desorption liquid, so that the desorption rate of the process can be ensured while the solution loss is reduced.
In the present invention, the adsorption section comprises two-stage adsorption. During the adsorption process, H + on the adsorbent is replaced with Li + in the brine, li + is adsorbed on the adsorbent, and H + is released into the brine, so that the pH value of the adsorption tail liquid is reduced. For high Li concentration brine, when more Li is adsorbed, the pH value of the brine is reduced more severely, so that further adsorption is inhibited, the adsorption efficiency is difficult to improve, the dissolution loss of active ingredients on the adsorbent is caused by low pH value, and the service life of the adsorbent is shortened. Therefore, the scheme adopts two-stage adsorption, and the Li adsorption rate of brine in each stage of adsorption is controlled to be 50% of the total lithium concentration, so that the rapid reduction of the pH value caused by excessive Li adsorption is avoided. The Li concentration of the brine and the pH value of the raw brine are combined, the flow rate and the total amount of the brine are controlled, and the yield of the total lithium adsorbed by one section is controlled to be about 50 percent. If the natural brine Li concentration is high (above 1 g/L) and the initial pH value is reduced (less than 5), the pH needs to be preset to 7-9. The adsorption tail liquid of the first stage of adsorption still contains high-concentration Li ions, however, the pH value of the tail liquid is low at the moment, and further adsorption is difficult, so that the pH value of the first stage of adsorption tail liquid is adjusted, the second stage of adsorption is carried out, the flow rate of brine and the total adsorption amount are controlled, li in the first stage of tail liquid is completely adsorbed, and the lithium recovery rate of the high-lithium concentration brine can reach more than 90 percent at the moment. The two sections of adsorbed adsorbents are respectively desorbed, the obtained desorption liquid is mixed and enters subsequent treatment, and the desorption step of each section uses acid with lower concentration, so that the higher desorption rate can be ensured while the dissolution loss is reduced.
In some specific embodiments of the invention, the pretreated brine flows through an adsorption section and lithium in the brine is separated, and optimal technological parameters including flow rate, total treatment capacity, tail liquid pH value, desorption liquid pH value and the like are designed according to the characteristics of lithium concentration, pH value and the like of different brines, so that the recovery rate of lithium is maximized, the dissolution loss of an adsorbent is reduced, and the high-lithium low-impurity desorption qualified liquid is obtained.
In some embodiments of the present invention, in step (4), the lithium precipitation reaction further obtains a lithium precipitation mother liquor, and the lithium precipitation mother liquor is mixed back into the adsorption tail liquor 1 as an alkali liquor to adjust the pH of the adsorption tail liquor 1, and lithium in the lithium precipitation mother liquor is recovered. The reuse of the lithium precipitation mother liquor is mixed with the adsorption tail liquid 1 of the first-stage adsorption, so that the pH value of the first-stage adsorption tail liquid can be adjusted, meanwhile, a large amount of lithium remained in the lithium precipitation mother liquor can be recovered in the subsequent second-stage adsorption, additional material consumption is not needed, additional lithium precipitation mother liquor treatment devices and processes are not needed, and the equipment cost and the operation cost are greatly reduced while the total lithium yield is improved.
In some specific embodiments of the present invention, the desorption qualified liquid obtained in the step (4) is subjected to impurity removal and concentration, and then is subjected to lithium precipitation reaction to obtain lithium carbonate.
In some embodiments of the present invention, in the step (4), the impurity removal is selected from one or more of extraction, ion exchange resin method, chemical impurity removal method, membrane technology, electrodialysis; the desorption qualified liquid contains high-concentration lithium ions and also contains other impurity ions with certain concentration, such as magnesium, calcium, potassium, sodium, boron and the like, and in order to ensure the purity of the final lithium carbonate product, the impurity ions in the solution need to be separated and removed to obtain the qualified liquid. The concentration is selected from one or more of membrane technology, electrodialysis and MVR; in order to improve the yield and stability of the lithium precipitation process, the solution needs to be concentrated to improve the lithium ion concentration.
In some specific embodiments of the present invention, in step (4), the impurities are removed and concentrated to obtain a concentrated qualified solution, and then the concentrated qualified solution is subjected to a lithium precipitation reaction with an alkaline solution, wherein the alkaline solution is selected from a sodium carbonate solution and/or a potassium carbonate solution, and preferably 100-200g/L sodium carbonate solution.
In some embodiments of the invention, in step (4), the lithium precipitation reaction temperature is 60-90 ℃, preferably 70-80 ℃.
In some embodiments of the present invention, in the step (4), the concentration of lithium ions in the concentrated qualified solution is 10-50g/L, preferably 15-25g/L; the magnesium ion concentration is less than 100mg/L, preferably less than 10mg/L; the calcium ion concentration is less than 100mg/L, preferably less than 10mg/L; the boron ion concentration is less than 100mg/L, preferably less than 10mg/L. When the concentration of lithium ions in the concentrated qualified liquid is in the range, the conversion rate of the lithium precipitation reaction is highest, and the concentration of residual lithium in the lithium precipitation mother liquid is lower.
In some embodiments of the present invention, in the step (4), the molar ratio of the concentrated qualified liquid to the alkaline liquid is 1:1-1.5, preferably 1:1.1-1.2.
In some embodiments of the present invention, in step (4), the coarse lithium carbonate is obtained after the lithium precipitation reaction, and the coarse lithium carbonate is washed, dried, crushed, and purified to obtain a battery grade lithium carbonate product.
The second aspect of the invention provides a system for preparing lithium carbonate by extracting lithium from high-lithium-concentration brine, wherein the system comprises: the lithium carbonate lithium ion battery pack comprises a pretreatment unit, a first-stage adsorption unit, a second pH regulation unit, a second-stage adsorption unit, a concentration impurity removal unit and a lithium precipitation reaction unit, wherein the pretreatment unit is used for regulating the pH value of lithium-containing brine to be 5-12, the first-stage adsorption unit is used for carrying out first-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1, the second pH regulation unit is used for regulating the second pH value of the adsorption tail liquid 1 to be 5-12 to obtain adsorption tail liquid 1 regulated by the second pH value, the second-stage adsorption unit is used for carrying out second-stage adsorption on the adsorption tail liquid 1 regulated by the pH value to obtain adsorption tail liquid 2, the first-stage adsorption unit and the second-stage adsorption unit are also used for carrying out desorption treatment on saturated adsorbents generated after the first-stage adsorption and the second-stage adsorption are respectively completed to obtain desorption qualified liquid, the concentration impurity removal unit is used for carrying out impurity removal and concentration on the qualified liquid to obtain concentration qualified liquid, and the lithium precipitation reaction unit is used for carrying out lithium precipitation reaction on the concentration qualified liquid to obtain lithium carbonate.
In some embodiments of the present invention, the high lithium concentration brine enters the pretreatment unit, the outlet of the pretreatment unit is connected to the inlet of the first stage adsorption unit, the outlet of the first stage adsorption unit is connected to the inlet of the second pH adjustment unit, the outlet of the second pH adjustment unit is connected to the inlet of the second stage adsorption unit, the outlet of the first stage adsorption unit and the outlet of the second stage adsorption unit are connected to the inlet of the concentrating and impurity removing unit, the outlet of the concentrating and impurity removing unit is connected to the inlet of the lithium precipitation reaction unit, and the outlet of the lithium precipitation reaction unit obtains the lithium carbonate.
The present invention will be described in detail by examples.
The following examples and comparative examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
Preparation example
The adsorbent powder is first synthesized using a high temperature solid phase method. The synthetic process of the manganese-based adsorbent powder comprises the following steps: weighing a certain amount of LiOH and MnO 2 powder according to Li: mn=1:1.1, fully grinding and stirring for 2 hours, then placing the mixture in a muffle furnace for high-temperature roasting at 500 ℃ at a heating rate of 10 ℃/min for 10 hours, cooling, grinding the product, and sieving the product by a 200-mesh sieve. The adsorbent powder obtained is then granulated. The granulation process is referred to patent CN109126750a. Sieving the adsorbent resin particles, and taking the particles with the particle diameter of 1-1.18mm for subsequent adsorption. 300mL (180 g) of the prepared manganese adsorbent is filled into an adsorption resin column, the filled adsorption resin is subjected to pre-desorption transformation by using hydrochloric acid with the concentration of 0.1mol/L, the acid flow rate is 10mL/min (2 BV/h), and the adsorption resin is washed for 2h.
The lithium-containing brine used in the embodiment and the comparative example is salt lake brine in south america, and the main component components are shown in the following table:
| Component (A) | Na | K | B | Mg | Ca | Li | Cl- | SO4 2- |
| Content g/L | 95.58 | 17.58 | 3.66 | 9.68 | 0.24 | 1.30 | 179.60 | 25.84 |
Example 1
The original pH value of the lithium-containing brine is 6.1, the pH value of the brine is regulated to 7.5 by using a 1mol/L sodium hydroxide solution, the brine is filtered by using a bag filter with the filtering precision of 1.0 mu m to remove solid particle impurities possibly existing in the brine, and the brine is pretreated to obtain the treated brine.
Taking 600mL of pretreated brine after treatment, introducing the pretreated brine into an adsorption resin column at a flow rate of 10mL/min for one-stage adsorption, collecting all adsorption tail liquid 1, and sampling for detecting the concentration of each component. After the one-stage adsorption is completed, residual brine in the adsorption column is emptied, and the adsorption resin is leached by using 1L of pure water, wherein the flow rate is 20mL/min. And after leaching, evacuating the adsorption column and starting desorption, taking 600mL of 0.1mol/L hydrochloric acid as desorption liquid, feeding the solution into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
The pH of the adsorption tail liquid 1 was adjusted to 7.5 by using 1mol/L sodium hydroxide solution. The adsorption tail liquid 1 after the pH adjustment is subjected to the adsorption-leaching-desorption-leaching operation (two-stage adsorption) again, and the adsorption cycle 1 (comprising the first-stage adsorption and the second-stage adsorption) is the above.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the lithium ion concentration in the desorption qualified liquid to 25g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
The pretreated brine is subjected to primary adsorption by using the adsorbent subjected to desorption and regeneration, the pH of the adsorption tail liquid 1 is regulated by using a 1mol/L sodium hydroxide solution, the pH is readjusted to 7.5, and then the adsorption cycle 2 (comprising primary adsorption and secondary adsorption) is carried out, wherein the method is consistent with the adsorption cycle 1. And collecting the adsorption tail liquid 2 and sampling to detect the concentration of each component.
And collecting and mixing the desorption qualified liquid 2 of the adsorption cycle 2 and the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the lithium ion concentration in the desorption qualified liquid to 25g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor. Collecting lithium precipitation mother liquor for sampling detection.
Example 2
The original pH value of the lithium-containing brine is 6.1, the pH value of the brine is regulated to 7.5 by using a 1mol/L sodium hydroxide solution, the brine is filtered by using a bag filter with the filtering precision of 1.0 mu m to remove solid particle impurities possibly existing in the brine, and the brine is pretreated to obtain the treated brine.
Taking 600mL of pretreated brine after treatment, introducing the pretreated brine into an adsorption resin column at a flow rate of 10mL/min for one-stage adsorption, collecting all adsorption tail liquid 1, and sampling for detecting the concentration of each component. After the one-stage adsorption is completed, residual brine in the adsorption column is emptied, and the adsorption resin is leached by using 1L of pure water, wherein the flow rate is 20mL/min. And after leaching, evacuating the adsorption column and starting desorption, taking 600mL of 0.1mol/L hydrochloric acid as desorption liquid, feeding the solution into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
The pH of the adsorption tail liquid 1 was adjusted to 7.5 by using 1mol/L sodium hydroxide solution. The adsorption tail liquid 1 after the pH adjustment is subjected to the adsorption-leaching-desorption-leaching operation (two-stage adsorption) again, and the adsorption cycle 1 (comprising the first-stage adsorption and the second-stage adsorption) is the above.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the concentration of lithium ions in the desorption qualified liquid to 15g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
The pretreated brine is subjected to primary adsorption by using the adsorbent subjected to desorption and regeneration, the pH of the adsorption tail liquid 1 is regulated by using a 1mol/L sodium hydroxide solution, the pH is readjusted to 7.5, and then the adsorption cycle 2 (comprising primary adsorption and secondary adsorption) is carried out, wherein the method is consistent with the adsorption cycle 1. And collecting the adsorption tail liquid 2 and sampling to detect the concentration of each component.
And collecting and mixing the desorption qualified liquid 2 of the adsorption cycle 2 and the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the concentration of lithium ions in the desorption qualified liquid to 15g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor. Collecting lithium precipitation mother liquor for sampling detection.
Example 3
The original pH value of the lithium-containing brine is 6.1, the pH value of the brine is regulated to 7.5 by using a 1mol/L sodium hydroxide solution, the brine is filtered by using a bag filter with the filtering precision of 1.0 mu m to remove solid particle impurities possibly existing in the brine, and the brine is pretreated to obtain the treated brine.
Taking 600mL of pretreated brine after treatment, introducing the pretreated brine into an adsorption resin column at a flow rate of 10mL/min for one-stage adsorption, collecting all adsorption tail liquid 1, and sampling for detecting the concentration of each component. After the one-stage adsorption is completed, residual brine in the adsorption column is emptied, and the adsorption resin is leached by using 1L of pure water, wherein the flow rate is 20mL/min. And after leaching, evacuating the adsorption column and starting desorption, taking 600mL of 0.1mol/L hydrochloric acid as desorption liquid, feeding the solution into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
The pH of the adsorption tail liquid 1 was adjusted to 7.5 by using 1mol/L sodium hydroxide solution. The adsorption tail liquid 1 after the pH adjustment is subjected to the adsorption-leaching-desorption-leaching operation (two-stage adsorption) again, and the adsorption cycle 1 (comprising the first-stage adsorption and the second-stage adsorption) is the above.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the lithium ion concentration in the desorption qualified liquid to 25g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
And (3) carrying out primary adsorption on the pretreated brine by using the adsorbent subjected to desorption regeneration, carrying out pH adjustment on the adsorption tail liquid 1 by using the lithium precipitation mother liquor obtained in the adsorption cycle 1, readjusting the pH to 7.5, and carrying out secondary adsorption, wherein the method is consistent with the adsorption cycle 1, namely the adsorption cycle 2 (comprising primary adsorption and secondary adsorption). And collecting the adsorption tail liquid 2 and sampling to detect the concentration of each component.
And collecting the desorption qualified liquid 2 in the adsorption cycle 2, and mixing the desorption qualified liquid 1. Removing impurities from the desorption qualified liquid by adopting a nanofiltration membrane, a reverse osmosis membrane and an evaporation concentration mode, and increasing the concentration of lithium ions in the desorption qualified liquid to 25g/L. 200g/L Na 2CO3 solution was used as Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. After the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting a lithium precipitation mother solution obtained by separation; the obtained lithium precipitation mother liquor can be continuously returned to the adsorption tail liquor 1 of the next cycle to be used as alkali liquor for pH value adjustment. Collecting lithium precipitation mother liquor for sampling detection.
Example 4
The original pH value of the lithium-containing brine is 6.1, the pH value of the brine is regulated to 7.5 by using a 1mol/L sodium hydroxide solution, the brine is filtered by using a bag filter with the filtering precision of 1.0 mu m to remove solid particle impurities possibly existing in the brine, and the brine is pretreated to obtain the treated brine.
Taking 600mL of pretreated brine after treatment, introducing the pretreated brine into an adsorption resin column at a flow rate of 10mL/min for one-stage adsorption, collecting all adsorption tail liquid 1, and sampling for detecting the concentration of each component. After the one-stage adsorption is completed, residual brine in the adsorption column is emptied, and the adsorption resin is leached by using 1L of pure water, wherein the flow rate is 20mL/min. And after leaching, evacuating the adsorption column and starting desorption, taking 600mL of 0.1mol/L hydrochloric acid as desorption liquid, feeding the solution into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
The pH of the adsorption tail liquid 1 was adjusted to 7.5 by using 1mol/L sodium hydroxide solution. The adsorption tail liquid 1 after the pH adjustment is subjected to the adsorption-leaching-desorption-leaching operation (two-stage adsorption) again, and the adsorption cycle 1 (comprising the first-stage adsorption and the second-stage adsorption) is the above.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the concentration of lithium ions in the desorption qualified liquid to 15g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
And (3) carrying out primary adsorption on the pretreated brine by using the adsorbent subjected to desorption regeneration, carrying out pH adjustment on the adsorption tail liquid 1 by using the lithium precipitation mother liquor obtained in the adsorption cycle 1, readjusting the pH to 7.5, and carrying out secondary adsorption, wherein the method is consistent with the adsorption cycle 1, namely the adsorption cycle 2 (comprising primary adsorption and secondary adsorption). And collecting the adsorption tail liquid 2 and sampling to detect the concentration of each component.
And collecting the desorption qualified liquid 2 in the adsorption cycle 2, and mixing the desorption qualified liquid 1. Removing impurities from the desorption qualified liquid by adopting a nanofiltration membrane, a reverse osmosis membrane and an evaporation concentration mode, and increasing the concentration of lithium ions in the desorption qualified liquid to 25g/L. 200g/L Na 2CO3 solution was used as Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. After the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting a lithium precipitation mother solution obtained by separation; the obtained lithium precipitation mother liquor can be continuously returned to the adsorption tail liquor 1 of the next cycle to be used as alkali liquor for pH value adjustment. Collecting lithium precipitation mother liquor for sampling detection.
Example 5
The procedure of example 1 was followed, except that the pretreatment stage was carried out using 1mol/L sodium hydroxide solution to adjust the pH of the raw brine to 10, and the subsequent adsorption operation was the same.
Example 6
An adsorption tail 1 was obtained as in example 1, except that the adsorption tail 1 was pH-adjusted to 10 using 1mol/L sodium hydroxide solution.
Comparative example 1
Taking 600mL of treated brine, allowing the brine to enter an adsorption resin column at a flow rate of 2mL/min for adsorption, collecting all adsorption tail liquid 1, and sampling for detecting the concentration of each component. After the adsorption was completed, the residual brine in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min. And (3) after leaching is finished, evacuating the adsorption column and starting desorption, taking 600mL of 0.1mol/L salt acidolysis liquid, feeding the solution into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the lithium ion concentration in the desorption qualified liquid to 25g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
Comparative example 2
Taking 600mL of treated brine, allowing the brine to enter an adsorption resin column at a flow rate of 2mL/min for adsorption, collecting all adsorption tail liquid 1, and sampling for detecting the concentration of each component. After the adsorption was completed, the residual brine in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min. And after leaching, evacuating the adsorption column and starting desorption, taking 600mL of 0.2mol/L hydrochloric acid as desorption liquid, feeding the solution into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the lithium ion concentration in the desorption qualified liquid to 25g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
Comparative example 3
Taking 600mL of raw brine, filtering and adsorbing only without adjusting pH in the pretreatment stage, wherein the adsorption flow rate is 10mL/min, evacuating residual brine in an adsorption column after the adsorption is completed, and leaching the adsorption resin by using 1L of pure water, wherein the flow rate is 20mL/min. And after leaching, evacuating the adsorption column and starting desorption, taking 600mL of desorption liquid, feeding the desorption liquid into the adsorption resin column at a flow rate of 10mL/min for desorption, collecting all the desorption qualified liquid 1, and sampling for detecting the concentration of each component. After the desorption was completed, the residual desorption liquid in the adsorption column was evacuated, and the adsorption resin was rinsed with 1L of pure water at a flow rate of 20mL/min.
And collecting the desorption qualified liquid 2 and mixing with the desorption qualified liquid 1. Adopting nanofiltration membrane, reverse osmosis membrane and evaporating concentration mode to remove impurities from the desorption qualified liquid, and raising the lithium ion concentration in the desorption qualified liquid to 25g/L, using 200g/L Na 2CO3 solution to obtain Li: na=1: mixing according to a proportion of 1.2, wherein the reaction temperature is 80 ℃ and the reaction time is 30min. And after the reaction, carrying out solid-liquid separation on the suspension after the reaction by using a vacuum suction filtration device to obtain lithium carbonate, and collecting and separating the lithium precipitation mother liquor.
Test case
For each group of the adsorption tail liquid 1, the adsorption tail liquid 2, the desorption tail liquid 1 and the desorption tail liquid 2 of the examples and the comparative examples, lithium ion concentration and pH value are detected, the lithium yield and the desorption rate are calculated according to the results, the manganese or titanium concentration in the adsorption tail liquid 2 and the desorption qualified liquid is detected to compare the dissolution loss degree of the adsorbent under different conditions, and the lithium concentration, the pH value and the volume of the lithium precipitation mother liquid of the examples 1 and 2 are detected. The results are shown in tables 1 and 2. Wherein:
In the embodiment, the content of inlet lithium is the lithium content of lithium-containing brine, and the content of outlet lithium is the lithium content of two-stage adsorption tail liquid; in the comparative example, the inlet lithium content is lithium-containing brine lithium content, and the outlet lithium content is adsorption tail liquid lithium content;
TABLE 1
Note that: ND is not detected, N/A is not applicable to the item.
TABLE 2
As can be seen from the results of Table 1, the results of examples 1 and 2 show that the adsorption tail liquid and the desorption qualified liquid have similar lithium content under the same adsorption-desorption conditions, so that the adsorbent is stable, the lithium adsorption yield can reach 93%, and the lithium adsorption yield is greatly improved compared with the current production practice. In table 2, compared with example 2, the concentration of the lithium precipitation mother liquor of example 1 is lower and the volume is smaller, so that the higher the concentration of lithium in the concentrated qualified liquid is, the lower the concentration of lithium remained in the lithium precipitation mother liquor is, the smaller the volume of the lithium precipitation mother liquor is, and the more lithium in the desorption liquid is converted into lithium carbonate product, and the total lithium yield is higher. As is apparent from the results of comparative examples 1 and 2 and examples 1 and 2, by reducing the flow rate during adsorption, the retention time of brine in the adsorption column was increased, and the lithium adsorption rate was improved as compared with the one-stage adsorption, but was still lower than that of the two-stage adsorption method used in examples 1 and 2. In comparative examples 1 and 2, the decrease in pH of the adsorption tail liquid was remarkable due to the large decrease in lithium concentration during the adsorption, and Mn dissolution loss occurred during the adsorption, however, this phenomenon was not found in examples 1 and 2. Also, the desorption rate of comparative example 1 was low due to the limitation of the acid concentration, and the total lithium yield was not ideal. In the comparative example, the desorption rate can be improved to a certain extent by improving the acid concentration of the desorption liquid, but the Mn dissolution loss in the desorption process is aggravated due to the improvement of the acid concentration, so that the deterioration of the adsorbent is aggravated, the service life is shortened, and the production cost in the production process is increased. The comparison of the results shows that the two-stage adsorption method can greatly improve the lithium yield, and as the conditions of each stage of adsorption are mild, the method comprises the steps of small pH value reduction range in the adsorption step and low concentration of desorption acid, and the modes of detecting the tail liquid pH value in the adsorption step, desorbing the qualified liquid pH value in the desorption step and the like are adopted, the phenomenon of dissolution loss of the adsorbent is avoided to the greatest extent, and the service life of the adsorbent is prolonged. Therefore, the two-stage adsorption method has great advantages over the one-stage adsorption method.
The results of comparative examples 1 and 3 show that the original brine directly enters the adsorption section without the pH value being pre-adjusted, the yield of adsorbed lithium is far lower than that of brine with the pH value being pre-adjusted, the pH value of the adsorption tail liquid is greatly reduced, and the phenomenon of manganese dissolution loss occurs in the adsorption tail liquid. There is a great advantage in preconditioning the pH.
In the embodiment 3, the pH value of the adsorption tail liquid 1 can be readjusted to 7.56 by recycling the lithium precipitation mother liquid, so that the requirement of two-stage adsorption is met, the lithium in the lithium precipitation mother liquid can be recycled without an additional lithium precipitation mother liquid treatment device or process, the total lithium yield can reach 90.3%, and the improvement is obvious compared with the embodiments 1 and 2 in which the pH value is adjusted without using the lithium precipitation mother liquid. Since the pH of the adsorption tail liquid is adjusted by using the lithium precipitation mother liquid, the content of imported lithium in the embodiment 3 is obviously increased, the adsorption rate and the resolution rate of lithium are reduced, but the lithium adsorption rate and the resolution rate can still be maintained above 90%, and the production requirement is met. If the pH adjustment of the adsorption tail liquid 1 is performed by using the lithium precipitation mother liquor obtained by concentrating the desorption solution with a lower lithium concentration, that is, in example 4, the pH adjustment is performed by using the lithium precipitation mother liquor generated by concentrating the desorption solution with a concentration of 15g/L, the lithium adsorption rate is obviously reduced by 84%, the effect is not as good as that of example 3, but the total lithium yield is still improved. Therefore, the pH value of the absorption tail liquid 1 is adjusted by recycling the lithium precipitation mother liquid, the requirement of a two-stage absorption method can be met, the recovery rate of lithium can be maximized under the condition that no additional treatment process is added, the lithium precipitation mother liquid is treated, and the production cost is greatly saved. As is evident from the comparison between example 3 and example 4, the total lithium yield was relatively high when the concentration of lithium in the concentrated qualified solution was high.
In example 5, the pH of the raw brine was adjusted to 10 during the pretreatment stage, and the concentration of the tail liquid of the first stage of adsorption was reduced, but the concentration was not significantly increased, i.e., the higher pH did not significantly increase the lithium adsorption rate, nor did the lithium adsorption rate significantly increase; similarly, in example 6, the pH value of the adsorption tail liquid 1 was adjusted to 10, and the lithium concentration of the tail liquid of the two-stage adsorption was lower, but the effect was not obvious, and the improvement of the lithium adsorption rate was not obvious. The schemes of example 5 and example 6 are not optimal, as higher pH adjustment would require more base consumption and higher cost.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. The method for preparing lithium carbonate by extracting lithium from lithium-containing brine is characterized by comprising the following steps of:
(1) Carrying out first pH adjustment on lithium-containing brine to obtain pretreated brine with pH of 5-12;
(2) Carrying out one-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1;
(3) Adjusting the second pH value of the adsorption tail liquid 1 to 5-12, and then performing secondary adsorption;
(4) Carrying out desorption treatment on the saturated adsorbent generated after the first-stage adsorption and the second-stage adsorption are respectively completed, and carrying out lithium precipitation reaction on the obtained desorption qualified liquid to obtain lithium carbonate;
wherein the concentration of lithium ions in the lithium-containing brine is more than 0.8g/L.
2. The method according to claim 1, wherein the adsorbent used in the one-stage adsorption or two-stage adsorption is an ion sieve type lithium adsorbent;
Preferably, the adsorbent is represented by a general formula Li xMyOz, wherein M is selected from aluminum, manganese, iron or titanium, x is 1-4, y is 1-5, and z is 3-12.
3. The method of claim 1 or 2, wherein step (1) further comprises filtering the liquid resulting from the first pH adjustment to obtain the pretreated brine;
preferably, in step (1), the pH is 7-9;
preferably, in step (3), the pH is 7-9.
4. A method according to any one of claims 1-3, wherein in step (3), the adsorption tail liquid 2 is obtained after the two-stage adsorption;
Preferably, in step (4), the desorption treatment further includes: eluting the saturated adsorbent by using eluent, and desorbing the obtained leached adsorbent by using desorption liquid to obtain desorption qualified liquid.
5. The method according to claim 4, wherein in step (4), the desorption qualification liquid obtained by desorption is subjected to pH monitoring of more than 1, preferably more than 1.5;
preferably, in the step (4), the desorption solution is one or more selected from hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution, acetic acid solution and nitric acid solution;
preferably, in step (4), the flow rate of the desorption liquid is 0.1-20BV/h, preferably 2-7BV/h.
6. The process according to claim 4 or 5, wherein in step (4), the eluent is selected from one or more of water, 0.1-50wt% aqueous nacl solution, 0.1-50wt% aqueous sodium hydroxide solution, preferably water;
Preferably, in step (4), the flow rate of the eluent is between 0.1 and 20BV/h, preferably between 3 and 10BV/h.
7. The method according to any one of claims 1 to 6, wherein in step (4), the lithium precipitation reaction also yields a lithium precipitation mother liquor;
preferably, in the step (4), the lithium precipitation mother liquor is returned and mixed into the adsorption tail liquor 1 as alkali liquor to adjust the pH value of the adsorption tail liquor 1, and lithium in the lithium precipitation mother liquor is recovered;
preferably, the desorption qualified liquid obtained in the step (4) is subjected to impurity removal and concentration, and then lithium precipitation reaction is carried out to obtain lithium carbonate.
8. The method of claim 7, wherein in step (4), the impurity removal is selected from one or more of extraction, ion exchange resin method, chemical impurity removal method, membrane technology, electrodialysis;
preferably, the concentration is selected from one or more of membrane technology, electrodialysis and MVR;
Preferably, in the step (4), removing impurities, concentrating to obtain a concentrated qualified solution, and then carrying out the lithium precipitation reaction on the concentrated qualified solution and alkali liquor, wherein the alkali liquor is selected from sodium carbonate solution and/or potassium carbonate solution;
Preferably, in step (4), the lithium precipitation reaction temperature is 60-90 ℃, preferably 70-80 ℃.
9. The method of claim 8, wherein in step (4), the concentrated pass liquor has a lithium ion concentration of 10-50g/L, preferably 15-25g/L; the magnesium ion concentration is less than 100mg/L, preferably less than 10mg/L; the calcium ion concentration is less than 100mg/L, preferably less than 10mg/L; the boron ion concentration is less than 100mg/L, preferably less than 10mg/L.
10. The method according to claim 8 or 9, wherein in step (4), the molar ratio of the concentrated qualified liquid to the lye is 1 in terms of Li + to Na + or Li + to K +: 1-1.5, preferably 1:1.1-1.2;
Preferably, in the step (4), coarse lithium carbonate is obtained after the lithium precipitation reaction, and the coarse lithium carbonate is washed, dried, crushed and impurity-removed to obtain a battery grade lithium carbonate product.
11. A system for preparing lithium carbonate by extracting lithium from high-lithium-concentration brine, which is characterized by comprising: the lithium carbonate lithium ion battery pack comprises a pretreatment unit, a first-stage adsorption unit, a second pH regulation unit, a second-stage adsorption unit, a concentration impurity removal unit and a lithium precipitation reaction unit, wherein the pretreatment unit is used for regulating the pH value of lithium-containing brine to be 5-12, the first-stage adsorption unit is used for carrying out first-stage adsorption on the pretreated brine to obtain adsorption tail liquid 1, the second pH regulation unit is used for regulating the second pH value of the adsorption tail liquid 1 to be 5-12 to obtain adsorption tail liquid 1 regulated by the second pH value, the second-stage adsorption unit is used for carrying out second-stage adsorption on the adsorption tail liquid 1 regulated by the pH value to obtain adsorption tail liquid 2, the first-stage adsorption unit and the second-stage adsorption unit are also used for carrying out desorption treatment on saturated adsorbents generated after the first-stage adsorption and the second-stage adsorption are respectively completed to obtain desorption qualified liquid, the concentration impurity removal unit is used for carrying out impurity removal and concentration on the qualified liquid to obtain concentration qualified liquid, and the lithium precipitation reaction unit is used for carrying out lithium precipitation reaction on the concentration qualified liquid to obtain lithium carbonate.
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