CN1281497C - Method for separating magnesium and concentrating lithium from brine in salt lake - Google Patents
Method for separating magnesium and concentrating lithium from brine in salt lake Download PDFInfo
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- CN1281497C CN1281497C CN 200310122238 CN200310122238A CN1281497C CN 1281497 C CN1281497 C CN 1281497C CN 200310122238 CN200310122238 CN 200310122238 CN 200310122238 A CN200310122238 A CN 200310122238A CN 1281497 C CN1281497 C CN 1281497C
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- lithium
- electrodialyzer
- salt lake
- lake brine
- liquid
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- 239000011777 magnesium Substances 0.000 title claims abstract description 116
- 239000012267 brine Substances 0.000 title claims abstract description 70
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 57
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 44
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 32
- -1 Cl<-> Chemical class 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 239000012141 concentrate Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 105
- 239000000243 solution Substances 0.000 claims description 93
- 238000007865 diluting Methods 0.000 claims description 29
- 238000012986 modification Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 24
- 238000000909 electrodialysis Methods 0.000 claims description 21
- 241001131796 Botaurus stellaris Species 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 18
- 238000010612 desalination reaction Methods 0.000 claims description 18
- 238000011033 desalting Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-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
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- ZFRKEVMBGBIBGT-UHFFFAOYSA-N ethenyl benzenesulfonate Chemical compound C=COS(=O)(=O)C1=CC=CC=C1 ZFRKEVMBGBIBGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 17
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 229960002645 boric acid Drugs 0.000 abstract 1
- 235000010338 boric acid Nutrition 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 15
- 239000003513 alkali Substances 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000036470 plasma concentration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a method for separating magnesium and concentrating lithium in salt lake brine, which is suitable for separating magnesium boracic acid radicals and sulfate radicals from lithium in salt lake brine in which magnesium and lithium are contained and salt field concentrated aged brine in which magnesium and lithium are contained. In the method, a salt field in which univalent cations and divalent cations such as Mg<2+> and Ca<2+> and anions such as Cl<->, SO4<2-> and B2O3 are contained is evaporated by solarization to obtain lithium-contained concentrated brine, wherein the concentration of Li<+> is from 0.02 to 20 g/L, and the weight ratio of Mg<2+> to Li<+> is from 1:1 to 300:1. a univalent selective ion exchange membrane is utilized to carry out circulation (continuous type, continuous partial circulation type or batch circulation type)technology to concentrate lithium by a one-stage or multi-stage electric dialyzator, and lithium-enriched low-magnesium brine can be obtained. With the adoption of the method of the present invention, the recovery rate of Li<+> can not less than 80%, the removal rate of Mg<2+> can not less than 95%, the removal rate of B<3+> can not less than 99%, and the removal rate of SO4<2-> can not less than 99%. so the problem that magnesium and other impurities in high magnesium-lithium ratio salt lake brine are difficult to separate can be solved. The weight ratio of lithium-enriched brine (Mg<2+>/Li<+>) is from 0.3:1 to 10:1, and the concentration of contained Li<+> is from 2 to 20 g/L.
Description
Technical field
The present invention relates to a kind of from solution separating magnesium and reclaim the method for lithium, especially a kind ofly concentrate the method that contains separating magnesium and concentrated lithium the old halogen of lithium from containing lithium salts lake bittern water and salt pan.
Background technology
Lithium ion and a large amount of basic metal, alkaline-earth metal coexistence will reclaim lithium economically from natural polywater salt system high Mg/Li ratio salt lake brine, not only depend on to contain lithium concentration but also depend on to contain magnesium, calcium ion concn.Because magnesium is very similar to the chemical property of lithium, the magnesium lithium separates very difficult.The bittern of abroad having produced is carried lithium and is all only limited to contain the lower bittern of magnesium density now, the Mg/Li ratio value was less than 6: 1, and the Qinghai Salt Lake Bittern Mg/Li ratio can be up to 300: 1, can not directly use the simple method of low Mg/Li ratio value bittern Exposure to Sunlight desalination precipitation Quilonum Retard, alkali charge is excessive when making with extra care bittern loses serious with lithium salts otherwise can cause.It is to solve magnesium lithium separation problem that the high Mg/Li ratio salt lake brine extracts the lithium salts matter of utmost importance.
In the world high Mg/Li ratio value bittern is put forward the existing many methods of lithium, as salting-out process, organic solvent extractionprocess, adsorbents adsorb method, roasting method, the precipitator method etc.This several method respectively has characteristics at magnesium lithium isolation technique in the high Mg/Li ratio salt lake brine.Wherein the tbp extraction process adopt to concentrate rich lithium high-magnesium brine as raw materials for production, and the rate of recovery is than higher, but long flow path, equipment corrosion are serious, and the production cost height can't further be realized industrialization.Absorption method is to utilize Choice of Resin absorption lithium ion, but the resin price height, resin is polluted by bittern easily and is difficult to regeneration, and the resin absorption capacity is lower, and actual production is subjected to the dual restriction of industrial scale and economic benefit.Roasting method is wanted a large amount of hydrochloric acid of by-product and heavy MgO, and wherein heavy MgO faces the narrow problem in selling market, and hydrochloric acid is to the unusual serious problems of equipment corrosion, and whole process energy consumption height only carried out desk research work.Precipitator method feasible process, but long flow path, the rate of recovery are low, the material cycling amount is big, and repeatedly calcining is filtered, trivial operations, it is lower that hydrothermal decomposition or roasting leaching liquid contain lithium concentration, needs evaporated water bigger when concentrating.
Present situation at the high Mg/Li ratio in China's Qinghai Salt Lake Bittern, the method of producing Quilonum Retard in a kind of high Mg/Li ratio salt lake brine is disclosed in Chinese patent application 01128815.9, this method is to separate out bittern behind the potassium magnesium mixed salt through salt pan de-magging → add precipitation agent with the salt pan in bittern, adds saturated NaOH solution in the mother liquor of boron magnesium co-precipitation → after the co-precipitation of boron magnesium separates and carries out degree of depth demagging → precipitator method and produce Quilonum Retard; This method is owing to need to add a large amount of precipitation agents, and production cost can be very high.
A kind of method of producing Quilonum Retard with carborization separating magnesium lithium from the high Mg/Li ratio salt lake brine is disclosed in Chinese patent application 01128816.7, this method is to evaporate through the salt pan at the magnesium sulfate salt lake brine to separate out potassium magnesium mixed salt, take off again in the old saltwater brine behind the boron, adding alkali makes the magnesium lithium respectively with oxyhydroxide, carbonate, phosphoric acid salt, or the form of oxalate is precipitated out, this precipitation is carried out calcining and decomposing, by carbonization or carbonation, make the lithium pass into solution, magnesium still remains in the precipitation, thereby reaching the magnesium lithium separates, should carry out deep impurity-removing by richness lithium solution again, evaporation concentration or with soda ash precipitation preparation Quilonum Retard, cost also can be very high subsequently.
Summary of the invention
The objective of the invention is for provide a kind of from salt lake brine the method for separating magnesium and concentrated lithium, this method is to utilize the ion-exchange membrane electrodialysis method to concentrate lithium, this method provides from the high Mg/Li ratio salt lake brine high efficiency separation magnesium and highly selective to extract the technology of lithium, its technical process is simple, operation is reasonable, and the quality of the finished product that this method makes is good, the rate of recovery of lithium 〉=80%, Mg
2+Decreasing ratio 〉=95%, B
3+Decreasing ratio 〉=99%, SO
4 2-Decreasing ratio 〉=99%.
Purpose of the present invention can realize by following measure:
A kind of from salt lake brine the method for separating magnesium and concentrated lithium, comprise the steps: described salt lake brine is carried out one or more levels ion-exchange membrane electrodialysis, be about to the diluting compartment that salt lake brine is sent into electrodialyzer, through the electrodialysis of monovalent ion selectivity; Used monovalence selective ion exchange membrane comprises monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane in the described electroosmose process; Obtain spissated rich lithium concentrated brine solution in the concentration compartments of electrodialyzer, magnesium, borate, sulfate radical then are trapped in the diluting compartment, realize that magnesium, borate, sulfate radical separate with lithium.
Described salt lake brine is selected from concentrated brine, high Mg/Li ratio salt lake brine that the evaporation of high Mg/Li ratio salt lake brine, high Mg/Li ratio salt lake brine obtains and carries at least a in the old halogen that the old halogen evaporation behind the potassium obtains; Mg in the described salt lake brine
2+With Li
+Weight ratio be 300: 1～1: 1, bittern contains Li
+Concentration 0.02～20g/L.
Each the liquid stream that enters one-level or series multistage electrodialyzer in the described ion exchange method is for continous way, sequential portion is circulating or the batch cycle formula;
(1) described continous way is that one or more levels electrodialyzer moves continuously, and promptly demineralised liquid and concentrated solution enter continuously that desalting chamber and concentration compartments promptly discharge in one-level or the series multistage electrodialyzer;
(2) described sequential portion is circulating is one or more levels sequential portion circular flow, promptly the demineralised liquid of first step circulation groove is sent to first step electrodialyzer by first step recycle pump, get back to first step circulation groove again through after the desalination, the small portion of demineralised liquid enters second stage circulation groove, rest part mixes with new stoste of replenishing, and enters the circulation of first step electrodialyzer once more.By this desalination in following electrodialyzers at different levels in proper order, last demineralised liquid is stored in the desalination liquid bath; When moving with desalination system, the stoste of concentrated solution system will concentrate the liquid bath circulation fluid by concentrate pump and send into desalination circulation in each electrodialyzer;
(3) described batch cycle formula is that concentrated solution and demineralised liquid circulate by the extracorporeal circulation groove respectively, and promptly demineralised liquid in the electrodialyzer and concentrated solution are to carry out closed cycle separately, drains after reaching the desalination requirement.
Described monovalent cation selective ion exchange membrane is selected from a kind of in the film of the CMI-7000 that Selemion modification strong acid type film CMV that CMS that modification strong acid type (Na type) film K100 that Japanese Asahi Chemical company produces and K192, Japanese Tokuyama Soda company produce and CM-1 modification strong acid type (Na type) film, Japanese Asahi Glass company produce and CMR, U.S. Membranes International Inc. company produce; The matrix of this film is selected from least a in the multipolymer of styrene diethylene benzene copoly mer, vinylbenzene-co-polymer of sulfonate and Vinylstyrene; Its properties-correcting agent is selected from (R--SO
3H) active group, polymine.
Described univalent anion selective ion exchange membrane is selected from a kind of among quaternary amine (Cl type) modification highly basic film ACM that quaternary amine (Cl type) modification highly basic film A111 that Japanese Asahi Chemical company produces and A192, Japanese Tokuyama Soda company produce, Selemion modification strong base film TM ASV that Japanese Asahi Glass company produces, the AMI-7000 that U.S. Membranes International Inc. company produces; The matrix of this film is selected from least a in vinylbenzene-Vinylstyrene co-polymer, 4-vinylpyridine and divinylbenzene copolymer, 1-chloro-4-methyl-benzene and the divinylbenzene copolymer; Its properties-correcting agent is selected from (R--N (CH
2)
3Cl
-) active group, polyene propyl bromide salt.
The density of the initial concentration liquid in the concentration compartments of described electrodialyzer is 1.0～1.4g/ml; The density of the initial desalination solution in the diluting compartment of described electrodialyzer is 1.1～1.6g/ml.
Concentrated solution in the concentration compartments in the described electrodialyzer uses by following mode: A, circulation are as the batching mother liquor of the initial concentration liquid of its electrodialysis at the corresponding levels concentration compartments; Or B, as the initial demineralised liquid of the diluting compartment of next stage electrodialyzer.
The diluting compartment that demineralised liquid behind the diluting compartment separating Li of described next stage electrodialyzer returns its upper level electrodialyzer is made the batching mother liquor of its initial demineralised liquid.
The described temperature that enters the salt lake brine of electrodialyzer diluting compartment is 5～50 ℃, and the pH value is 0～12.
The current density range that applies at the electrode vessel two ends of electrodialyzer is 50A/m
2～650A/m
2
This method also comprises from salt lake brine through monovalence selective ion exchange membrane electrodialysis process and can reclaim boron simultaneously and remove sulfate radical from demineralised liquid; Gained boracic demineralised liquid is carried boron through hydrochloric acid or sulfuric acid acidation.
A kind of from salt lake brine the method for separating magnesium and concentrated lithium, comprise the steps:
(1) with Mg
2+With Li
+Weight ratio be 300: 1～1: 1, contain Li
+Concentration 0.02～20g/L, its proportion are the diluting compartment that the salt lake brine of 1.1～1.6g/ml is sent into first step electrodialyzer;
(2) the monovalence selective ion exchange membrane of utilizing first step electrodialyzer is carried out lithium ion to the salt lake brine in above-mentioned (1) step diluting compartment and is concentrated, and obtains first step concentrated solution;
(3) first step concentrated solution A, collection, or B, the concentration compartments that returns first step electrodialyzer carry out the batching of first step initial concentration liquid, and the density of the first step initial concentration liquid after the batching is 1.0～1.4g/ml; Or C, as the initial demineralised liquid of the diluting compartment of second stage electrodialyzer; Its density is 1.0～1.6g/ml;
(4) the monovalence selective ion exchange membrane of utilizing second stage electrodialyzer is carried out lithium ion to the demineralised liquid in above-mentioned (3) step and is concentrated, and obtains second stage concentrated solution;
(5) second stage concentrated solution A, collection; Or B, the concentration compartments that returns second stage electrodialyzer carry out the batching of second stage initial concentration liquid, and the density of the second stage initial concentration liquid after the batching is 1.0～1.4g/ml;
(6) diluting compartment that the demineralised liquid after the initial demineralised liquid of the diluting compartment of second stage electrodialyzer separates returns the first step electrodialyzer in above-mentioned (1) step is made the batching mother liquor of initial demineralised liquid.
Used monovalence selective ion exchange membrane comprises monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane in the described electroosmose process; Wherein said monovalent cation selective ion exchange membrane is selected from modification strong acid type (Na type) film K100 and the K192 that Japanese Asahi Chemical company produces, modification strong acid type (Na type) film CMS and CM-1 that Japan Tokuyama Soda company produces, Selemion modification strong acid type film CMV and CMR that Japan Asahi Glass company produces, a kind of in the film of the CMI-7000 that U.S. Membranes International Inc. company produces; The matrix of this film is selected from least a in vinylbenzene-Vinylstyrene co-polymer, vinylbenzene-sulfonate polymer and the divinyl benzene polymers; Its properties-correcting agent is selected from (R--SO
3H) active group, polymine; Described univalent anion selective ion exchange membrane is selected from quaternary amine (Cl type) the modification highly basic film ACM that quaternary amine (Cl type) modification highly basic film A111 that Japanese Asahi Chemical company produces and A192 or Japanese Tokuyama Soda company produce, the Selemion modification strong base film TM ASV that Japan Asahi Glass company produces, a kind of in the film of the AMI-7000 that U.S. Membranes International Inc. company produces; The matrix of this film is selected from least a in styrene diethylene benzene copoly mer, 4-vinylpyridine and divinylbenzene copolymer, 1-chloro-4-methyl-benzene and the divinylbenzene copolymer; Its properties-correcting agent is selected from (R--N (CH
2)
3Cl) active group, polyene propyl bromide salt.
The present invention compares with prior art has following advantage:
1, the invention provides the new technology of high efficiency separation magnesium, borate, sulfate radical and highly selective extraction lithium from the high Mg/Li ratio salt lake brine.
2, the present invention produces through the test of different bittern, different scales, proves economical and practical technology and the technology of carrying lithium from Qinghai high Mg/Li ratio bittern.Its advantages of simple technological process, easy to operate.
3, rich lithium bittern provided by the invention is produced Quilonum Retard or lithium chloride, and its product cost has competitive power; Simple, the suitable local condition of operating process; Good product quality, meet the world market requirement.
4, the mother liquor reusable edible that produces of the present invention has improved the utilization ratio of lithium, the single extraction yield of lithium more than 80% wherein, Mg
2+Decreasing ratio 〉=95%, B
3+Decreasing ratio 〉=99%, SO
4 2-Decreasing ratio 〉=99%.
5, raw material resources reserves of the present invention are abundant.
6, utilization the present invention has realized the comprehensive utilization of resources such as salt lake lithium, boron, potassium.
Concrete embodiment
The present invention also will be described in further detail in conjunction with the embodiments:
Embodiment:
To contain that salt pan that negatively charged ion such as lithium, magnesium etc., divalent cation and chlorine root, sulfate radical and borate are formed or that is made up of above-mentioned ion is concentrated to contain the diluting compartment that the old halogen of lithium is sent into electrodialyzer, this electrodialyzer is made up of diluting compartment, concentration compartments and utmost point chamber.
The end face of concentration compartments and diluting compartment is equipped with monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane, the film logarithm 1～500 of each membrane stack of electrodialyzer, and negative electrode and anode are equipped with respectively in cathode compartment and anolyte compartment.When getting bittern, the salt pan of the diluting compartment of sending into electrodialyzer solar evaporation contains Li
+Concentration 0.02～20g/L, bittern is turbulence state, determine and stable control electrode working current value at 50～650A/m
2In the scope, its error is stabilized in ± 10A/m
2In the time of in the scope, stable control working current value, lithium ion is moved to the concentration compartments by diluting compartment with fast speeds, and magnesium relative with the travelling speed of, borate, sulfate ion will be slowly many, lithium ion is constantly enrichment in concentrated solution, and most of magnesium, borate and sulfate ion then are trapped in the desalination solution.(Mg in initial desalination solution
2+/ Li
+) weight ratio is 300: 1～1: 1 o'clock, through monovalent ion selectivity electrodialysis process, separates concentrating that magnesium lithium weight ratio can be reduced to 10～0.1 in the rich lithium concentrated brine solution that obtains, the lithium ion in the concentrated solution can be enriched to 200 grams per liters, bittern Li in this process
+The rate of recovery 〉=80%, Mg
2+Decreasing ratio 〉=95%, B
3+Decreasing ratio 〉=99%, SO
4 2-Decreasing ratio 〉=99%.
Specific embodiments of the invention are as follows:
Embodiment one:
By the electrodialyzer that the rectangle synthetic glass constitutes, 10 desalting chamber, 9 concentration compartmentss.Monovalent ion selective membrane model is CMI-7000 and AMI-7000.The anode material is the platinum plate, and negative electrode is a stainless steel plate.Advancing desalting chamber's raw brine total salt concentration is 520g/L, wherein contains 6g/L Li
+, 120g/L Mg
2+Advancing the initial liquid in concentration compartments is 0.5M HCl; Advancing the initial liquid of electrode vessel is 0.5M NaCl.Turbulence state, current density 100A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table I.
Table I
| Li +，g/L | Mg 2+，g/L | (Mg 2+/Li +) Constr | |
| The demineralised liquid concentrated solution | 1.2 5.6 | 112 11.8 | 94 2.1 |
Find out (Mg from the result of Table I
2+/ Li
+)
ConstrBe 2.1, can directly produce Quilonum Retard with alkali precipitation.(Mg wherein
2+/ Li
+)
ConstrBe the Mg in the concentrated solution
2+With Li
+Concentration ratio.
Embodiment two:
The small-sized electrodialysis unit of fastening type is made of 50 desalting chamber and 51 concentration compartmentss, and monovalent ion selective membrane model is CMS and ACM.The anode material is that titanium is coated with the ruthenium plate, and negative electrode is that titanium is coated with ruthenium plate or stainless steel galvanized sheet.Advancing desalting chamber's raw brine total salt concentration is 510g/L, wherein contains 6g/L Li
+, 108g/L Mg
2+Advancing the initial liquid in concentration compartments is from dosing; Advance the initial liquid 0.5M of electrode vessel Na
2SO
4Demineralised liquid house line speed 8cm/sec., current density 100A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table II.
Table II
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 0.68 100.28 0.32 10.42 29.38 | 4.56 9.28 2.21 0.34 0.08 |
Find out (Mg/Li) of calculating from the result of Table II
ConstrBe 2.0, can directly produce Quilonum Retard with alkali precipitation.(Na/Li) that calculates
ConstrBe 0.49, (B/Li)
ConstrBe 0.075, (SO
4/ Li)
ConstrBe 0.018.Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
Embodiment three:
With embodiment two, advance desalting chamber's raw brine and contain 6g/L Li
+, 108g/L Mg
2+Advancing the initial liquid in concentration compartments is from dosing; Advance the initial liquid 0.5M of electrode vessel Na
2SO
4Demineralised liquid house line speed 8cm/sec., current density 200A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table III.
Table III
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 0.8 105.2 0.3 10.6 29.38 | 11.4 19.3 5.0 0.75 0.08 |
Find out from the result of Table III, (Mg/Li)
ConstrBe 1.7, can directly produce Quilonum Retard with alkali precipitation.Compare with the result of Table II, (Mg/Li)
ConstrReduce.(Na/Li) that calculates
ConstrBe 0.44, (B/Li)
ConstrBe 0.066, (SO
4/ Li)
ConstrBe 0.007.Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
Embodiment four:
Adopt the two-stage electrodialyzer, first step electrodialysis separates with embodiment three, and the second stage electrodialysis of carrying out separates as follows: advancing desalting chamber's raw brine total salt concentration is 40g/L, wherein contains 3g/L Li
+, 5.1g/L Mg
2+Advancing the initial liquid in concentration compartments is from dosing; Advance the initial liquid 0.5M of electrode vessel Na
2SO
4Demineralised liquid house line speed 8cm/sec., current density 200A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table IV.
Table IV
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 0.25 7.67 0.14 0.33 0.004 | 10.47 5.15 5.96 0.11 0.0002 |
Find out from the result of Table IV, (Mg/Li)
ConstrBe 0.49, can directly produce Quilonum Retard with alkali precipitation.(Na/Li) that calculates
ConstrBe 0.57, (B/Li)
ConstrBe 0.01, (SO
4/ Li)
ConstrBe 2 * 10
-5Compare Mg, Na, B, SO in the concentrated solution with the result of Table II
4Ionic concn reduces, (Mg/Li)
ConstrReduce.Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
Embodiment five:
Adopt the two-stage electrodialyzer, first step electrodialysis separates with embodiment three, and the second stage electrodialysis of carrying out separates as follows: advancing desalting chamber's raw brine total salt concentration is 90g/L, wherein contains 6.9g/L Li
+, 11.7g/LMg
2+Advancing the initial liquid in concentration compartments is from dosing; Advance O.5M Na of the initial liquid of electrode vessel
2SO
4Demineralised liquid house line speed 8cm/sec., current density 400A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table V.
Table V
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 0.19 6.1 0.10 0.27 0.004 | 10.4 5.12 5.37 0.08 0.0002 |
Find out from the result of Table V, (Mg/Li)
ConstrBe 0.49, can directly produce Quilonum Retard with alkali precipitation.(Na/Li) that calculates
ConstrBe 0.52, (B/Li)
ConstrBe 7.7 * 10
-3, (SO
4/ Li)
ConstrBe 1.9 * 10
-5Compare with the result of Table IV, (Na/Li)
Constr, (B/Li)
Constr, (SO
4/ Li)
ConstrReduce, promptly Mg, Na, B ionic concn reduce in the concentrated solution.Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
Embodiment six:
Adopt two-stage electrodialysis series operation, the concentrated solution of one-level is made the demineralised liquid of secondary, and the demineralised liquid of secondary is made single stage desalting liquid batching.One progressive desalting chamber raw brine total salt concentration is 510g/L, wherein contains 6g/LLi
+, 108g/L Mg
2+Advancing the initial liquid in concentration compartments is from dosing.Demineralised liquid house line speed 8cm/sec., current density 200A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table VI.
Table VI
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 0.9 100.6 0.3 10.6 29.38 | 11.2 19.6 5.0 0.75 0.08 |
Find out from the result of Table VI, (Mg/Li)
ConstrBe 1.7, can directly produce Quilonum Retard with alkali precipitation.(Na/Li) that calculates
ConstrBe 0.45, (B/Li)
ConstrBe 0.067, (SO
4/ Li)
ConstrBe 7.1 * 10
-3
The second stage electrodialysis of carrying out separates as follows: advancing desalting chamber's raw brine total salt concentration is 150g/L, wherein contains 11.2g/L Li
+, 19.6g/L Mg
2+Advancing the initial liquid in concentration compartments is from dosing; Advance the initial liquid 0.5M of electrode vessel NaNO
3Demineralised liquid house line speed 8cm/sec., current density 400A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculating (Mg/Li)
Constr, the results are shown in Table VII.
Table VII
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 0.89 17.8 0.10 0.27 0.004 | 10.3 4.77 5.37 0.08 0.0002 |
Find out from the result of Table VII, (Mg/Li)
ConstrBe 0.46, can directly produce Quilonum Retard with alkali precipitation.(Na/Li) that calculates
ConstrBe 0.52, (B/Li)
ConstrBe 7.8 * 10
-3, (SO
4/ Li)
ConstrBe 1.9 * 10
-5Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
Embodiment seven:
With embodiment one, to low lithium amount, high Mg/Li ratio bittern three-stage electrodialysis device separating magnesium and the concentrated lithium of extraction of containing.Advance first step desalting chamber raw brine and contain 0.5g/L Li
+, 100g/L Mg
2+, advance the initial liquid in concentration compartments for from dosing, advance the initial liquid 0.5M of electrode vessel NaCl.Turbulence state, current density 250A/m
2Demineralised liquid, concentrated solution, each self-circulation of electrode solution.Analyze the Li of demineralised liquid and concentrated solution
+, Mg
2+Concentration, and calculate (Mg
2+/ Li
+)
Constr
Table VIII
| Element | Demineralised liquid g/L | Concentrated solution I g/L | Concentrated solution II g/L | Concentrated solution III g/L |
| Li Mg Na B SO 4 | 0.15 94.5 0.029 10.6 30.1 | 5.1 60.0 1.183 0.49 1.32 | 10.3 17.2 1.165 0.155 0.087 | 10.6 4.7 1.080 0.052 0.005 |
The result finds out from Table VIII, (Mg/Li)
ConstrBe 12, can not directly produce Quilonum Retard with alkali precipitation, alkali charge is excessive when making with extra care bittern loses serious with lithium salts otherwise can cause.Concentrate lithium, (Mg/Li) of calculating by three-stage electrodialysis device separating magnesium and extraction
ConstrBe 0.44, (Na/Li)
ConstrBe 0.10, (B/Li)
ConstrBe 4.9 * 10
-3, (SO
4/ Li)
ConstrBe 4.7 * 10
-4Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
First step efficient low, (Mg/Li)
ConstrHigher, but can be used as the recoverying and utilizing method of lithium.
Embodiment eight:
Adopt each liquid stream of multistage electrodialysis group to be continuous, semicontinuous or andnon-continuous operation manner, the concentrated solution of previous stage is made the demineralised liquid of next stage, and the demineralised liquid of next stage is made its upper level demineralised liquid batching.Electrodialysis group operational conditionss at different levels are with embodiment six.Analyze Li in first step desalination end of a period liquid and the last grade concentrated solution
+, Mg
2+Plasma concentration, and calculate (Mg
2+/ Li
+)
Constr, the results are shown in Table IX.
Table I X
| Element | Demineralised liquid, g/L | Concentrated solution, g/L |
| Li Mg Na B SO 4 | 1.1 100.6 1.5 10.8 29.36 | 10.63 5.05 5.86 0.09 0.0003 |
Find out from the result of Table I X, (Mg/Li)
ConstrBe 0.475, can directly produce Quilonum Retard with alkali precipitation.(Mg/Li) that calculates
ConstrBe 0.44, (Na/Li)
ConstrBe 0.55, (B/Li)
ConstrBe 4.7 * 10
-3, (SO
4/ Li)
ConstrBe 2.8 * 10
-5Wherein (Na/Li)
ConstrBe the concentration ratio of Na in the concentrated solution and Li, (B/Li)
ConstrBe the concentration ratio of B in the concentrated solution and Li, (SO
4/ Li)
ConstrBe the SO in the concentrated solution
4Concentration ratio with Li.
Claims (13)
1, a kind of from salt lake brine the method for separating magnesium and concentrated lithium, comprise the steps: described salt lake brine is carried out one or more levels ion-exchange membrane electrodialysis, be about to salt lake brine and send into the diluting compartment of electrodialyzer, through the electrodialysis of monovalent ion selectivity, described monovalence selective ion exchange membrane comprises monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane; Obtain spissated rich lithium concentrated brine solution in the concentration compartments of electrodialyzer, magnesium, borate, sulfate radical then are trapped in the diluting compartment, realize that magnesium, borate, sulfate radical separate with lithium.
2, as claimed in claim 1 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that described salt lake brine is selected from concentrated brine, high Mg/Li ratio salt lake brine that high Mg/Li ratio salt lake brine, the evaporation of high Mg/Li ratio salt lake brine obtain and carries at least a in the old halogen that the old halogen evaporation behind the potassium obtains; Mg in the described salt lake brine
2+With Li
+Weight ratio be 300: 1～1: 1, bittern contains Li
+Concentration 0.02～20g/L.
3, the method that concentrates lithium from salt lake brine as claimed in claim 1 is characterized in that entering in the described ion exchange method each liquid stream of one-level or series multistage electrodialyzer for continous way, sequential portion is circulating or the batch cycle formula;
(1) described continous way is that one or more levels electrodialyzer moves continuously, and promptly demineralised liquid and concentrated solution enter continuously that desalting chamber and concentration compartments promptly discharge in one-level or the series multistage electrodialyzer;
(2) described sequential portion is circulating is one or more levels sequential portion circular flow, promptly the demineralised liquid of first step circulation groove is sent to first step electrodialyzer by first step recycle pump, get back to first step circulation groove again through after the desalination, the small portion of demineralised liquid enters second stage circulation groove, rest part mixes with new stoste of replenishing, and enters the circulation of first step electrodialyzer once more; By this desalination in following electrodialyzers at different levels in proper order, last demineralised liquid is stored in the desalination liquid bath; When moving with desalination system, the stoste of concentrated solution system will concentrate the liquid bath circulation fluid by concentrate pump and send into desalination circulation in each electrodialyzer;
(3) described batch cycle formula is that concentrated solution and demineralised liquid circulate by the extracorporeal circulation groove respectively, and promptly demineralised liquid in the electrodialyzer and concentrated solution are to carry out closed cycle separately, drains after reaching the desalination requirement.
4, as claimed in claim 1 or 2 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that described monovalent cation selective ion exchange membrane is selected from a kind of in the film of the CMI-7000 that Selemion modification strong acid type film CMV that CMS that modification strong acid type (Na type) film K100 that Japanese Asahi Chemical company produces and K192, Japanese Tokuyama Soda company produce and CM-1 modification strong acid type (Na type) film, Japanese Asahi Glass company produce and CMR, U.S. Membranes International Inc. company produce; The matrix of this film is selected from least a in the multipolymer of styrene diethylene benzene copoly mer, vinylbenzene-co-polymer of sulfonate and Vinylstyrene; Its properties-correcting agent is selected from (R-SO
3H) active group, polymine.
5, as claimed in claim 1 or 2 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that a kind of among quaternary amine (Cl type) modification highly basic film ACM that described univalent anion selective ion exchange membrane is selected from quaternary amine (Cl type) modification highly basic film A111 that Japanese Asahi Chemical company produces and A192, Japanese Tokuyama Soda company and produces, Selemion modification strong base film TM ASV that Japanese Asahi Glass company produces, the AMI-7000 that U.S. Membranes International Inc. company produces; The matrix of this film is selected from least a in vinylbenzene-Vinylstyrene co-polymer, 4-vinylpyridine and divinylbenzene copolymer, 1-chloro-4-methyl-benzene and the divinylbenzene copolymer; Its properties-correcting agent is selected from (R--N (CH
2)
3Cl
-) active group, polyene propyl bromide salt.
6, as claimed in claim 1 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that the density of the initial concentration liquid in the concentration compartments of described electrodialyzer is 1.0～1.4g/ml; The density of the initial desalination solution in the diluting compartment of described electrodialyzer is 1.1～1.6g/ml.
7, as claimed in claim 1 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that the concentrated solution in the concentration compartments in the described electrodialyzer uses by following mode: A, circulation are as the batching mother liquor of the initial concentration liquid of its electrodialysis at the corresponding levels concentration compartments; Or B, as the initial demineralised liquid of the diluting compartment of next stage electrodialyzer.
8, as claimed in claim 7 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that diluting compartment that demineralised liquid behind the diluting compartment separating Li of described next stage electrodialyzer returns its upper level electrodialyzer makes the batching mother liquor of its initial demineralised liquid.
9, as claimed in claim 1 from salt lake brine the method for separating magnesium and concentrated lithium, the temperature that it is characterized in that entering the salt lake brine of electrodialyzer diluting compartment is 5～50 ℃, the pH value is 0～12.
10, as claimed in claim 1 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that at the current density range that the electrode vessel two ends of electrodialyzer apply be 50A/m
2～650A/m
2
11, as claimed in claim 1 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that this method also comprises from salt lake brine from demineralised liquid, can reclaim boron simultaneously and remove sulfate radical through monovalence selective ion exchange membrane electrodialysis process; Gained boracic demineralised liquid is carried boron through hydrochloric acid or sulfuric acid acidation.
12, a kind of from salt lake brine the method for separating magnesium and concentrated lithium, comprise the steps:
(1) with Mg
2+With Li
+Weight ratio be 300: 1～1: 1, contain Li
+Concentration 0.02～20g/L, its proportion are the diluting compartment that the salt lake brine of 1.1～1.6g/ml is sent into first step electrodialyzer;
(2) the monovalence selective ion exchange membrane of utilizing first step electrodialyzer is carried out lithium ion to the salt lake brine in above-mentioned (1) step diluting compartment and is concentrated, and obtains first step concentrated solution;
(3) first step concentrated solution A, collection, or B, the concentration compartments that returns first step electrodialyzer carry out the batching of first step initial concentration liquid, and the density of the first step initial concentration liquid after the batching is 1.0～1.4g/ml; Or C, as the initial demineralised liquid of the diluting compartment of second stage electrodialyzer; Its density is 1.0～1.6g/ml;
(4) the monovalence selective ion exchange membrane of utilizing second stage electrodialyzer is carried out lithium ion to the demineralised liquid in above-mentioned (3) step and is concentrated, and obtains second stage concentrated solution;
(5) second stage concentrated solution A, collection; Or B, the concentration compartments that returns second stage electrodialyzer carry out the batching of second stage initial concentration liquid, and the density of the second stage initial concentration liquid after the batching is 1.0～1.4g/ml;
(6) diluting compartment that the demineralised liquid after the initial demineralised liquid of the diluting compartment of second stage electrodialyzer separates returns the first step electrodialyzer in above-mentioned (1) step is made the batching mother liquor of initial demineralised liquid.
13, as claimed in claim 12 from salt lake brine the method for separating magnesium and concentrated lithium, it is characterized in that monovalence selective ion exchange membrane used in the described electroosmose process comprises monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane; Wherein said monovalent cation selective ion exchange membrane is selected from modification strong acid type (Na type) film K100 and the K192 that Japanese Asahi Chemical company produces, modification strong acid type (Na type) film CMS and CM-1 that Japan Tokuyama Soda company produces, Selemion modification strong acid type film CMV and CMR that Japan Asahi Glass company produces, a kind of in the film of the CMI-7000 that U.S. Membranes International Inc. company produces; The matrix of this film is selected from least a in vinylbenzene-Vinylstyrene co-polymer, vinylbenzene-sulfonate polymer and the divinyl benzene polymers; Its properties-correcting agent is selected from (R--SO
3H) active group, polymine; Described univalent anion selective ion exchange membrane is selected from quaternary amine (Cl type) the modification highly basic film ACM that quaternary amine (Cl type) modification highly basic film A111 that Japanese Asahi Chemical company produces and A192 or Japanese Tokuyama Soda company produce, the Selemion modification strong base film TM ASV that Japan Asahi Glass company produces, a kind of in the film of the AMI-7000 that U.S. Membranes International Inc. company produces; The matrix of this film is selected from least a in styrene diethylene benzene copoly mer, 4-vinylpyridine and divinylbenzene copolymer, 1-chloro-4-methyl-benzene and the divinylbenzene copolymer; Its properties-correcting agent is selected from (R--N (CH
2)
3Cl) active group, polyene propyl bromide salt.
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| US11365128B2 (en) | 2017-06-15 | 2022-06-21 | Energysource Minerals Llc | Process for selective adsorption and recovery of lithium from natural and synthetic brines |
| CN108060308B (en) * | 2017-12-12 | 2020-01-03 | 中南大学 | Method and device for separating lithium from lithium-containing solution |
| CN110917882B (en) * | 2019-11-04 | 2020-11-17 | 杭州匠容道环境科技有限公司 | Four-channel electrodialysis device for extracting lithium from salt lake and method for extracting lithium from salt lake |
| CN115386740A (en) * | 2022-08-30 | 2022-11-25 | 中南大学 | Method and device for extracting lithium from brine or seawater based on electrodialysis principle |
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2003
- 2003-12-20 CN CN 200310122238 patent/CN1281497C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022177999A1 (en) * | 2021-02-16 | 2022-08-25 | Energy Exploration Technologies, Inc. | Polymeric materials and methods for selective ion separation or transport |
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