CN100408705C - Nano-filtration method for separating magnesium and enriching lithium from salt lake brine - Google Patents
Nano-filtration method for separating magnesium and enriching lithium from salt lake brine Download PDFInfo
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- CN100408705C CN100408705C CNB03108088XA CN03108088A CN100408705C CN 100408705 C CN100408705 C CN 100408705C CN B03108088X A CNB03108088X A CN B03108088XA CN 03108088 A CN03108088 A CN 03108088A CN 100408705 C CN100408705 C CN 100408705C
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- lithium
- salt lake
- bittern
- nanofiltration
- brine
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 106
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000012267 brine Substances 0.000 title claims abstract description 63
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 63
- 239000011777 magnesium Substances 0.000 title claims abstract description 52
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000012528 membrane Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract 2
- 241001131796 Botaurus stellaris Species 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 230000004087 circulation Effects 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000012530 fluid Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000009874 alkali refining Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005206 flow analysis Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- -1 lithium salt compound Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 239000000126 substance Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention uses a nanofiltration method to separate and enrich lithium in salt lake brine and is suitable for the separation of magnesium and lithium and the enrichment of the lithium in lithium containining brine or a lithium containing solution obtained from a salt lake, and lithium carbonate or lithium chloride is prepared from the obtained lithium enriched brine. In the method, the lithium in the lithium containing brine obtained by evaporating a salt field containing the cations of Mg<2+>, Ca<2+>, etc. and the anions of SO4<2->, BxOy<n->, etc. is separated and enriched through nanofiltration membranes, wherein the Li<+> concentration of the lithium containing brine is from 0.1 to 11.5 g/L, the weight ratio of the magnesium to the lithium is from 1:1 to 200: 1, and qualified lithium enriched brine needed by the preparation of the lithium carbonate or the lithium chloride is obtained. The present invention provides an effective method for extracting the lithium from the salt lake brine with high magnesium lithium ratio, the weight ratio of Mg<2+> to Li<+> of the lithium enriched brine obtained by separation is from 0.6:1 to 5:1, and the Li<+> concentration of the lithium containing brine is from 0.6 to 20 g/L.
Description
Technical field
The present invention relates to a kind of method, especially a kind of method that contains separating magnesium and enriching lithium lithium bittern or the lithium-containing solution that obtains from the salt lake with nano filtering process separating magnesium and enriching lithium from salt lake brine.
Background of invention
In traditional technology of from ore, carrying lithium, at first together carry out roasting with sulfuric acid and triphane, water embathes calcining matter then, and the gained lithium sulfate solution is handled with lime and soda ash, to remove magnesium and calcium wherein, then Quilonum Retard is precipitated out.Other treatment process comprises so-called alkaline process and ion exchange method, and these method gained lithium solution are lithium hydroxide, lithium chloride or Lithium Sulphate, and these methods also comprise the step that removes magnesium and calcium in the solution with lime and soda ash.
Yet, reclaiming lithium from having the complicated chloride type salt lake brine of forming, its economy depends on that not only bittern contains lithium concentration, and depends on the especially concentration of magnesium and calcium of interfering ion in the bittern.Magnesium has the chemical property similar to lithium, makes that both separation are very difficult.The external now bittern of industrialization is put forward the lithium technology and is all only limited to the Mg/Li ratio value less than 6: 1 bittern, and the Qinghai Salt Lake Bittern Mg/Li ratio was up to 200: 1, can not directly use Exposure to Sunlight to analyse the simple method of salt, alkali refining and precipitation Quilonum Retard, otherwise excessive, the serious and too high problem of cost of lithium salts loss of alkali charge can cause brine refining the time.
High Mg/Li ratio value bittern is carried internal and international the going up of lithium have many methods, as electrolysis or film electrolytic process, salting-out process, organic solvent extractionprocess, adsorbents adsorb method and the precipitator method etc.Wherein, electrolytic process and film electrolytic process are purpose to produce lithium salt compound, but still need in advance magnesium and calcium to be removed, and can produce a large amount of hydrogen and chlorine, and be seriously unfavorable for producing.The tbp extraction process adopt to concentrate rich lithium high-magnesium brine as raw materials for production, and yield is than higher, but long flow path, equipment corrosion is serious, production cost is high, is difficult to realize industrialization.Absorption method is to utilize Choice of Resin absorption lithium ion, but resin price height, loading capacity are low, is easily polluted by bittern and is difficult to regeneration, and its industrialization is subjected to the dual restriction of scale and cost.Precipitator method feasible process, but long flow path, yield is low, the material cycling amount is big, repeatedly calcining is filtered, trivial operations, and it is lower that hydrothermal decomposition or roasting leaching liquid contain lithium concentration, needs evaporated water big when concentrating.
Summary of the invention
The objective of the invention is for a kind of method with nano filtering process separating magnesium and enriching lithium from salt lake brine is provided.This method can be from the high Mg/Li ratio salt lake brine separating magnesium and extract lithium effectively.Its technical process is simple, operation is reliable, energy consumption is low, and quality traitor, the cost of the finished product Quilonum Retard that makes and lithium chloride are lower.
Purpose of the present invention can realize by following measure:
The method of a kind of nano filtering process lithium in separating magnesium and the enrichment salt lake brine from salt lake brine, it is the high-tension side of salt lake brine being sent into the nanofiltration device, the formation pressure reduction of exerting pressure in the nanofiltration membrane both sides, a large amount of lithium ions and portion water are moved to low-tension side from the high-tension side through nanofiltration membrane in the raw brine becomes rich lithium bittern; The high-tension side rest solution becomes poor lithium and is rich in other ionic bittern such as magnesium, borate, sulfate radical; The nanofiltration membrane of described nanofiltration device is a monovalent ion selectivity nanofiltration membrane; Mg in the described salt lake brine
2+With Li
+Weight ratio be 1: 1～200: 1, bittern contains Li
+Concentration 0.1～11.5g/L; The pressure reduction that described nanofiltration device puts on the nanofiltration membrane both sides is 450kPa～3500kPa.
Wherein nanofiltration device is made of membrane module, security personnel's strainer, raw water pump, high-pressure pump and former liquid bath and production fluid groove.Wherein, membrane module is a rolled membrane module, and its inside is divided into dope side (high-tension side) and production fluid side (low-tension side); Raw brine (stoste) enters the high-tension side, and under the effect that applies the enough pressure reduction in film both sides, a large amount of lithium ions and portion water are moved to low-tension side by the high-tension side through film in the stoste becomes rich lithium bittern from producing mouth of a river discharge; The high-tension side rest solution becomes poor lithium bittern and discharges from concentrated water spout.
Described contain lithium bittern comprise chloride type contain lithium salts lake bittern water, chloride type salt lake brine evaporation gained and contain lithium bittern and chloride type salt lake brine and carry potassium after the evaporation gained contain the old halogen of lithium.
Utilize monovalence selectivity nanofiltration membrane that the lithium in the salt lake brine is carried out flash trapping stage and enrichment at least, being about to contain the lithium salts lake bittern water pumps in the nanofiltration device as stoste, under the effect of enough pressure reduction lithium is carried out selective separation and enrichment, the production fluid that obtains being rich in lithium ion is rich lithium bittern.
Used monovalent ion selectivity nanofiltration membrane is a kind of among the NF-40HF of the NTR7410 of MPT 20, Nitto of CML-DC010, Membrane Products of Desal 5L series membranes, CM-celfa of U.S. Osmonics company and DOW-filmtec.This nanofiltration membrane material is at least a in cellulose acetate and derivative, aromatic polyamide, polyimide and the SPSF.
Ingress's stoste density of nanofiltration device is 1.0～1.2g/ml; The density of the rich lithium bittern of production fluid is 1.0-1.2g/ml.
Entering the temperature that the nanofiltration device contains the lithium raw brine is 5～50 ℃, and the pH value is 2～11.
The rich lithium bittern of certain one-level nanofiltration device gained can collect as the qualified lithium solution of carrying, and also can obtain the higher-quality lithium solution of carrying through next stage or multistage nanofiltration device again.
In order to guarantee the yield of lithium, can be that poor lithium bittern turns back to the batching mother liquor of its upper level nanofiltration device as its raw brine with certain one-level nanofiltration device gained dope.
This method also comprises separating obtained bittern spissated process in addition.
The method of a kind of nano filtering process separating magnesium and enriching lithium from salt lake brine specifically comprises the steps:
(1) with Mg
2+With Li
+Weight ratio be 1: 1～200: 1, contain Li
+Concentration 0.1～11.5g/L, density is that the salt lake brine of 1.1～1.2g/m1 pumps into first step nanofiltration device;
(2) applying under the enough differential pressure actions in nanofiltration membrane both sides, the lithium in the bittern by enrichment, obtains the rich lithium bittern of the first step through nanofiltration membrane in the production fluid exit;
(3) the rich lithium of the first step produces water A, collection, or B is as the raw brine of second stage nanofiltration device, and its density is 1.0～1.2g/ml;
(4) utilize the nanofiltration membrane of second stage nanofiltration device that lithium ion in " raw brine " in (3) is separated and enrichment, obtain the rich lithium bittern in the second stage;
(5) the rich lithium bittern in second stage A, collection; Or B, as its next stage nanofiltration device stock liquid; Its density is 1.0～1.2g/ml; Reuse rich lithium bittern as the stock liquid of the nanofiltration device of next stage and lithium ion is separated and enrichment;
(6) the batching mother liquor of above-mentioned (1) middle first step nanofiltration device as its stoste returned in dense water water outlet after second stage nanofiltration device gained separated; The dope of circulation next stage is as the on high-tension side batching mother liquor that the nanofiltration device of rich lithium bittern is provided;
The pressure reduction that described nanofiltration device applies the nanofiltration membrane both sides is 450～3500kPa.
By adopting stage trapping magnesium and dope round-robin technology, this method makes the enrichment degree of lithium improve greatly, and has guaranteed the yield of lithium.
The nanofiltration separation technology that this method provided also can be held back the sulfate radical that exists in the bittern efficiently and reduce boron in the rich lithium bittern effectively.
The present invention compares with prior art has following advantage:
1, the invention provides from the high Mg/Li ratio salt lake brine economical, reclaim the new technology of lithium effectively.
2, through different bittern evidences: the present invention is a feasible method carrying lithium from the high Mg/Li ratio bittern of Qinghai.Its advantages of simple technological process, operation is reliable, energy consumption is low.
3, raw material resources reserves of the present invention are abundant.
4, rich lithium bittern provided by the invention is produced Quilonum Retard or lithium chloride, and its product cost has international competitiveness, and quality product meets or exceeds national standard.
Concrete embodiment
Below by concrete and non-limiting embodiment the present invention is described in detail.
Embodiment one:
The separating effect of present embodiment explanation one-level nanofiltration device.
With the CML-DC nanofiltration membrane salt lake brine is separated, film effective film area is 1.77m
2The nanofiltration device is made of parts such as membrane module, security personnel's strainer, raw water pump, high-pressure pump and former tank and product tanks.To contain lithium 0.369g/L, magnesium 7.0g/L, boron 0.392g/L and sulfate radical 1.508g/L, the raw brine of pH=5.5 is squeezed in the former tank, down with under the pressure reduction of 850kPa raw brine is separated at 18～30 ℃.Lock out operation is intermittent cyclic operation, and promptly the exit dope turns back to former liquid bath and circulates.Sampling analysis after 4.5 hours, each feed liquid is formed as shown in table 1:
Table 1.
As can be seen, through flash trapping stage, the Mg content that produces in the water reduces greatly, and lithium content obtains enrichment, and sulfate radical is almost all held back simultaneously, and its rejection is 98.8%, and the content that produces boron in the water simultaneously also has reduction significantly.By being reduced to 4.5 in the product water by 18.9 in the raw brine, this ratio has been suitable for the rich lithium bittern of gained is made with extra care and produce Quilonum Retard with alkaline process through one-level nanofiltration device separating magnesium lithium weight ratio.The apparent separation factor of process is respectively: P
Mg/Li=7.0, P
B/Li=4.8, P
SO4/Li=116.9, the penetrant yield is 35%.Therefore this method can efficiently remove the sulfate radical in the bittern, helps the refining of rich lithium bittern.
Implication and formula to each parameter are described as follows:
Film is to Mg
2+With Li
+Apparent separation factor: P
Mg/Li=(Mg
2+/ Li
+)
C/ (Mg
2+/ Li
+)
P
Film is to B and Li
+Apparent separation factor: P
B/Li=(B/Li
+)
C/ (B/Li
+)
P
Film is to SO
4 2-With Li
+Apparent separation factor: P
SO4/Li=(SO
4 2-/ Li
+)
C/ (SO
4 2-/ Li
+)
P
Wherein, subscript C and P represent nanofiltration gained dope and production fluid respectively.
Embodiment two:
Present embodiment description operation temperature is to the diactinic influence of nanofiltration separation.With embodiment one.Under 25～40 ℃, raw brine is carried out separation and concentration, after 4.5 hours to each sample sampling analysis, result such as table 2:
Table 2
When improving temperature as can be seen, compare with embodiment one, the separation performance of nanofiltration membrane is slightly with low, but the penetrant yield has brought up to 42% by 35%, makes the single-stage yield of lithium bring up to 75% by 65%, has improved utilization ratio of raw materials.
Embodiment three:
Present embodiment illustrates the separating effect of multistage nanofiltration.With embodiment one.To contain lithium 0.202g/L, magnesium 20.1g/L, boron 0.357g/L and sulfate radical 0.943g/L, the raw brine of pH=6.0 is sent into former liquid bath, raw brine is being carried out three grades of circulations separating under 20～35 ℃ the temperature with under the effect of the pressure reduction of 1000kPa, be about to the rich lithium production fluid of I and II nanofiltration device gained respectively as two, three grades of isolating raw brines of nanofiltration device, with the dense water of poor lithium of two, three grades of nanofiltration device gained respectively as the batching mother liquor of the isolating stoste of I and II nanofiltration device.Separating obtained main feed liquid is formed and separation factor such as table 3:
Table 3
As can be seen, separate through three grades of nanofiltration devices, Mg/Li ratio is reduced to 1.18 of three grades of rich lithium bittern by 100 of raw brine; Sulfate radical is removed completely; Boron in the product liquid also has reduction significantly.This feed liquid can be directly with alkali refining with produce Quilonum Retard, its consumption alkali cost reduces greatly.Through three grades of separation, the enrichment degree of lithium reaches large increase.In three grades of separation processes, owing to the batching mother liquor of two, three grades dopes as one-level stoste, the yield of lithium is guaranteed.
Embodiment four:
Present embodiment explanation nanofiltration membrane is to separating the concentrated effect of the rich lithium bittern in back.Three grades of embodiment three gained are produced water to be concentrated with Filmtec NF-40HF nanofiltration membrane, the operation of being adopted still is the intermittent cyclic mode, the mould difference is 1200kPa, former liquid temp is 20～35 ℃, pH=6.0, cyclical operation 5 hours, the gained dope turns back to the nanofiltration process of embodiment three, as the proportion liquid of its third stage stoste.Each liquid flow analysis result such as table 3:
Table 3
As can be seen, above-mentioned nanofiltration process removes lithium is further separated with magnesium, boron, sulfate radical, and the relative content of magnesium, boron and sulfate radical further obtains outside low, and lithium ion has obtained concentrating largely, and its concentration is brought up to original 6 times nearly.The concentration and the relative content of the rich lithium production fluid of gained are more suitable for producing in alkali refining and Quilonum Retard.
Claims (13)
1. the method for nano filtering process separating magnesium and enriching lithium from salt lake brine comprises the steps:
Salt lake brine is sent into the high-tension side of nanofiltration device, the formation pressure reduction of exerting pressure in the nanofiltration membrane both sides, a large amount of lithium ions and portion water are moved to low-tension side from the high-tension side through nanofiltration membrane in the raw brine becomes rich lithium bittern; The high-tension side rest solution becomes poor lithium and is rich in the bittern of magnesium, borate, sulfate ion; The nanofiltration membrane of described nanofiltration device is a monovalent ion selectivity nanofiltration membrane; The described Mg that contains in the lithium bittern
2+With LI
+Weight ratio be 1: 1～200: 1, bittern contains Li
+Concentration 0.1～11.5g/L; The pressure reduction that described nanofiltration device puts on the nanofiltration membrane both sides is 450kPa～3500kPa.
2. the method for nano filtering process as claimed in claim 1 separating magnesium and enriching lithium from salt lake brine is characterized in that described salt lake brine is that chloride type contains lithium salts lake bittern water, chloride type salt lake brine evaporation gained salt lake brine and chloride type salt lake brine and carries behind the potassium at least a in the old halogen in evaporation gained salt lake.
3. the method for nano filtering process as claimed in claim 1 separating magnesium and enriching lithium from salt lake brine, flash trapping stage magnesium lithium and enrichment get rich lithium bittern to it is characterized in that utilizing the nanofiltration device to carry out at least by described salt lake brine.
4. as the method for claim 1 or 3 described nano filtering process separating magnesium and enriching lithium from salt lake brine, the material that it is characterized in that described monovalent ion selectivity nanofiltration membrane is selected from least a in cellulose acetate and derivative, aromatic polyamide, polyimide and the SPSF; Described monovalent ion selectivity nanofiltration membrane is selected from a kind of among the Filmtec NF-40HF of the NTR7410 of MPT 20, Nitto company of CML-DC010, the Membrane Products company of Desal 5L series membranes, the CM-celfa company of U.S. Osmonics company and DOW company.
5. as the method for claim 1 or 3 described nano filtering process separating magnesium and enriching lithium from salt lake brine, it is characterized in that described Density of Saline Brine is 1.0～1.2g/ml; The density of described rich lithium bittern is 1.0～1.2g/ml.
6. as the method for claim 1 or 3 described nano filtering process separating magnesium and enriching lithium from salt lake brine, it is characterized in that the former liquid bath that on high-tension side dope turns back to the nanofiltration device circulates.
7. the method for nano filtering process as claimed in claim 3 separating magnesium and enriching lithium from salt lake brine is characterized in that the nanofiltration device on high-tension side raw brine of the rich lithium bittern of described nanofiltration device low-tension side as next stage.
8. the method for nano filtering process as claimed in claim 7 separating magnesium and enriching lithium from salt lake brine is characterized in that the dope of low-tension side of the nanofiltration device of described next stage returns the high-tension side that the nanofiltration of rich lithium bittern device is provided, preparation raw material bittern.
9. the method with nanofiltration device separating magnesium and enriching lithium from salt lake brine as claimed in claim 1, the raw brine temperature that it is characterized in that entering the nanofiltration device is 5～50 ℃, the pH value is 2～11.
10. the method for nano filtering process separating magnesium and enriching lithium from salt lake brine comprises the steps:
(1) with Mg
2+With Li
+Weight ratio be 1: 1～200: 1, contain Li
+Concentration 0.1～11.5g/L, its density is that the lithium bittern that contains of 1.0～1.2g/ml is sent into first step nanofiltration device as stoste;
(2) under the effect that puts on both sides differential pressure of membrane, the magnesium in the stoste, borate, sulfate ion are separated and enriching lithium with lithium, obtain the rich lithium bittern of the first step in the low-tension side of nanofiltration device; Its density is 1.0～1.2g/ml;
(3) the rich lithium bittern of first step A, collection, or B, as second stage nanofiltration device stock liquid; Its density is 1.0～1.2g/ml;
(4) utilize second stage nanofiltration device that lithium ion in " stock liquid " in the step (3) is separated and enrichment, get the rich lithium bittern in the second stage:
(5) the rich lithium bittern in second stage A, collection; Or B, as next stage nanofiltration device stock liquid; Its density is 1.0～1.2g/ml; Reuse rich lithium bittern as the stock liquid of the nanofiltration device of next stage and lithium ion is separated and enrichment;
(6) second stage nanofiltration device gained dope returns the batching mother liquor of the middle first step nanofiltration device of step (1) as its stoste; The dope of circulation next stage is as the on high-tension side batching mother liquor that the nanofiltration device of rich lithium bittern is provided;
The pressure reduction that described nanofiltration device puts on the nanofiltration membrane both sides is 450kPa～3500kPa.
11. the method for nano filtering process as claimed in claim 10 separating magnesium and enriching lithium from salt lake brine, it is characterized in that this method also comprises carries out spissated process to separating obtained rich lithium bittern.
12. the method for nano filtering process as claimed in claim 10 separating magnesium and enriching lithium from salt lake brine is characterized in that the nanofiltration membrane in the described nanofiltration device is a monovalent ion selectivity nanofiltration membrane.
13. as claimed in claim 12ly with the nanofiltration device rich lithium bittern is carried out spissated method, the material that it is characterized in that described monovalent ion selectivity nanofiltration membrane is at least a in cellulose acetate and derivative, aromatic polyamide, polyimide and the SPSF; Described monovalent ion selectivity nanofiltration membrane is selected from a kind of among the Filmtec NT-40HF that Desal 5L series membranes that U.S. Osmonics company produces, CML-DC010 that CM-celfa company produces, MPT 20 that Membrane Products company produces, NTR7410 that Nitto company produces and DOW company produce.
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