CN103114211A - Method for extracting lithium from primary lithium extraction solution of lithium ore - Google Patents
Method for extracting lithium from primary lithium extraction solution of lithium ore Download PDFInfo
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- CN103114211A CN103114211A CN2013100536194A CN201310053619A CN103114211A CN 103114211 A CN103114211 A CN 103114211A CN 2013100536194 A CN2013100536194 A CN 2013100536194A CN 201310053619 A CN201310053619 A CN 201310053619A CN 103114211 A CN103114211 A CN 103114211A
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- lithium
- solution
- salts
- monovalent cation
- precipitation
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 113
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000000605 extraction Methods 0.000 title abstract description 7
- 238000001728 nano-filtration Methods 0.000 claims abstract description 48
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 34
- -1 cation salts Chemical class 0.000 claims description 27
- 238000001556 precipitation Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001620 barium bromide Inorganic materials 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- 229940045511 barium chloride Drugs 0.000 claims description 4
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000000909 electrodialysis Methods 0.000 claims description 4
- 229910052670 petalite Inorganic materials 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052822 amblygonite Inorganic materials 0.000 claims description 3
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001638 barium iodide Inorganic materials 0.000 claims description 3
- 229940075444 barium iodide Drugs 0.000 claims description 3
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 3
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 3
- 229940046413 calcium iodide Drugs 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 229910000174 eucryptite Inorganic materials 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000013535 sea water Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 73
- 150000001768 cations Chemical class 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 18
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 3
- 238000000926 separation method Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 3
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- COLRBPHEBSHUAG-UHFFFAOYSA-L disodium bromide chloride Chemical compound [Na+].[Na+].[Cl-].[Br-] COLRBPHEBSHUAG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for extracting lithium from a primary lithium extraction solution of lithium ore, mixing inorganic salt with the primary lithium extraction solution, and removing precipitates to obtain a secondary lithium extraction solution; (b) carrying out nanofiltration treatment on the secondary lithium extraction solution, and separating a monovalent cation salt solution from a multivalent cation salt solution; (c) extracting lithium salt from monovalent cation salt solution. Other monovalent and multivalent salt separation solution can be concentrated, crystallized or precipitated to obtain corresponding salts. The invention provides a new technology for economically and effectively recovering lithium from lithium ore, which has the advantages of rich raw material resource storage, simple and reasonable process flow, reliable operation and low energy consumption, and achieves the purposes of reducing cost and energy consumption.
Description
Technical field
The present invention relates to be specifically related to a kind of method of separating magnalium and enriching lithium from a sulfuric acid to leach liquid in lithium ore deposit from the method for lithium ore deposit extraction lithium.
Background technology
The present lithium industry of China is mainly to be processed as the master with the lithium ore deposit, and mainly carries lithium from triphane and lithionite.Carry lithium, with a long history from the lithium ore deposit, and constantly bring forth new ideas in its development, its technique is divided into two large classes: i.e. alkaline process and acid system.The limestone sintering method is arranged in alkaline process, and soda ash is pressed cooking method; Sulfuric acid process, sodium-acetate method and chlorination process etc. are arranged in acid system, and wherein, limestone sintering method and sulfuric acid process are the Main Means that lithium is carried in the lithium ore deposit.Limestone sintering method streams flux is large, and energy consumption is high, and the lithium rate of recovery is low, and product cost is high.
Sulfuric acid process is traditional production technique, first high temperature roast, and then water embathes calcining matter, and the gained sulphuric acid soln is processed with lime and soda ash, removes wherein magnesium and calcium, then precipitates lithium with carbonate, the high challenge of consuming energy.Therefore, this area also needs sulfuric acid process is improved.
Summary of the invention
The object of the present invention is to provide a kind of novel method of carrying lithium from the lithium ore deposit, advantages of simple technological process, operation is reliable, energy consumption is low.
The method of lithium of carrying from the lithium ore deposit that provides of the present invention is characterized in that, comprises the following steps:
(a) with inorganic salt with once carry lithium solution and mix, removing precipitation obtains secondary and carries lithium solution, wherein, described once carry lithium solution be after described lithium ore deposit and sulfuric acid baking again water embathe the solution of gained, described inorganic salt are selected from: at least a in calcium chloride, bariumchloride, Calcium Bromide, barium bromide, calcium iodide, barium iodide;
(b) secondary that step (1) is obtained is carried lithium solution and is carried out the nanofiltration processing, and the monovalent cation salts solution that secondary is carried in lithium solution separates with the polyvalent cation salts solution;
(c) extract lithium salts from the monovalent cation salts solution that step (2) obtains.
In another preference, described secondary is carried and is contained univalent anion (Cl in lithium solution
-, Br
-, I
-Or its combination).
In another preference, described monovalent cation is Li
+, Na
+, K
+, Rb
+, Cs
+Or its combination.
In another preference, described polyvalent cation is Ca
2+, Mg
2+, Al
3+Or its combination.
In another preference, described lithium ore deposit is selected from: lithionite, triphane, petalite, amblygonite, eucryptite, rich lithium tonstein, seawater mineral deposit, hot spring mineral deposit and pile up the mineral deposit.
In another preference, in described step (a), the described lithium solution of once carrying is mixed with described inorganic salt, standing mixing solutions after the inorganic salt dissolving, sulfate precipitation is separated out, and removes precipitation by centrifugal, filtration, obtains secondary and carries lithium solution.
In another preference, be precipitated as calcium sulfate or barium sulfate in described step (a).
In another preference, turn at rotating speed 1000-8000/min, centrifugal under 2-20min when turning, filter and remove precipitation, obtain secondary and carry lithium solution.
In another preference, the pH that described secondary is carried lithium solution is 2-11.
In another preference, described secondary is carried lithium solution and is contained Cl
-, Br
-, I
-, Li
+, Na
+, K
+, Rb
+, Cs
+, Ca
2+, Mg
2+, Al
3+Or its combination.
In another preference, the negatively charged ion that described secondary is carried in lithium solution is selected from: Cl
-, Br
-, I
-Or its combination; Described secondary is carried the positively charged ion Li in lithium solution
+, Na
+, K
+, Rb
+, Cs
+, Ca
2+, Mg
2+, Al
3+Or its combination.
In another preference, described secondary is carried in lithium solution and is contained sodium-chlor, Sodium Bromide, calcium chloride and/or Repone K etc.
In another preference, one or more in described step (b) in employing cellulose acetate membrane, polyamide membrane, polyimide film and sulfonated polysulfone membrane carry out nanofiltration to be processed.
In another preference, the surface of described nanofiltration membrane can be lotus positive electricity or bear electricity.
In another preference, described nanofiltration membrane can be tubulose, can be also tabular.
In another preference, described nanofiltration membrane can be assembled into tubular type, frame or rolling.
In another preference, described step (b) is carried out the nanofiltration processing, and nanofiltration pressure reduction is 0.25-3Mpa.
In another preference, to extract lithium salts in described step (c) and refer to the monovalent cation salts solution is mixed with alkali or carbonate, precipitation obtains LiOH or LiCO
3
In another preference, described alkali is sodium hydroxide or potassium hydroxide.
In another preference, described carbonate is sodium carbonate or salt of wormwood.
In another preference, extract lithium salts in described step (c) and refer to the monovalent cation salts solution is separated, concentrates and obtain lithium salts with membrane distillation concentration crystallization or electrodialysis.
In another preference, described method also comprises:
The polyvalent cation salts solution that step (2) is obtained carries out the step that condensing crystal or precipitation obtain polyvalent cation salt; And/or
The monovalent cation salts solution that step (2) is obtained carries out the step of condensing crystal or other the monovalent cation salt of precipitation except lithium salts.
A kind of method of separating magnalium and enriching lithium the lithium leaching liquid of carrying from the lithium ore deposit that the present invention proposes, compared with prior art, method of the present invention, economical from the lithium ore deposit, effectively reclaim lithium, and the raw material resources reserves are abundant; The advantages of simple technological process that provides, operation is reliable, energy consumption is low, reaches to reduce costs, reduce power consumption ground purpose, makes its product cost have international competitiveness, and quality product meets or exceeds national standard.The present invention not only can produce lithium chloride, LiOH or LiCO
3, also can and then produce other lithium salts.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus consist of new or preferred technical scheme.As space is limited, this tired stating no longer one by one.
Embodiment
The present inventor is through extensively and in depth research, and accident is developed a kind of novel lithium method of putting forward first, carries out abundant pre-treatment to once carrying lithium solution, is not affecting Li
+Situation under, with divalent sulfur acid group precipitate and separate, introduce simultaneously univalent anion, improve Li
+Efficient by the nanofiltration membrane Surface charge layer.No matter that monovalent cation (as Li, Na, K plasma) and the polyvalent cation (as Mg, Ca, Al plasma) that the nanofiltration membrane of lotus positive electricity or negative electricity is carried in lithium solution the secondary of removing the divalent sulfur acid radical anion has higher separating effect.After nanofiltration membrane treatment gained do not contain Mg, the isoionic Li of the containing solution of Ca and Al can obtain highly purified lithium-containing compound such as Li with methods such as precipitation, concentrated and crystallizations
2CO
3, LiOH and Li
2O etc.The method advantages of simple technological process, operation is reliable, energy consumption is low, reaches to reduce costs, reduce power consumption ground purpose.On this basis, completed the present invention.
Once carry lithium solution
" once carrying lithium solution " described in the present invention refers to adopt sulfuric acid process known in the art to process to obtain in the process of lithium ore deposit once carries lithium solution, namely after lithium ore deposit and sulfuric acid baking again water embathe the solution of gained.
In another preference, the described lithium solution of once carrying adopts following steps to obtain: lithionite is sieved in 80～100 mesh sieve, take 200g lithionite powder and concentrated sulfuric acid aqueous solution in the four-hole boiling flask of 1000mL, at 100 ~ 130 ℃ of lower back flow reaction 4-10 hours, cooling, distilled water leaching is filtered, and what get the sulfur acid lithium once carries the lithium extracting solution.
Put forward the lithium method
The method of carrying lithium from the lithium ore deposit provided by the invention comprises the following steps:
(a) with inorganic salt with once carry lithium solution and mix, removing precipitation obtains secondary and carries lithium solution, wherein, described once carry lithium solution be after described lithium ore deposit and sulfuric acid baking again water embathe the solution of gained, described inorganic salt are selected from: calcium chloride, bariumchloride, Calcium Bromide, barium bromide, calcium iodide, barium iodide;
(b) secondary that step (1) is obtained is carried lithium solution and is carried out the nanofiltration processing, and the monovalent cation salts solution that secondary is carried in lithium solution separates with the polyvalent cation salts solution;
(c) extract lithium salts from the monovalent cation salts solution that step (2) obtains.
Described secondary is carried and is contained univalent anion (Cl in lithium solution
-, Br
-, I
-Or its combination).
Described monovalent cation is Li
+, Na
+, K
+, Rb
+, Cs
+Or its combination.
Described polyvalent cation is Ca
2+, Mg
2+, Al
3+Or its combination.
Described lithium ore deposit is selected from: lithionite, triphane, petalite, amblygonite, eucryptite, rich lithium tonstein, seawater mineral deposit, hot spring mineral deposit and pile up the mineral deposit.
In described step (a), the described lithium solution of once carrying is mixed with described inorganic salt, standing mixing solutions after the inorganic salt dissolving, sulfate precipitation is separated out, and removes precipitation by centrifugal, filtration, obtains secondary and carries lithium solution.
In another preference, be precipitated as calcium sulfate or barium sulfate in described step (a).
In another preference, turn at rotating speed 1000-8000/min, centrifugal under 2-20min when turning, filter and remove precipitation, obtain secondary and carry lithium solution.
The pH that described secondary is carried lithium solution is 2-11, preferably, is 2-8, more preferably, is 2-6.
Described secondary is carried lithium solution and is contained Cl
-, Br
-, I
-, Li
+, Na
+, K
+, Rb
+, Cs
+, Ca
2+, Mg
2+, Al
3+Or its combination.
One or more in described step (b) in employing cellulose acetate membrane, polyamide membrane, polyimide film and sulfonated polysulfone membrane carry out nanofiltration to be processed.
The surface of described nanofiltration membrane can be lotus positive electricity or bear electricity.
Described nanofiltration membrane can be tubulose, can be also tabular.
Described nanofiltration membrane can be assembled into tubular type, frame or rolling.
Can in accordance with known methods nanofiltration membrane be made the nanofiltration membrane element, and form single-stage or multistage nanofiltration equipment with cartridge filter, raw water pump, high-pressure pump, former liquid bath and production fluid groove, process thereby carry out nanofiltration.
Described step (b) is carried out the nanofiltration processing, and nanofiltration pressure reduction is 0.25-3Mpa, preferably, is 0.5-2MPa, more preferably, is 0.5-1.5MPa.
Extract lithium salts in described step (c) and refer to the monovalent cation salts solution is mixed with alkali or carbonate, precipitation obtains LiOH or LiCO
3
In another preference, described alkali is sodium hydroxide or potassium hydroxide.In another preference, described carbonate is sodium carbonate or salt of wormwood.
Extracting lithium salts in described step (c) refers to the monovalent cation salts solution is separated, concentrates and obtain lithium salts with membrane distillation concentration crystallization or electrodialysis.
Described method also comprises:
The polyvalent cation salts solution that step (2) is obtained carries out the step that condensing crystal or precipitation obtain polyvalent cation salt; And/or
The monovalent cation salts solution that step (2) is obtained carries out the step of condensing crystal or other the monovalent cation salt of precipitation except lithium salts.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can arbitrary combination.All features that this case specification sheets discloses can with any composition forms and use, each feature that discloses in specification sheets can be replaced by any alternative characteristics of identical, impartial or similar purpose that provides.Therefore except special instruction is arranged, the feature that discloses is only the general example of equalization or similar features.
Usefulness of the present invention is:
(1) provide a kind of economic from the lithium ore deposit, novel method of effectively reclaiming lithium.
(2) method advantages of simple technological process of the present invention, operation is reliable, energy consumption is low.
(3) lithium salts of the inventive method acquisition, quality product meets or exceeds national standard.
The advantages such as (4) the present device investment is little, is easy to realize large-scale industrial production, and production cost is low.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Unless otherwise defined, the same meaning that all specialties and scientific words and the one skilled in the art who uses in literary composition is familiar with.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Embodiment 1
Step 1: will from lithionite with get vitriolization once to carry lithium solution 5000ml standby without processing.
Step 2: with the dull and stereotyped nanofiltration membrane of aromatic polyamide, make rolling nanofiltration membrane element, and form single-stage nanofiltration equipment with cartridge filter, raw water pump, high-pressure pump, former liquid bath and production fluid groove.
Step 3: will once carry lithium solution through nanofiltration equipment, be under 0.6MPa at working pressure, carry out monovalence and polyvalent cation separating and filtering, with monovalence and the multivalence saline solution that obtains in the present embodiment, test I CP, analyze, measuring and calculating knows that the transmitance of other ions of Li is less than 1%, can not realize separating of effective Li and Ca, Mg and Al.
Step 4: will obtain the concentrated solution alkaline purification, Li and Ca, Mg and Al coprecipitation can't separate.
Embodiment 2
Step 1: the lithium solution 5000ml that once carries that will get from lithionite adds 700 gram calcium chloride, stirring and dissolving calcium chloride under normal temperature, and then standing 24h so that precipitation turns at rotating speed 5000/min, centrifugal under 4min when turning, removes by filter most of CaSO
4, obtain pH value and be 3 secondary and carry lithium solution;
Step 2: with the dull and stereotyped nanofiltration membrane of aromatic polyamide, make rolling nanofiltration membrane element, and form single-stage nanofiltration equipment with cartridge filter, raw water pump, high-pressure pump, former liquid bath and production fluid groove.
Step 3: secondary is carried lithium solution through nanofiltration equipment, is under 0.6MPa at working pressure, carries out monovalence and polyvalent cation separating and filtering, separates the monovalent cation muriate saline solution that obtains containing Li.With monovalence and the multivalence saline solution that obtains in the present embodiment, test I CP, analytical results is as shown in table 1, and a polyvalent salt such as Ca are known in measuring and calculating, and Mg and Al ion rejection rate are more than 90%, and transmitance is below 5%, and the transmitance of Li ion reaches 80%.
Step 4: the monovalent cation muriate saline solution that contains Li that will obtain again at last obtains Quilonum Retard through the sodium carbonate precipitation.
Table 1ICP analytical results
Embodiment 3
Step 1: the lithium solution 8000ml that once carries that will get from triphane adds 1500 gram bariumchlorides, stirring and dissolving bariumchloride under normal temperature, and then standing 24h so that precipitation turns at rotating speed 4000/min, centrifugal under 10min when turning, removes by filter most of BaSO
4, obtain pH value and be 4 secondary and carry lithium solution;
Step 2: with the tubulose nanofiltration membrane of cellulose acetate, make tubular type nanofiltration membrane element, and form two-stage nanofiltration equipment with cartridge filter, raw water pump, high-pressure pump, former liquid bath and production fluid groove.
Step 3: secondary is carried lithium solution through nanofiltration equipment, is under 0.8MPa at working pressure, carries out monovalence and polyvalent cation separating and filtering, separates the monovalent cation muriate saline solution that obtains containing Li.With monovalence and the multivalence saline solution that obtains in the present embodiment, test analysis knows that a polyvalent salt such as Ca, Mg and Al ion rejection rate are more than 90%, and transmitance is below 5%, and the transmitance of Li ion reaches 70%.
Step 4: obtain LiOH finally by crossing membrane distillation equipment condensing crystal.
Embodiment 4
Step 1: the lithium solution 7000ml that once carries that will get from petalite adds 1000 gram Calcium Bromides, stirring and dissolving inorganic salt under normal temperature, and then standing 24h so that precipitation turns at rotating speed 7000/min, centrifugal under 5min when turning, removes by filter most of CaSO
4, obtain pH value and be 2 secondary and carry lithium solution;
Step 2: with the dull and stereotyped nanofiltration membrane of polyimide, make frame nanofiltration membrane element, and form two-stage nanofiltration equipment with cartridge filter, raw water pump, high-pressure pump, former liquid bath and production fluid groove.
Step 3: secondary is carried lithium solution through nanofiltration equipment, is under 0.8MPa at working pressure, carries out monovalence and polyvalent cation separating and filtering, separates the monovalent cation bromide saline solution that obtains mainly containing Li.With monovalence and the multivalence saline solution that obtains in the present embodiment, test analysis knows that a polyvalent salt such as Ca, Mg and Al ion are more than 90% in the rejection of nanofiltration process, and transmitance is below 5%, and the transmitance of Li ion reaches 79%.Step 4: electrodialysis separates finally by crossing, the concentrated LiOH that obtains.
Embodiment 5
Step 1: the lithium solution 6000ml that once carries that will get from lithionite adds 1400 gram barium bromides, stirring and dissolving barium bromide under normal temperature, and then standing 24h so that precipitation turns at rotating speed 5000/min, centrifugal under 4min when turning, removes by filter most of BaSO
4, obtain pH value and be 3 secondary and carry lithium solution;
Step 2: with the dull and stereotyped nanofiltration membrane of SPSF, make rolling nanofiltration membrane element, and form single-stage nanofiltration equipment with cartridge filter, raw water pump, high-pressure pump, former liquid bath and production fluid groove.
Step 3: secondary is carried lithium solution through nanofiltration equipment, is under 0.5MPa at working pressure, carries out monovalence and polyvalent cation separating and filtering, separates the monovalent cation bromide saline solution that obtains mainly containing Li.With monovalence and the multivalence saline solution that obtains in the present embodiment, test analysis knows that a polyvalent salt such as Ca, Mg and Al ion are more than 90% in the rejection of nanofiltration process, and transmitance is below 5%, and the transmitance of Li ion reaches 75%.
Step 4: the monovalent cation bromide saline solution that will obtain again at last containing Li obtains Quilonum Retard through the sodium carbonate precipitation.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a method of carrying lithium from the lithium ore deposit, is characterized in that, comprises the following steps:
(a) with inorganic salt with once carry lithium solution and mix, removing precipitation obtains secondary and carries lithium solution, wherein, described once carry lithium solution be after described lithium ore deposit and sulfuric acid baking again water embathe the solution of gained, described inorganic salt are selected from: at least a in calcium chloride, bariumchloride, Calcium Bromide, barium bromide, calcium iodide, barium iodide;
(b) secondary that step (1) is obtained is carried lithium solution and is carried out the nanofiltration processing, and the monovalent cation salts solution that secondary is carried in lithium solution separates with the polyvalent cation salts solution;
(c) extract lithium salts from the monovalent cation salts solution that step (2) obtains.
2. the method for claim 1, is characterized in that, described lithium ore deposit is selected from: lithionite, triphane, petalite, amblygonite, eucryptite, rich lithium tonstein, seawater mineral deposit, hot spring mineral deposit and pile up the mineral deposit.
3. the method for claim 1, is characterized in that, in described step (a), the described lithium solution of once carrying is mixed with described inorganic salt, standing mixing solutions after the inorganic salt dissolving, sulfate precipitation is separated out, remove precipitation by centrifugal, filtration, obtain secondary and carry lithium solution.
4. the method for claim 1, is characterized in that, the pH that described secondary is carried lithium solution is 2-11.
5. the method for claim 1, is characterized in that, described secondary is carried lithium solution and contained Cl
-, Br
-, I
-, Li
+, Na
+, K
+, Rb
+, Cs
+, Ca
2+, Mg
2+, Al
3+Or its combination.
6. the method for claim 1, is characterized in that, one or more in described step (b) in employing cellulose acetate membrane, polyamide membrane, polyimide film and sulfonated polysulfone membrane carry out nanofiltration to be processed.
7. the method for claim 1, is characterized in that, described step (b) is carried out the nanofiltration processing, and nanofiltration pressure reduction is 0.25-3Mpa.
8. the method for claim 1, is characterized in that, extracts lithium salts in described step (c) and refer to the monovalent cation salts solution is mixed with alkali or carbonate, and precipitation obtains LiOH or LiCO
3
9. the method for claim 1, is characterized in that, extracts lithium salts in described step (c) and refer to the monovalent cation salts solution is separated, concentrates and obtain lithium salts with membrane distillation concentration crystallization or electrodialysis.
10. the method for claim 1, is characterized in that, described method also comprises:
The polyvalent cation salts solution that step (2) is obtained carries out the step that condensing crystal or precipitation obtain polyvalent cation salt; And/or
The monovalent cation salts solution that step (2) is obtained carries out the step of condensing crystal or other the monovalent cation salt of precipitation except lithium salts.
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| CN103980009A (en) * | 2014-05-26 | 2014-08-13 | 武汉工程大学 | Method for extracting soluble potassium ions by adopting hydromica barium ion exchange method |
| CN106086473A (en) * | 2016-08-24 | 2016-11-09 | 厦门世达膜科技有限公司 | A kind of lithium sulfate leachate separation purifying technique |
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