CN117305583A - Salt lake lithium extraction system and method based on membrane separation coupling adsorption - Google Patents
Salt lake lithium extraction system and method based on membrane separation coupling adsorption Download PDFInfo
- Publication number
- CN117305583A CN117305583A CN202311274894.9A CN202311274894A CN117305583A CN 117305583 A CN117305583 A CN 117305583A CN 202311274894 A CN202311274894 A CN 202311274894A CN 117305583 A CN117305583 A CN 117305583A
- Authority
- CN
- China
- Prior art keywords
- lithium
- adsorption
- liquid
- water
- ultrafiltration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 221
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 166
- 239000012528 membrane Substances 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims abstract description 112
- 238000000926 separation method Methods 0.000 title claims abstract description 94
- 238000000605 extraction Methods 0.000 title claims abstract description 84
- 230000008878 coupling Effects 0.000 title claims abstract description 39
- 238000010168 coupling process Methods 0.000 title claims abstract description 39
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 39
- 238000001728 nano-filtration Methods 0.000 claims abstract description 174
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 127
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 116
- 238000001556 precipitation Methods 0.000 claims abstract description 65
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 59
- 238000009287 sand filtration Methods 0.000 claims abstract description 55
- 229910052796 boron Inorganic materials 0.000 claims abstract description 49
- 238000011084 recovery Methods 0.000 claims abstract description 47
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 22
- 150000002367 halogens Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 250
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 134
- 239000007788 liquid Substances 0.000 claims description 133
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 67
- 239000012267 brine Substances 0.000 claims description 56
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 56
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 42
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 38
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 14
- 239000000084 colloidal system Substances 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 40
- 239000003463 adsorbent Substances 0.000 abstract description 32
- 150000002500 ions Chemical class 0.000 abstract description 32
- 230000002829 reductive effect Effects 0.000 abstract description 20
- 238000001704 evaporation Methods 0.000 abstract description 15
- 230000008020 evaporation Effects 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 13
- 239000011777 magnesium Substances 0.000 abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 239000011575 calcium Substances 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 238000003795 desorption Methods 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000010413 mother solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- -1 boron ions Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000013505 freshwater Substances 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000000909 electrodialysis Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- MVDSPIQMADQKKM-UHFFFAOYSA-N lithium potassium sodium Chemical compound [Li+].[Na+].[K+] MVDSPIQMADQKKM-UHFFFAOYSA-N 0.000 description 1
- STJUJXONQFLCOP-UHFFFAOYSA-L lithium;sodium;carbonate Chemical compound [Li+].[Na+].[O-]C([O-])=O STJUJXONQFLCOP-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application discloses a salt lake lithium extraction system and a method based on membrane separation coupling adsorption, wherein the salt lake lithium extraction system comprises an ultrafiltration device, a nanofiltration device, an adsorption device, a sand filtration ultrafiltration combined treatment device, a reverse osmosis device, boron removal resin, a lithium chloride MVR device, a lithium precipitation device and a separation recovery device which are sequentially connected; the membrane process treatment is carried out by an ultrafiltration, nanofiltration, sand filtration and ultrafiltration combined treatment device and a reverse osmosis device, and the adsorption treatment is carried out by an adsorption device and boron removal resin, namely, the coupling adsorption lithium extraction process of the original halogen membrane method is adopted, the separation of calcium, magnesium, sulfate radicals, carbonate radicals and other divalent ions from lithium and other divalent ions is realized by the membrane method, and then the adsorption, membrane method and evaporation concentration are utilized, so that the evaporation scale is reduced, and the extraction of high-purity lithium resources is realized under the conditions of low energy consumption and low cost; in addition, by adopting a method combining a membrane method and adsorption, impurities can be thoroughly removed, the purity of lithium is improved, the consumption of the adsorbent is low, and the adsorption and desorption efficiency is high.
Description
Technical Field
The application relates to the technical field of lithium ion recovery, in particular to a salt lake lithium extraction system and method based on membrane separation coupling adsorption.
Background
The salt lake brine is water body containing high concentration salt and mineral matters in salt lake, and is formed by long-term accumulation and evaporation of natural underground water. The salt lake brine is a natural resource and has wide application fields. The salt lake brine contains a large amount of lithium resources, and compared with the hard rock ore for extracting lithium, the development of the salt lake brine lithium resources has the advantages of simple process, low cost, high product purity, strong market competitiveness and the like, and gradually becomes a main way for developing and producing lithium at home and abroad.
The salt lake brine contains a great amount of sodium, potassium, boron, magnesium and other elements besides lithium, so that impurity ions need to be separated and purified in the lithium extraction process, wherein the separation of magnesium and lithium is the most difficult. Compared with overseas countries, most of salt lake brine in China (such as Qinghai salt lake) has high magnesium-lithium ratio, high sodium-lithium ratio and high separation difficulty, so that the lithium loss rate in the lithium extraction process is high, the development cost is high, and the comprehensive exploitation and utilization degree is low.
Because of different parameters such as components, magnesium-lithium ratio, sodium-lithium ratio and the like, the salt lake lithium extraction method generally adopts a plurality of processes such as a precipitation method, a calcination method, an adsorption method, an extraction method, a solar cell and a carbonization method, and is generally a one-lake-one process aiming at different types of salt lakes.
The principle of solvent extraction is that a second liquid which is not compatible with the solution but has larger solubility for the solute is added into the solution containing the solute, and the solubility difference of the solute in two phases is utilized to promote part of the solute to migrate into the second phase through an interface, so that the purpose of phase inversion concentration is achieved. The solvent extraction method is suitable for treating brine with high magnesium-lithium ratio, and has long process flow, organic extractant and high environmental protection pressure.
The precipitation method is to naturally evaporate, concentrate and make salt in an evaporation pond by utilizing solar energy, then make lithium exist in the old brine through the procedures of removing boron, calcium and magnesium and the like, and after the lithium content reaches a proper concentration, the carbonate is taken as a precipitant to make the lithium precipitate in the form of lithium carbonate. The precipitation method has mature process and high reliability, but is not applicable to brine containing a large amount of alkaline earth metals and brine with low lithium concentration, and has low efficiency.
The calcination leaching method is to evaporate the brine after boron extraction to obtain old brine, then add a precipitant into the old brine to make magnesium and lithium come out in a form of precipitation, finally precipitate, calcine and decompose, and make lithium dissolved in solution magnesium still remain in the precipitation through carbonation, thereby realizing magnesium-lithium separation. The calcination leaching method can comprehensively utilize magnesium and lithium resources, but has complex process flow, serious environmental pollution, higher energy consumption, higher cost and larger investment.
The adsorption method is to adsorb lithium ions by using an adsorbent which selectively adsorbs the lithium ions, and then elute the lithium ions so as to achieve the purpose of separating the lithium ions from other impurity ions. Therefore, the key point is to search for an adsorbent with good adsorption selectivity, high cyclic utilization rate and relatively low cost, and the adsorption method is a better method for brine with low lithium content. The adsorption method has simple process and is particularly suitable for separating lithium from brine, but the process has higher requirement on the adsorbent, the cost of the adsorbent is high, the aluminum base has the problem of high fresh water consumption, and the titanium-based adsorbent has high acid-base consumption.
The selective semipermeable membrane method is classified into a nanofiltration membrane method and an electrodialysis method. Nanofiltration membrane processes are pressure driven membrane separations between reverse osmosis and ultrafiltration that can effectively separate monovalent and multivalent ions. The electrodialysis method is to circularly concentrate lithium through a one-stage or multi-stage electrodialysis device by utilizing a monovalent cation selective ion exchange membrane and a monovalent anion selective ion exchange membrane, and add sodium carbonate to precipitate lithium carbonate. The method is suitable for solving the separation of lithium from magnesium and other ions in relatively high-magnesium high-lithium brine, but the lithium content is more than 2 g/L, otherwise, the power consumption is too large.
Thus, the various lithium extraction processes described above have several drawbacks in general: the extraction method has long process flow, is easy to cause equipment corrosion, and the extractant generally has physicochemical properties of water solubility, flammability, volatility and the like. The precipitation method has long process flow, large material consumption and complicated operation, and is only suitable for salt lakes with low magnesium-lithium ratio. The calcination method has complex flow, easy equipment corrosion and high energy consumption. In the adsorption method, since the adsorbent is mostly powder, fluidity and adsorptivity are poor, and adsorption performance is easily degraded. The selective semi-permeable membrane method is used as an emerging separation technology, has a plurality of technologies of ultrafiltration and nanofiltration, namely reverse osmosis, and can effectively separate mono-valent and divalent anions and cations so as to realize recovery and purification of lithium ions. However, the existing lithium purification technology based on membrane separation still has the problems of poor purification efficiency, low purity and the like, and the cost of the lithium purification technology based on membrane separation is generally higher. Therefore, a new technical solution is needed to solve the problems existing in the prior art.
Disclosure of Invention
The application provides a salt lake lithium extraction system and method based on membrane separation coupling adsorption, which are used for solving the problems of high treatment cost and low lithium purification purity of the existing salt lake lithium extraction.
In order to achieve the above object, the present application provides the following technical solutions:
in a first aspect, the application provides a salt lake lithium extraction system based on membrane separation coupling adsorption, which comprises an ultrafiltration device, a nanofiltration device, an adsorption device, a sand filtration ultrafiltration combined treatment device, a qualified liquid reverse osmosis device, boron removal resin, a lithium chloride MVR device, a lithium precipitation device and a separation recovery device which are sequentially connected;
the water inlet end of the ultrafiltration device is connected with a pipeline for conveying salt lake brine, the water outlet end of the ultrafiltration device is connected with the nanofiltration device, the nanofiltration device is connected with the adsorption device, the qualified liquid outlet of the adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device, the water outlet end of the sand filtration ultrafiltration combined treatment device is connected with the water inlet end of the qualified liquid reverse osmosis device, the concentrated water outlet end of the qualified liquid reverse osmosis device is connected with the boron removal resin, the water outlet end of the boron removal resin is connected with the water inlet end of the lithium chloride MVR device, the water outlet end of the lithium chloride MVR device is connected with the water inlet of the lithium precipitation device, the lithium precipitation device is provided with a sodium carbonate inlet, sodium carbonate in the lithium precipitation device reacts with lithium chloride solution to generate lithium carbonate precipitate, the discharge port of the lithium precipitation device is connected with the separation recovery device, and the separation recovery device is used for realizing solid-liquid separation and recovering lithium carbonate precipitate.
In the above technical scheme, optionally, the adsorption device is a titanium adsorption device, and the titanium adsorption device is provided with a water inlet, an acid water adding inlet, a qualified liquid outlet and a disqualified liquid outlet.
Optionally, the nanofiltration device comprises a first-stage nanofiltration module, the water inlet end of the first-stage nanofiltration module is connected with the water producing end of the ultrafiltration device, the concentrated water outlet end of the first-stage nanofiltration module is connected with the water inlet of the titanium adsorption device, and the qualified liquid outlet of the titanium adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device.
Optionally, the titanium adsorption device is further provided with a lithium precipitation mother solution inlet, the lithium precipitation mother solution inlet is connected with a mother solution outlet of the lithium precipitation device, and the lithium precipitation mother solution inlet is connected with a regeneration solution outlet of the boron removal resin.
In the above technical scheme, optionally, the adsorption device is an aluminum adsorption device, and the aluminum adsorption device is provided with a liquid inlet, a qualified liquid outlet, a water inlet and a tail halogen outlet.
Optionally, the nanofiltration device comprises a multi-stage nanofiltration module, and the multi-stage nanofiltration module at least comprises a primary nanofiltration module and a secondary nanofiltration module; the water inlet end of the primary nanofiltration module is connected with the water producing end of the ultrafiltration device, the water producing end of the primary nanofiltration module is connected with the water inlet end of the secondary nanofiltration module, the water producing end of the secondary nanofiltration module is connected with the liquid inlet of the aluminum adsorption device, and the qualified liquid outlet of the aluminum adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device; and an alkali adding port is arranged on a pipeline for connecting the water producing end of the primary nanofiltration module and the water inlet end of the secondary nanofiltration module.
Optionally, the secondary nanofiltration module is connected with the aluminum adsorption device through a carbon remover, and the carbon remover is provided with a first inlet, an exhaust port and a liquid outlet; the water producing end of the secondary nanofiltration module is connected with the first inlet, the liquid outlet is connected with the liquid inlet of the aluminum adsorption device, and the air outlet is used for discharging carbon dioxide gas; an acid adding port is arranged on a pipeline for connecting the water producing end of the secondary nanofiltration module and the first inlet of the carbon remover.
Optionally, the carbon remover is further provided with a second inlet, and the second inlet is connected with the sodium carbonate nanofiltration device; the inlet end of the sodium carbonate nanofiltration device is connected with the concentrated water outlet end of the secondary nanofiltration module through a connecting pipeline, and a water adding port is arranged on the connecting pipeline; the water producing port of the sodium carbonate nanofiltration device is connected with the second inlet, the concentrated water outlet end of the sodium carbonate nanofiltration device is connected with the sodium carbonate recovery device, and the discharge port of the sodium carbonate recovery device is connected with the sodium carbonate adding port on the lithium precipitation device.
Optionally, the sodium carbonate recovery device comprises a sodium carbonate MVR device and a boron removal device.
In the above technical scheme, optionally, the water producing end of the qualified liquid reverse osmosis device is connected with the inlet end of the water producing reverse osmosis device, and the concentrated water outlet end of the water producing reverse osmosis device is connected with the inlet end of the sand filtration and ultrafiltration combined treatment device; the water producing end of the water producing reverse osmosis device is connected with the water using end of the user.
In the above technical scheme, optionally, the sand filtration ultrafiltration combined treatment device comprises a sand bed and an ultrafiltration membrane component connected to the water outlet side of the sand bed.
In a second aspect, the present application further provides a method for extracting lithium from a salt lake based on membrane separation coupling adsorption, which adopts the above salt lake lithium extraction system based on membrane separation coupling adsorption, and the method for extracting lithium from a salt lake comprises the following steps:
s1: inputting salt lake brine into an ultrafiltration device, and removing suspended matters and colloid in the salt lake brine through the ultrafiltration device;
s2: the salt lake brine treated by the ultrafiltration device enters a primary nanofiltration module, and the primary nanofiltration module is used for removing sulfate radicals and carbonate radicals in the salt lake brine;
s3: the liquid discharged from the concentrated water outlet end of the primary nanofiltration module enters a titanium adsorption device, and the titanium adsorption device is used for adsorbing lithium in the liquid;
s4: the adsorption qualified liquid discharged by the titanium adsorption device enters the sand filtration and ultrafiltration combined treatment device, and the sand filtration and ultrafiltration combined treatment device is used for removing liquid suspended matters and colloid and reducing turbidity;
s5: the liquid treated by the sand filtration and ultrafiltration combined treatment device enters the qualified liquid reverse osmosis device, and the liquid discharged from the concentrated water outlet end of the qualified liquid reverse osmosis device enters boron removal resin for removing boron;
S6: liquid flowing out from the water producing end of the boron-removing resin enters the lithium chloride MVR device, and the lithium chloride MVR device concentrates the liquid entering the lithium chloride MVR device;
s7: and (3) enabling the lithium chloride concentrated solution obtained by concentrating the lithium chloride MVR device to enter a lithium precipitation device to react with sodium carbonate solution, generating lithium carbonate precipitate in the solution, and separating and recovering the generated lithium carbonate precipitate from the solution by the separation and recovery device.
In a third aspect, the present application further provides another method for extracting lithium from a salt lake based on membrane separation coupling adsorption, which adopts the above salt lake lithium extraction system based on membrane separation coupling adsorption, and the method for extracting lithium from a salt lake includes the following steps:
s1: inputting salt lake brine into an ultrafiltration device, and removing suspended matters and colloid in the salt lake brine through the ultrafiltration device;
s2: the salt lake brine treated by the ultrafiltration device enters a primary nanofiltration module, and the primary nanofiltration module is used for removing sulfate radicals and carbonate radicals in the salt lake brine;
s3: liquid discharged from the water producing end of the primary nanofiltration module enters the secondary nanofiltration module to remove carbonate;
s4: liquid discharged from the water producing end of the secondary nanofiltration module enters a carbon remover to remove bicarbonate;
S5: the liquid discharged from the carbon remover enters an aluminum adsorption device, and the aluminum adsorption device is used for adsorbing lithium in the liquid;
s6: the adsorption qualified liquid discharged by the aluminum adsorption device enters the sand filtration and ultrafiltration combined treatment device, and the sand filtration and ultrafiltration combined treatment device is used for removing liquid suspended matters and colloid and reducing turbidity;
s7: the liquid treated by the sand filtration and ultrafiltration combined treatment device enters the qualified liquid reverse osmosis device, and the liquid discharged from the concentrated water outlet end of the qualified liquid reverse osmosis device enters boron removal resin for removing boron;
s8: liquid flowing out from the water producing end of the boron-removing resin enters the lithium chloride MVR device, and the lithium chloride MVR device concentrates the liquid entering the lithium chloride MVR device;
s9: and (3) enabling the lithium chloride concentrated solution obtained by concentrating the lithium chloride MVR device to enter a lithium precipitation device to react with sodium carbonate solution, generating lithium carbonate precipitate in the solution, and separating and recovering the generated lithium carbonate precipitate from the solution by the separation and recovery device.
In the step S3, alkali is added into the liquid discharged from the water producing end of the primary nanofiltration module, and then the liquid is discharged into the secondary nanofiltration module;
in the step S4, acid is added to the liquid discharged from the water producing end of the secondary nanofiltration module, and then the liquid is discharged into the carbon remover.
Compared with the prior art, the application has the following beneficial effects:
1. the application provides a salt lake lithium extraction system based on membrane separation coupling adsorption, which comprises an ultrafiltration device, a nanofiltration device, an adsorption device, a sand filtration ultrafiltration combined treatment device, a qualified liquid reverse osmosis device, boron removal resin, a lithium chloride MVR device, a lithium precipitation device and a separation recovery device which are sequentially connected, wherein salt lake brine is subjected to functional treatment through the devices, membrane treatment is realized through the ultrafiltration, nanofiltration, sand filtration ultrafiltration combined treatment device and the reverse osmosis device, and adsorption treatment is realized through the adsorption device and the boron removal resin, namely, the application adopts a raw halogen membrane method coupling adsorption lithium extraction process, divalent ions such as calcium, magnesium, sulfate radicals, carbonate radicals and the like are separated from monovalent ions such as lithium by using a membrane method, adsorption, membrane method and evaporation concentration are reused, evaporation scale is reduced, and the purpose of extracting high-purity lithium resources under the conditions of low energy consumption and low cost is achieved; in addition, by adopting a method combining a membrane method and adsorption, impurities can be thoroughly removed, the purity of lithium is improved, the consumption of an adsorbent is reduced, and the adsorption and desorption efficiency is high.
2. Aiming at the raw bittern with low lithium content and high sodium sulfate and sodium chloride content, the traditional process is to directly concentrate the lithium-containing bittern by solar energy, which has the problems of large water quantity and low efficiency and the problem of more difficult treatment after concentration of the easily-scaled magnesium carbonate; the salt lake lithium extraction system provided by the application can carry out high-purity lithium extraction on the raw halogen with low lithium content and high mineralization degree, and the sodium sulfate and sodium chloride content are high, so that the factors such as calcium, magnesium, sulfate radical, carbonate radical and the like which are easy to scale are removed by using a membrane method, and the lithium extraction system can realize high-purity lithium extraction by using adsorption, the membrane method and evaporation concentration, so that the evaporation scale is reduced, the energy consumption is reduced, and impurities can be thoroughly removed.
3. The traditional adsorption method has the problems of high acid-base consumption of the titanium-based adsorbent, high adsorbent cost, small capacity of the aluminum-based adsorbent, high fresh water consumption and the like, and the salt lake lithium extraction system provided by the application is characterized in that the titanium adsorption device and the aluminum adsorption device are respectively combined with membrane separation technologies (such as an ultrafiltration device, a nanofiltration device, a sand filtration ultrafiltration combined treatment device and a reverse osmosis device) to realize a membrane separation coupling adsorption process, so that the problems are solved in a targeted manner, the adsorbent consumption is reduced, the fresh water resource consumption is reduced, and the operation and investment cost is reduced as a whole.
4. In the salt lake lithium extraction system provided by the application, more membrane separation equipment, less evaporation equipment and high-temperature equipment are adopted, the probability of equipment failure is reduced, and the maintenance quantity and the difficulty are correspondingly reduced.
5. The ultrafiltration device in the salt lake lithium extraction system provided by the application is preferably immersed ultrafiltration, compared with traditional multi-medium and external pressure type ultrafiltration, the immersed ultrafiltration used in the application is extremely high in suspended solids resistance, high in turbidity impact resistance, extremely strong in impact resistance, simple and convenient to operate and manage, good in effluent quality, low in operation cost and quite investment cost, and the recovery rate can reach 95%.
6. Based on the salt lake lithium extraction system provided by the application, the application also provides a corresponding salt lake lithium extraction method, the lithium extraction route is short, the aging is high, about 20% of electric energy can be saved compared with the traditional lithium extraction method, the total operation cost is reduced by 10-15%, and under the condition of equivalent investment cost, the higher return rate of investment can be obtained by using the lithium extraction method provided by the application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. It should be understood that the specific shape and configuration shown in the drawings should not be considered in general as limiting upon the practice of the present application; for example, based on the technical concepts and exemplary drawings disclosed herein, those skilled in the art have the ability to easily make conventional adjustments or further optimizations for the add/subtract/assign division, specific shapes, positional relationships, connection modes, dimensional scaling relationships, etc. of certain units (components).
Fig. 1 is a schematic process flow diagram of a salt lake lithium extraction system based on membrane separation coupling adsorption provided in the present application in one embodiment;
FIG. 2 is a schematic view of a first process flow of a first lithium extraction route for extracting lithium using a titanium adsorption device in the present application;
FIG. 3 is a schematic view of a partial process flow of a second lithium extraction route for extracting lithium using an aluminum adsorption device in the present application, showing only the process between the secondary nanofiltration module and sand filtration+ultrafiltration;
Fig. 4 is a schematic view of a process flow of the sodium carbonate recovery route provided herein, showing only the process after the secondary nanofiltration module.
Detailed Description
The present application is further described in detail below with reference to the attached drawings.
In the description of the present application: unless otherwise indicated, the meaning of "a plurality" is two or more. The terms "first," "second," "third," and the like in this application are intended to distinguish between the referenced objects without a special meaning in terms of technical connotation (e.g., should not be construed as emphasis on degree or order of importance, etc.). The expressions "comprising", "including", "having", etc. also mean "not limited to" (certain units, components, materials, steps, etc.).
The terms such as "upper", "lower", "left", "right", "middle", and the like, as referred to in this application, are generally used for convenience in visual understanding with reference to the drawings, and are not intended to be an absolute limitation of the positional relationship in actual products. Such changes in relative positional relationship are considered to be within the scope of the present description without departing from the technical concepts disclosed herein.
Example 1
In order to solve the problems in the prior art, the application provides a salt lake lithium extraction system based on membrane separation coupling adsorption, which can carry out lithium extraction treatment on low-grade lithium ores with low lithium content and low mineralization degree. The process treatment route of the salt lake lithium extraction system based on membrane separation coupling adsorption provided by the application considers the separation of a divalent ion, removes alkalinity and boron, and simultaneously ensures the resource recycling of sodium carbonate, sodium chloride, potassium chloride and lithium carbonate. In the whole, the salt lake lithium extraction system based on membrane separation coupling adsorption adopts a raw halogen membrane method coupling adsorption lithium extraction process route, and mainly comprises a raw halogen filtration process, a membrane separation process, an adsorption process, a membrane purification concentration process, a bipolar membrane electrolysis process, a lithium chloride evaporation crystallization process, a lithium precipitation process, a bipolar membrane acid and alkali preparation process and the like.
The application provides a salt lake draws lithium system based on membrane separation coupling absorption mainly includes ultrafiltration device, nanofiltration device, titanium adsorption equipment, sand filtration ultrafiltration combination processing apparatus, qualification liquid reverse osmosis unit, removes boron resin, lithium chloride MVR device, heavy lithium device and separation recovery unit that link to each other in proper order. The functional devices are matched with each other in the whole process treatment route and are used in a related mode according to the process requirements in order, and the purpose of extracting lithium from the salt lake is achieved.
The functional structure of each device in the structural principle and system architecture of the salt lake lithium extraction system provided by the application is described in detail below.
1. Ultrafiltration device
In this application, salt lake brine can directly send into ultrafiltration unit's membrane pond in, also can carry out prefiltering with salt lake brine in accordance with specific process conditions before discharging into the membrane pond again.
In the application, the submerged flat ultrafiltration is adopted to reduce the content of suspended matters in salt lake brine, so as to meet the water inlet requirement of subsequent equipment. The ultrafiltration device in the application directly immerses the immersed flat ultrafiltration in a membrane pool, adopts a pump or siphon mode to realize that negative pressure pumps out water and solubility micromolecules from the membrane so as to remove suspended matters, colloid particles and macromolecular organic matters in the water and promote the clarity of water.
In the present application, the ultrafiltration device may include a membrane tank, submerged ultrafiltration immersed in the membrane tank, and a suction pump, a cleaning pump, a backwash fan, and the like provided outside the membrane tank. The submerged ultrafiltration in the membrane basin may be submerged flat plate ultrafiltration, comprising one or more submerged ultrafiltration membrane modules.
The immersed ultrafiltration membrane component comprises a hollow fiber membrane fixed on a horizontal or vertical frame and permeate water collecting pipes arranged at the top and the bottom of the frame. Each water collection pipe comprises a layer of special resin for sealing the membrane wires, so that the inner cavity of the membrane is connected with a pipeline to collect product water. Several or tens of membrane modules are connected to form a complete membrane tank. A plurality of membrane boxes are immersed in the membrane pool in parallel to form a membrane column, and a plurality of membrane columns are connected in parallel to form membrane treatment systems with different treatment scales, and the membrane pollution rate can be reduced by adopting operation modes such as periodic back flushing, gentle air scrubbing and the like during operation. Unlike traditional pressure membrane filtration, immersed ultrafiltration membrane operates in lower negative pressure state, and its principle is to utilize siphon or pump suction mode to carry out negative pressure suction filtration from outside to inside on water, so as to realize smooth operation with low transmembrane pressure difference and moderate membrane flux. The immersed ultrafiltration membrane component has overall energy consumption cost lower than that of pressure type membrane filtration, and is characterized by mainly comprising the following aspects: 1) The solid-liquid separation can be effectively carried out, the separation effect is far better than that of the traditional sedimentation tank, the water quality of the effluent is good, the suspended matters and turbidity of the effluent are close to zero, the effluent can be directly recycled, and the sewage recycling is realized; 2) The membrane component is standardized and modularized in design, is suitable for different water treatment amounts, and is flexible in water supply scale; 3) Is favorable for interception, growth and propagation of nitrifying bacteria with slow proliferation, improves the nitrifying efficiency of the system, and combines the immersed ultrafiltration membrane component with a biochemical process to form a Membrane Bioreactor (MBR) process, and has better denitrification and dephosphorization functions than the traditional biological treatment process.
Compared with pressure type ultrafiltration, the submerged flat plate ultrafiltration device can tolerate high suspended matter content, inlet water can directly enter the high-strength membrane without filtering, high-quality produced water is obtained, and the traditional pressure type ultrafiltration usually needs sand filtration to enter the ultrafiltration. Therefore, the immersed flat ultrafiltration device is used without a sand filter or a multi-medium filter, so that the flow is greatly simplified; meanwhile, negative pressure suction is adopted, the operation pressure is low, the energy consumption is saved, and the risk of overpressure operation is avoided; besides, the open membrane pool is adopted, so that the condition of membrane wires can be directly observed, and the operation and management are convenient.
In a specific installation application example, the working pressure of the immersed flat ultrafiltration device is-0.02 MPa to-0.08 MPa, the filtration period is 30-50 min, the total backwashing duration is 90 seconds, and the design flux is not more than 20L/m 2 H, water backwash strength: 25-50L/m 2 H, the self-water consumption rate is less than or equal to 5 percent, and the turbidity of produced water<1NTU。
2. Nanofiltration device
The application uses a nanofiltration device to remove sulfate radical, carbonate radical and the like in salt lake brine. The nanofiltration device comprises a multi-stage nanofiltration module, and the various stages of nanofiltration modules are sequentially connected.
In a specific embodiment, the multi-stage nanofiltration module comprises a primary nanofiltration module and a secondary nanofiltration module; of course, three-stage nanofiltration modules can be reserved as required. The nanofiltration modules at all levels have the same structure and comprise a corrosion-resistant shell, wherein nanofiltration membrane components are arranged in the shell, and a water inlet, a concentrated water outlet and a water producing port are formed on the shell. In order to realize cleaning and stability monitoring, the nanofiltration modules of each stage are provided with a cleaning system and a control system, and the cleaning system is used for cleaning the nanofiltration membrane assembly periodically or according to requirements so as to remove dirt and blockage on the surface of the membrane, thereby ensuring the normal operation of the device and maintaining long service life. The cleaning system may include physical cleaning (e.g., back flushing) and chemical cleaning (e.g., acid-base cleaning) methods. The control system is used for monitoring and regulating the running state of the device, can monitor the parameters such as water inlet and outlet pressure, temperature and the like, and automatically controls according to the set parameters so as to ensure the stability of the nanofiltration device.
The treatment route of the salt lake lithium extraction system provided by the application can be divided into three parallel treatment routes at the first-stage nanofiltration module and the second-stage nanofiltration module: A. the concentrated water of the first-stage nanofiltration module is used for subsequent lithium precipitation and is used as a first lithium extraction route; B. the water producing end of the first-stage nanofiltration module is connected with the second-stage nanofiltration module, and the concentrated water of the second-stage nanofiltration module participates in the subsequent recovery of sodium carbonate, and is a sodium carbonate recovery route or a lithium precipitation reactant preparation route; C. and (3) the produced water of the secondary nanofiltration module is further adsorbed to prepare adsorption qualified liquid, and the adsorption qualified liquid is used for subsequent lithium precipitation and is a second lithium extraction route.
The system architecture of processing route a is: the water inlet end of the ultrafiltration device is connected with a pipeline for conveying salt lake brine, the water producing end of the ultrafiltration device is connected with the inlet end of the first-stage nanofiltration module, the concentrated water outlet end of the first-stage nanofiltration module is connected with the titanium adsorption device, the qualified liquid outlet of the titanium adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device, the water producing end of the sand filtration ultrafiltration combined treatment device is connected with the water inlet end of the qualified liquid reverse osmosis device, the concentrated water outlet end of the qualified liquid reverse osmosis device is connected with boron-removing resin, the water producing end of the boron-removing resin is connected with the water inlet end of the lithium chloride MVR device, the water outlet end of the lithium chloride MVR device is connected with the liquid inlet of the lithium precipitation device, the lithium precipitation device is provided with a sodium carbonate inlet, sodium carbonate in the lithium precipitation device reacts with lithium chloride solution to generate lithium carbonate precipitation, the discharge port of the lithium precipitation device is connected with the separation recovery device, and the separation recovery device (lithium carbonate centrifuge) realizes solid-liquid separation and lithium carbonate precipitation recovery.
The system architecture of processing route B is: the water producing end of the first-stage nanofiltration module is connected with the water inlet end of the second-stage nanofiltration module, the concentrated water outlet end of the second-stage nanofiltration module is connected with the inlet end of the sodium carbonate nanofiltration device, the concentrated water outlet end of the sodium carbonate nanofiltration device is connected with the sodium carbonate recovery device, and the discharge port of the sodium carbonate recovery device is connected with the sodium carbonate adding port on the lithium precipitation device.
Wherein, the sodium carbonate recovery device comprises a sodium carbonate MVR device and a boron removal device; an alkali adding port is arranged on a pipeline for connecting the water producing end of the primary nanofiltration module and the water inlet end of the secondary nanofiltration module; a water inlet is arranged on a pipeline for connecting the concentrated water outlet end of the secondary nanofiltration module and the inlet end of the sodium carbonate nanofiltration device.
The system architecture of processing route C is: the water producing end of the secondary nanofiltration module is connected with the first inlet of the carbon remover, the water producing port of the sodium carbonate nanofiltration device is connected with the second inlet of the carbon remover, the liquid discharging port of the carbon remover is connected with the liquid inlet of the aluminum adsorption device, and the qualified liquid outlet of the aluminum adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device.
Wherein, a pipeline for connecting the water producing end of the secondary nanofiltration module and the first inlet of the carbon remover is provided with an acid adding port for removing bicarbonate and converting the bicarbonate into CO in the carbon remover 2 Discharging; the carbon remover is provided with an exhaust port for exhausting carbon dioxide gas; the aluminum adsorption device is provided with a water inlet and a tail halogen outlet.
In a specific example of installation use, the nanofiltration device uses a membrane with a nanoscale pore size, typically between 0.001 and 0.01 microns. Compared with the ultrafiltration membrane, the nanofiltration membrane has smaller pore diameter, and can remove dissolved matters, most inorganic salts and organic matters more effectively. According to actual needs, different nanofiltration membrane materials, operation pressures and operation conditions can be selected, so that different separation effects and different transmittance can be realized.
The principle of operation of the nanofiltration device is described below:
nanofiltration membranes have ion selectivity, lower removal rate for monovalent ions and higher removal rate for multivalent ions, because nanofiltration membranes are mostly charged membranes, and the Donnan (Donnan) equilibrium effect exists for anions of different valence states. The positively charged ions in the water can permeate the membrane under the action of concentration difference, but the negatively charged ions are blocked by the negatively charged membrane, so that the negatively charged ions cannot (or rarely) permeate the membrane to reach the fresh water side, and the positively charged ions are limited to diffuse to the fresh water side due to the electric neutrality principle, so that the aim of desalting is fulfilled. The permeability of nanofiltration membranes to salts is mainly determined by the valence of the ions, monovalent ions can permeate through the membrane in large amounts (but not without blocking) whereas multivalent ions (e.g. sulphates and carbonates) are removed more efficiently. Thus, the nanofiltration device is used for effectively separating monovalent salt from divalent salt concentrated water.
The nanofiltration membrane is separated by adopting an anti-pollution material, the rejection rate of sulfate ions can reach more than 98%, and the sulfate ions in the strong brine are efficiently trapped and are effectively separated into two parts after being treated by a nanofiltration system: nanofiltration of almost all NaCl component to produce water, and Na 2 SO 4 The nano-filtration concentrated water which is the main component realizes the primary salt separation target of the concentrated brine.
Because inorganic salt can permeate the nanofiltration membrane, the osmotic pressure of the inorganic salt is far lower than that of the reverse osmosis membrane, and therefore, the external pressure required by the nanofiltration membrane process is much lower than that of the reverse osmosis membrane at a certain flux; whereas at equal pressure the flux of nanofiltration is much greater than reverse osmosis. Nanofiltration enables concentration to be performed simultaneously with desalination. Therefore, when nanofiltration is used instead of reverse osmosis, the concentration process can be effectively and rapidly carried out, and a larger concentration multiple is achieved.
By utilizing the advantages of the special nanofiltration membrane in salt separation and the high-efficiency interception of organic matters with molecular weight of more than 200, the method can realize concentration and decrement of divalent brine, reduce the processing capacity of subsequent nanofiltration concentrated water fractional crystallization, obtain sodium sulfate products through evaporative crystallization and freeze crystallization, simultaneously separate by nanofiltration, lighten the pressure of the nanofiltration produced water polluted by the organic matters when the nanofiltration produced water is subjected to reverse osmosis concentration treatment due to low TOC (Total Organic Carbon) and divalent ion content in the permeate water, and ensure the effective control of TOC impurity residual content in the products through the subsequent sodium chloride evaporative crystallization process, thereby obtaining sodium chloride products with high purity.
3. Titanium adsorption device
The inorganic ion adsorbent has strong selectivity to lithium ions and a specific memory effect, and can effectively extract lithium selectively from a dilute solution. Inorganic ion exchange adsorbents can be classified as aluminum-based, manganese-based, and titanium-based adsorbents. The application selects the aluminum-based and titanium-based adsorbents.
The liquid discharged from the concentrated water outlet end of the first-stage nanofiltration module belongs to neutral alkaline brine, and the titanium adsorption device is used for carrying out adsorption treatment on the concentrated water discharged from the first-stage nanofiltration module.
Specifically, the titanium adsorbent in the titanium adsorption device is used for adsorbing lithium, and lithium ions are mainly adsorbed from salt lake brine through the selective adsorption function of the adsorbent. Titanium adsorbents are usually filled with titanium fibers, titanium particles or titanium nano materials, the surface area and pore structure of the titanium adsorbents are increased to improve adsorption performance, lithium can be captured and stored by the adsorbents, then the lithium on the adsorbents is desorbed and collected through desorption to obtain qualified liquid, for example, desorption is carried out under the action of an eluent to obtain lithium-rich solution, and separation and purification of lithium are realized; and the unqualified liquid (or tail halogen) after adsorption is directly discharged to a salt lake.
The titanium adsorption device has the advantages of large adsorption capacity, wide application range, high selectivity and low dissolution loss rate.
In this application, the titanium adsorption device has a water inlet, an acid water inlet, a lithium precipitation mother liquor inlet, a qualified liquor outlet and a disqualified liquor outlet. Because the mother solution of the lithium precipitation device and the regeneration solution of the boron-removing resin both contain a certain amount of lithium, the mother solution is refluxed to the titanium adsorption device for treatment according to the principle of the highest resource recovery rate. Thus, the lithium precipitation mother liquor inlet is connected to the mother liquor discharge port of the lithium precipitation device, and the lithium precipitation mother liquor inlet is connected to the regeneration liquor discharge port of the boron-removing resin.
4. Sand filtering ultrafiltration combined treatment device
The sand filtration and ultrafiltration combined treatment device in the present application can be understood as "sand filtration and ultrafiltration". Sand filtration is a technique of filtering through multiple layers of sand beds; when water passes through the sand bed, suspended matters, sediment and large particulate matters are filtered out, so that relatively clear water is obtained; sand filtration is commonly used in the primary filtration stage to remove larger solid particles, reducing turbidity and suspended matter content in water. Ultrafiltration is a membrane filtration technique that utilizes microporous membranes for separation. The aperture of the ultrafiltration membrane is usually between 0.01 and 0.1 micron, so that suspended matters, colloid, bacteria, viruses and most of high molecular organic matters can be effectively removed, and the requirement of higher water quality can be met.
The sand filtration and ultrafiltration combined treatment device can obtain better water treatment effect, firstly, the sand filtration can be used as a pretreatment step to remove larger particulate matters and suspended matters in water, so that the burden of an ultrafiltration membrane is reduced, and the service life of the ultrafiltration membrane is prolonged; and secondly, ultrafiltration is arranged on the water outlet side of the sand filter, and as a fine filtering step, substances such as smaller particles, colloid and the like which cannot be completely removed by the sand filter are removed.
5. Qualified liquid reverse osmosis device
The qualified liquid reverse osmosis device in the application is a reverse osmosis device for treating and adsorbing qualified liquid, and the structural principle can be briefly described as follows: the reverse osmosis device mainly comprises a water inlet system, a high-pressure pump, a reverse osmosis membrane assembly, a concentrated water discharge pipeline, a pure water collection pipeline and a corresponding control system, wherein: the water inlet system comprises a water inlet pipeline, a water inlet valve and pretreatment equipment, wherein the water inlet pipeline, the water inlet valve and the pretreatment equipment are used for introducing a water source to be treated, and the pretreatment equipment generally comprises a particulate matter filter, an activated carbon filter and the like and is used for removing suspended particles, chlorine, organic compounds and the like in the water. The high-pressure pump is connected with the back of the water inlet system and is used for providing enough water pressure to overcome the osmotic resistance of the reverse osmosis membrane; the high pressure pump increases the pressure of the water stream through the membrane, forcing water molecules through the membrane pores, while solutes and particulates are trapped. The reverse osmosis membrane component is a core part of the whole device and consists of a plurality of layers of films; the membrane layer is usually a semipermeable membrane (semi-permeable membrane) with micropores or nanoscale pores, which can trap most ions, solutes and particulates and only allow water molecules to pass through; as the water passes through the membrane, solutes and particulates therein are retained on the membrane surface or are drained off. During reverse osmosis, a portion of the water that does not pass through the membrane (concentrate) is discharged from the concentrate discharge line to dilute the concentrated solute in the feed water. Purified water (purified water) trapped on the membrane module flows out through the membrane pores and is collected in the purified water collecting pipe. The control system is used for monitoring parameters such as water inlet and outlet pressure, membrane assembly state and the like, and automatically controlling according to the needs so as to ensure the normal operation of the device.
The water producing end of the qualified liquid reverse osmosis device is connected with the inlet end of the water producing reverse osmosis device, and the concentrated water outlet end of the water producing reverse osmosis device also contains a certain amount of lithium, so that the concentrated water outlet end of the water producing reverse osmosis device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device, lithium in the concentrated water discharged by the water producing reverse osmosis device is recovered, and the lithium recovery rate is improved; the water treated by the water-producing reverse osmosis device can be used as pure water, so that the water-producing end of the water-producing reverse osmosis device can be connected with the water-using end of a user. Therefore, the salt lake lithium extraction system provided by the application not only can realize high-purity lithium resource extraction, but also can generate pure water for self-use, and the resource recycling rate is extremely high.
6. Boron-removing resin
The boron removal resin is an adsorption material for removing boron in water, and can help to purify water sources and reduce the boron content in water.
The boron removal resin generally adopts organic functional resin as a base material, and after special treatment, the surface of the boron removal resin has specific adsorption performance and can selectively adsorb boron ions in water. The resin material has larger surface area and pore diameter, and provides sufficient contact opportunity and adsorption capacity to effectively remove boron in water.
The working principle of the boron removal resin is mainly that boron ions in water are captured and fixed on the resin through the adsorption action of the resin surface. As the water passes through the boron removal resin apparatus, the boron ions will undergo an adsorption reaction with active sites on the resin surface, thereby removing the boron ions from the water. Once the resin is saturated, a regeneration operation is required to restore its adsorption properties. Generally, the regeneration process of the boron-removing resin includes acid washing, alkali washing or other special regeneration processes.
7. Lithium chloride MVR device
The lithium chloride MVR (Mechanical Vapor Recompression) plant is a device that utilizes mechanical compression steam regeneration techniques to recover and purify lithium chloride solution.
The lithium chloride MVR device realizes the regeneration of lithium chloride solution through the following steps: heating the lithium chloride solution by using an evaporator to evaporate water and generate steam; compressing the vapor using a compressor to increase temperature and pressure; heat exchange is carried out on the high-temperature high-pressure steam and the lithium chloride solution by using a heat exchanger, so that the temperature of the lithium chloride solution is increased and part of water is evaporated; cooling the high-temperature high-pressure steam by using a condenser to condense the high-temperature high-pressure steam into steam with higher heat; separating the condensed water and lithium chloride solution using a separator; the lithium chloride solution in the separator was recycled back to the evaporator using a recycle pump for the next round of recycling.
Through the continuous circulation of the steps, the lithium chloride MVR device realizes the removal of water in the lithium chloride solution and the concentration of lithium chloride. Compared with the traditional thermal evaporation method, the MVR technology utilizes the high temperature and high pressure of compressed steam, realizes the cyclic utilization of energy and reduces the energy consumption and the running cost; the quality and stability of the lithium chloride solution are improved, the recycling of lithium chloride is realized, and the discharge of waste liquid is reduced.
8. Lithium deposition device
In this application, when lithium chloride and sodium carbonate enter the lithium precipitation device, they react in the lithium precipitation device to generate lithium carbonate precipitate, and the discharged lithium precipitation mother solution refers to a solution containing lithium ions, which mainly contains lithium chloride, sodium carbonate and other impurities. In the lithium precipitation device, lithium chloride and sodium carbonate react to generate lithium carbonate precipitate and sodium chloride. The reaction equation is as follows:
2LiCl+Na 2 CO 3 →Li 2 CO 3 +2NaCl
after the reaction, the aqueous lithium carbonate precipitate enters a separation recovery device to remove water. Some unreacted lithium chloride, sodium carbonate and other impurity substances such as metal ions, impurity salts and the like can also exist in the lithium precipitation mother liquor discharged from the self-precipitation device. The lithium precipitation mother liquor may be further processed as needed to extract and purify lithium carbonate therein for use in the preparation of lithium compounds or other industrial applications. Common treatment methods comprise the processes of filtrate, leaching, crystallization, ion exchange and the like, and lithium carbonate in the lithium precipitation mother solution can be separated and purified through the steps to obtain a high-purity lithium compound product.
In the application, the lithium precipitation mother liquor is discharged into a titanium adsorption device for further treatment and purification, and the purification rate and the resource recovery rate are improved.
9. Separation recovery device
The separation and recovery device comprises a lithium carbonate centrifuge, and the main structural principle of the separation and recovery device comprises a centrifuge body, a feeding system, a centrifugal separation system, a liquid phase discharge system, a solid phase collection system and a corresponding control system. Wherein: the centrifuge body includes a housing, centrifuge rotor, motor, etc., typically made of corrosion resistant materials (e.g., stainless steel) to accommodate the particular properties of the lithium carbonate solution.
The feeding system comprises a feeding pipeline and a feeding pump, wherein the aqueous lithium carbonate sediment discharged from the self-precipitating lithium device is input into the centrifugal machine through the feeding pipeline, and the pressure and the flow speed are provided by the feeding pump. The core part of the lithium carbonate centrifuge is a centrifugal separation system, which comprises a centrifuge rotor and a centrifugal force field, wherein the centrifugal rotor rotating at high speed generates strong centrifugal force to separate solid particles (lithium carbonate sediment) in the aqueous lithium carbonate sediment, and a centrifugal plate or a centrifugal basket is generally arranged in the centrifugal rotor and is used for collecting the separated solid particles. After centrifugation, the liquid phase (lithium carbonate-rich solution) needs to be discharged, and the centrifuge discharges the liquid phase from the centrifugal rotor through a liquid phase discharge system, and can be discharged to a titanium adsorption device for reprocessing. The solid phase (solid particles of lithium carbonate containing impurities) needs to be collected and processed, and is typically collected by a centrifuge plate or basket within a centrifuge rotor, and may be further processed by drying, filtration, etc. The control system is used for monitoring the running state, the rotating speed, the temperature and other parameters of the centrifugal machine and automatically controlling according to the set conditions so as to ensure the safe and stable running of the device.
Therefore, the present application realizes dehydration and solid-liquid separation by effectively separating out solid particles in a lithium carbonate solution using the centrifugal separation principle of a lithium carbonate centrifuge.
10. Carbon remover
The carbon remover in this application can realize gas-liquid separation and remove carbon, and the carbon remover is gone into to the acid addition in the product water of second grade nanofiltration module, and the carbon remover can be gone into to the product water of sodium carbonate nanofiltration, and the bicarbonate in the liquid and acid reaction generate gaseous discharge, have realized liquid decarbonization.
11. Aluminum adsorption device
The aluminum adsorption device comprises an aluminum-based adsorbent, is suitable for sulfate or chloride type brine, and has neutral and slightly acidic application environment. The aluminum adsorbent is used after the two-stage nanofiltration module, because sulfuric acid is separated in concentrated water of the first-stage nanofiltration module, and the produced water of the second-stage nanofiltration module is mainly chloride; the titanium adsorbent is mainly used after the first-stage nanofiltration module is concentrated, the concentration of sulfate radical is high, and in addition, the water quantity of the concentrated water is generally much smaller than that of produced water, so that the aluminum adsorption device can meet the use requirement.
According to the method, liquid discharged from the carbon remover is discharged into an aluminum adsorption device to adsorb lithium ions through an aluminum-based adsorbent, and then the lithium on the adsorbent is desorbed and collected through desorption to obtain qualified liquid, for example, the qualified liquid is desorbed under the action of an eluent to obtain a lithium-rich solution, so that the separation and purification of lithium are realized; and the disqualified liquid (or tail halogen) after adsorption is discharged for further treatment (such as reprocessing according to actual conditions to recover potassium and sodium resources), and the tail halogen can also be discharged to a salt lake.
The aluminum adsorption device in the application is provided with a liquid inlet, a qualified liquid outlet, a water adding port and a tail halogen outlet, wherein the liquid inlet is connected with a carbon remover, and the qualified liquid outlet is connected with a sand filtration and ultrafiltration combined treatment device.
The aluminum adsorption device has the advantages of being suitable for industrial production, good in selectivity and environment-friendly.
12. Sodium carbonate nanofiltration device
The difference between the sodium carbonate nanofiltration device and the common nanofiltration device is mainly reflected in the characteristics and treatment effect of the filter membrane, the filter membrane adopted by the sodium carbonate nanofiltration device has a specific pore size, usually from a few nanometers to tens of nanometers, and most of tiny particles, dissolved matters and organic matters can be filtered. Whereas a typical nanofiltration device may use different kinds of filter membranes, the pore size range may be wider. In the aspect of treatment effect, due to the difference of the pore diameters of the filter membranes, the sodium carbonate nanofiltration device is more suitable for removing tiny particles and organic matters in water and concentrating solutes. Therefore, the main functions of the sodium carbonate nanofiltration device are to remove impurities and dissolved substances in water by nanofiltration technology, and to realize separation and concentration of water.
In summary, the salt lake lithium extraction system provided by the application realizes the coupling adsorption lithium extraction process of the original halogen membrane method through the ultrafiltration device, the nanofiltration device, the adsorption device, the sand filtration ultrafiltration combined treatment device, the qualified liquid reverse osmosis device, the boron removal resin, the lithium chloride MVR device, the lithium precipitation device and the separation recovery device which are sequentially connected, utilizes the membrane method to separate divalent ions such as calcium, magnesium, sulfate radical, carbonate radical and the like from monovalent ions such as lithium and the like, and then utilizes the adsorption, membrane method and evaporation concentration to reduce the evaporation scale, thereby achieving the purpose of extracting high-purity lithium resources under the conditions of low energy consumption and low cost; in addition, by adopting a method combining a membrane method and adsorption, impurities can be thoroughly removed, the purity of lithium is improved, the consumption of an adsorbent is reduced, and the adsorption and desorption efficiency is high.
Example two
By adopting the salt lake lithium extraction system based on membrane separation coupling adsorption, the application provides a salt lake lithium extraction method based on membrane separation coupling adsorption, and the embodiment mainly embodies a first lithium extraction route, and the process principle of the lithium extraction method is as follows:
the raw halogen firstly enters an ultrafiltration device (immersed ultrafiltration), and turbidity such as suspended matters, colloid and the like in water is removed through the ultrafiltration device, so that a subsequent membrane unit is prevented from being blocked; the immersed ultrafiltration produced water enters a first-stage nanofiltration module to realize separation of divalent ions such as sulfate radical, carbonate radical and the like from monovalent ions such as lithium, chlorine and the like, the concentrated water of the first-stage nanofiltration module contains a large amount of divalent ions, but the flow rate is smaller, the concentrated water of the first-stage nanofiltration module is discharged into a titanium adsorption device, after the lithium is adsorbed by the titanium adsorption device, the lithium adsorption qualified liquid enters a sand filtration ultrafiltration combined treatment device (ultrafiltration and sand filtration), and the residual brine (unqualified liquid) returns to a salt lake; the titanium adsorption device adsorbs qualified liquid and enters ultrafiltration and sand filtration to remove turbidity such as suspended matters in brine; the ultrafiltration and sand filtration effluent enters a qualified liquid reverse osmosis device (qualified liquid RO), so that lithium is concentrated and enriched on the RO concentrated water side, the qualified liquid RO concentrated water enters a lithium chloride MVR device for concentration after boron is removed by boron removal resin, then enters a lithium precipitation device, lithium reacts with sodium carbonate to generate lithium carbonate precipitate, and finally solid-liquid separation is carried out by a centrifugal machine, so that the recovery of lithium carbonate solid is realized.
In this embodiment, the mother liquor of the lithium precipitation device and the regeneration liquor of the boron-removing resin both contain a certain amount of lithium, and the mother liquor and the regeneration liquor are refluxed to the titanium adsorption device for treatment under the principle of the highest resource recovery rate.
In this embodiment, the produced water (pure water) of the qualified liquid RO after being treated by the produced water reverse osmosis device (produced water RO) is reused in the production process, and the produced water reverse osmosis concentrated water is returned to the ultrafiltration and sand filtration unit for further extraction of lithium.
Example III
By adopting the salt lake lithium extraction system based on membrane separation coupling adsorption, the application provides a salt lake lithium extraction method based on membrane separation coupling adsorption, and the embodiment mainly embodies a second lithium extraction route, and the process principle of the lithium extraction method is as follows:
the raw halogen firstly enters an ultrafiltration device (immersed ultrafiltration), and turbidity such as suspended matters, colloid and the like in water is removed through the ultrafiltration device, so that a subsequent membrane unit is prevented from being blocked; the immersed ultrafiltration produced water enters a first-stage nanofiltration module to realize separation of bivalent ions such as sulfate radical, carbonate radical and the like from monovalent ions such as lithium, chlorine and the like; the water produced by the first-stage nanofiltration module contains a large amount of HCO besides lithium 3 - 、Cl - And adding alkali into the produced water, and adding bicarbonate alkalinity (HCO) into brine 3 - ) Conversion to Carbonate (CO) 3 2- ) The produced water is added with alkali to react and then enters a secondary nanofiltration module to intercept and retain carbonate on the concentrated water side, the secondary nanofiltration module adds acid into the produced water, and a small amount of HCO is produced in the produced water 3 - Converted into carbon dioxide byThe carbon dioxide in the brine is removed by the carbon remover; the effluent of the carbon remover is adsorbed with lithium by an aluminum adsorbent device, and the aluminum adsorption qualified liquid enters ultrafiltration and sand filtration to remove turbidity such as suspended matters in brine; the aluminum adsorption disqualified liquid can be discharged into a salt lake or reprocessed as tail halogen, ultrafiltration and sand filtration water enters a qualified liquid reverse osmosis device (RO), so that lithium is concentrated and enriched on the RO concentrated water side, the qualified liquid RO concentrated water enters a lithium chloride MVR device for concentration after boron is removed by boron removal resin, then enters a lithium precipitation device, lithium reacts with sodium carbonate to generate lithium carbonate precipitate, and finally solid-liquid separation is carried out by a centrifugal machine, so that the recovery of lithium carbonate solid is realized.
Example IV
Based on the third embodiment, the method for extracting lithium from salt lake based on membrane separation coupling adsorption is provided, and the sodium carbonate is recovered on the basis of the method for extracting lithium provided in the third embodiment, so that the method can be used as a source of sodium carbonate added in a lithium precipitation device.
On the basis of the third embodiment, the concentrated water of the second-stage nanofiltration module is discharged into a sodium carbonate nanofiltration device, carbonate is trapped on the concentrated water side for separation, the produced water of the sodium carbonate nanofiltration device and the produced water of the second-stage nanofiltration module are combined and then enter a carbon remover, and after boron is removed from the concentrated water of the sodium carbonate nanofiltration device, sodium carbonate is recovered by utilizing a sodium carbonate MVR device.
Example five
The lithium extraction methods provided in the second to third embodiments can be combined, and the flow chart can be seen in fig. 1, and the combined lithium extraction method has two parallel lithium extraction routes, so that not only is sufficient lithium extraction realized, but also sodium carbonate can be recovered, and the sodium carbonate can be used as a source of sodium carbonate added in a lithium precipitation device, so that the operation investment cost is reduced.
The salt lake lithium extraction method based on membrane separation coupling adsorption provided by the embodiment can be suitable for salt lakes with low lithium content and mineralization degree and high sodium sulfate and sodium chloride content. In one embodiment, the method may extract lithium from salt lake brine of the quality as shown in table 1 below.
Table 1 salt lake brine quality table
| Ion name | Unit (B) | Numerical value |
| mg 2+ | mg/L | 3.7 |
| K + | mg/L | 16230 |
| Ca 2+ | mg/L | 3.3 |
| Na + | mg/L | 78000 |
| Li + | mg/L | 200 |
| B - | mg/L | 860 |
| SO 4 2- | mg/L | 14200 |
| CL - | mg/L | 56700 |
| CO 3 2- | mg/L | 13500 |
| HCO 3 - | mg/L | 4500 |
The method for extracting lithium from the salt lake provided by the application considers the separation of a divalent ion, removes alkalinity and boron, and simultaneously ensures the recycling of resources of sodium carbonate, sodium chloride, potassium chloride and lithium carbonate.
The lithium extraction method provided in the present application is compared with the conventional lithium extraction method, as shown in table 2 below.
Table 2 comparison of the advantages of the lithium extraction method provided herein with respect to the conventional lithium extraction method
In summary, the application provides a salt lake lithium extraction system based on membrane separation coupling adsorption, which comprises an ultrafiltration device, a nanofiltration device, an adsorption device, a sand filtration ultrafiltration combined treatment device, a qualified liquid reverse osmosis device, a boron removal resin, a lithium chloride MVR device, a lithium precipitation device and a separation recovery device which are sequentially connected, wherein the salt lake brine is subjected to functional treatment through the devices, membrane treatment is realized through the ultrafiltration, nanofiltration, sand filtration ultrafiltration combined treatment device and the reverse osmosis device, and adsorption treatment is realized through a titanium adsorption device and the boron removal resin, namely, the application adopts a primary halogen membrane method coupling adsorption lithium extraction process, realizes separation of calcium, magnesium, sulfate radicals, carbonate radicals and other divalent ions such as lithium by using a membrane method, and then utilizes adsorption, membrane method and evaporation concentration to reduce evaporation scale, thereby realizing high-purity lithium resource extraction under the conditions of low energy consumption and low cost; in addition, by adopting a method combining a membrane method and adsorption, impurities can be thoroughly removed, the purity of lithium (the purity of a lithium product is more than 94%), the consumption of the adsorbent is low, the backwashing frequency of the adsorbent is reduced, the efficiency of the adsorbent is improved, and the fresh water consumption of backwashing is reduced.
Furthermore, the comprehensive recovery system for lithium potassium sodium resources can also be used for preparing sodium carbonate, and the sodium carbonate can be used as a source of precipitated lithium sodium carbonate, so that the preparation investment cost is reduced; in addition, pure water can be prepared for self-use in the lithium extraction process, so that the input cost of water resources is reduced, the recovery rate of salt lake brine resources is improved, and the return on investment is improved.
Example six
Based on the lithium extraction method provided in the third embodiment, the tail halogen discharged by the aluminum adsorption device in the third embodiment is reprocessed, so that the recovery of potassium ions, sodium ions and chloride ions in the salt lake brine is realized.
Specifically, the tail halogen of the aluminum adsorption device contains a large amount of monovalent ions such as potassium ions, sodium ions and chloride ions, wherein a small part of the tail halogen is recycled or exported by acid and alkali production through nanofiltration and bipolar membrane electrodialysis, a large part of the tail halogen enters a chloride production unit, sodium chloride is firstly evaporated by first/second-stage solar low-temperature evaporation and solar hot melting by utilizing the precipitation temperature difference of sodium chloride and potassium chloride, and finally a potassium chloride product is precipitated through cold precipitation.
In this embodiment, the process of recovering potassium, sodium and chloride ions from the tail halogen of the aluminum adsorption device is parallel to the lithium extraction route provided in the third to fifth embodiments, and the construction and operation of the potassium, sodium and chloride ion recovery system and the construction and operation of the lithium extraction system are not affected, and the construction and operation of the lithium extraction system can be performed independently.
Any combination of the technical features of the above embodiments may be performed (as long as there is no contradiction between the combination of the technical features), and for brevity of description, all of the possible combinations of the technical features of the above embodiments are not described; these examples, which are not explicitly written, should also be considered as being within the scope of the present description.
The foregoing has outlined and detailed description of the present application in terms of the general description and embodiments. It should be appreciated that numerous conventional modifications and further innovations may be made to these specific embodiments, based on the technical concepts of the present application; but such conventional modifications and further innovations may be made without departing from the technical spirit of the present application, and such conventional modifications and further innovations are also intended to fall within the scope of the claims of the present application.
Claims (10)
1. The salt lake lithium extraction system based on membrane separation coupling adsorption is characterized by comprising an ultrafiltration device, a nanofiltration device, an adsorption device, a sand filtration ultrafiltration combined treatment device, a qualified liquid reverse osmosis device, boron removal resin, a lithium chloride MVR device, a lithium precipitation device and a separation recovery device which are connected in sequence;
the water inlet end of the ultrafiltration device is connected with a pipeline for conveying salt lake brine, the water outlet end of the ultrafiltration device is connected with the nanofiltration device, the nanofiltration device is connected with the adsorption device, the qualified liquid outlet of the adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device, the water outlet end of the sand filtration ultrafiltration combined treatment device is connected with the water inlet end of the qualified liquid reverse osmosis device, the concentrated water outlet end of the qualified liquid reverse osmosis device is connected with the boron removal resin, the water outlet end of the boron removal resin is connected with the water inlet end of the lithium chloride MVR device, the water outlet end of the lithium chloride MVR device is connected with the water inlet of the lithium precipitation device, the lithium precipitation device is provided with a sodium carbonate inlet, sodium carbonate in the lithium precipitation device reacts with lithium chloride solution to generate lithium carbonate precipitate, the discharge port of the lithium precipitation device is connected with the separation recovery device, and the separation recovery device is used for realizing solid-liquid separation and recovering lithium carbonate precipitate.
2. The lithium extraction system of salt lake based on membrane separation coupling adsorption of claim 1, wherein the adsorption device is a titanium adsorption device having a water inlet, an acid water inlet, a qualified liquid outlet, and a reject liquid outlet;
the nanofiltration device comprises a primary nanofiltration module, the water inlet end of the primary nanofiltration module is connected with the water production end of the ultrafiltration device, the concentrated water outlet end of the primary nanofiltration module is connected with the water inlet of the titanium adsorption device, and the qualified liquid outlet of the titanium adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device.
3. The membrane separation coupled adsorption-based salt lake lithium extraction system of claim 2, wherein the titanium adsorption device further has a lithium precipitation mother liquor inlet connected to a mother liquor discharge outlet of the lithium precipitation device, and the lithium precipitation mother liquor inlet connected to a regeneration liquor discharge outlet of the boron removal resin.
4. The lithium extraction system of salt lake based on membrane separation coupling adsorption of claim 1, wherein the adsorption device is an aluminum adsorption device, and the aluminum adsorption device is provided with a liquid inlet, a qualified liquid outlet, a water inlet and a tail halogen outlet;
The nanofiltration device comprises a multi-stage nanofiltration module, wherein the multi-stage nanofiltration module at least comprises a primary nanofiltration module and a secondary nanofiltration module;
the water inlet end of the primary nanofiltration module is connected with the water producing end of the ultrafiltration device, the water producing end of the primary nanofiltration module is connected with the water inlet end of the secondary nanofiltration module, the water producing end of the secondary nanofiltration module is connected with the liquid inlet of the aluminum adsorption device, and the qualified liquid outlet of the aluminum adsorption device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device;
and an alkali adding port is arranged on a pipeline for connecting the water producing end of the primary nanofiltration module and the water inlet end of the secondary nanofiltration module.
5. The lithium extraction system of salt lake based on membrane separation coupling adsorption of claim 4 wherein the secondary nanofiltration module is connected to the aluminum adsorption device by a carbon remover, the carbon remover having a first inlet, an exhaust port, and a liquid drain port;
the water producing end of the secondary nanofiltration module is connected with the first inlet, the liquid outlet is connected with the liquid inlet of the aluminum adsorption device, and the air outlet is used for discharging carbon dioxide gas;
an acid adding port is arranged on a pipeline for connecting the water producing end of the secondary nanofiltration module and the first inlet of the carbon remover.
6. The membrane separation coupled adsorption-based salt lake lithium extraction system of claim 5 wherein the carbon remover further has a second inlet, the second inlet being connected to a sodium carbonate nanofiltration device;
the inlet end of the sodium carbonate nanofiltration device is connected with the concentrated water outlet end of the secondary nanofiltration module through a connecting pipeline, and a water adding port is arranged on the connecting pipeline; the water outlet of the sodium carbonate nanofiltration device is connected with the second inlet, the concentrated water outlet end of the sodium carbonate nanofiltration device is connected with a sodium carbonate recovery device, and the discharge outlet of the sodium carbonate recovery device is connected with the sodium carbonate adding port on the lithium precipitation device;
the sodium carbonate recovery device comprises a sodium carbonate MVR device and a boron removal device.
7. The salt lake lithium extraction system based on membrane separation coupling adsorption of claim 1, wherein the water producing end of the qualified liquid reverse osmosis device is connected with the inlet end of the water producing reverse osmosis device, and the concentrated water outlet end of the water producing reverse osmosis device is connected with the inlet end of the sand filtration ultrafiltration combined treatment device; the water producing end of the water producing reverse osmosis device is connected with the water using end of the user;
the sand filtration and ultrafiltration combined treatment device comprises a sand bed and an ultrafiltration membrane component connected to the water outlet side of the sand bed.
8. A method for extracting lithium from a salt lake based on membrane separation coupling adsorption, which is characterized by adopting the salt lake lithium extraction system based on membrane separation coupling adsorption as claimed in any one of claims 2-3, and comprising the following steps:
s1: inputting salt lake brine into an ultrafiltration device, and removing suspended matters and colloid in the salt lake brine through the ultrafiltration device;
s2: the salt lake brine treated by the ultrafiltration device enters a primary nanofiltration module, and the primary nanofiltration module is used for removing sulfate radicals and carbonate radicals in the salt lake brine;
s3: the liquid discharged from the concentrated water outlet end of the primary nanofiltration module enters a titanium adsorption device, and the titanium adsorption device is used for adsorbing lithium in the liquid;
s4: the adsorption qualified liquid discharged by the titanium adsorption device enters the sand filtration and ultrafiltration combined treatment device, and the sand filtration and ultrafiltration combined treatment device is used for removing liquid suspended matters and colloid and reducing turbidity;
s5: the liquid treated by the sand filtration and ultrafiltration combined treatment device enters the qualified liquid reverse osmosis device, and the liquid discharged from the concentrated water outlet end of the qualified liquid reverse osmosis device enters boron removal resin for removing boron;
s6: liquid flowing out from the water producing end of the boron-removing resin enters the lithium chloride MVR device, and the lithium chloride MVR device concentrates the liquid entering the lithium chloride MVR device;
S7: and (3) enabling the lithium chloride concentrated solution obtained by concentrating the lithium chloride MVR device to enter a lithium precipitation device to react with sodium carbonate solution, generating lithium carbonate precipitate in the solution, and separating and recovering the generated lithium carbonate precipitate from the solution by the separation and recovery device.
9. The method for extracting lithium from the salt lake based on the membrane separation coupling adsorption is characterized by adopting the salt lake lithium extraction system based on the membrane separation coupling adsorption as claimed in claim 5, and comprises the following steps:
s1: inputting salt lake brine into an ultrafiltration device, and removing suspended matters and colloid in the salt lake brine through the ultrafiltration device;
s2: the salt lake brine treated by the ultrafiltration device enters a primary nanofiltration module, and the primary nanofiltration module is used for removing sulfate radicals and carbonate radicals in the salt lake brine;
s3: liquid discharged from the water producing end of the primary nanofiltration module enters the secondary nanofiltration module to remove carbonate;
s4: liquid discharged from the water producing end of the secondary nanofiltration module enters a carbon remover to remove bicarbonate;
s5: the liquid discharged from the carbon remover enters an aluminum adsorption device, and the aluminum adsorption device is used for adsorbing lithium in the liquid;
s6: the adsorption qualified liquid discharged by the aluminum adsorption device enters the sand filtration and ultrafiltration combined treatment device, and the sand filtration and ultrafiltration combined treatment device is used for removing liquid suspended matters and colloid and reducing turbidity;
S7: the liquid treated by the sand filtration and ultrafiltration combined treatment device enters the qualified liquid reverse osmosis device, and the liquid discharged from the concentrated water outlet end of the qualified liquid reverse osmosis device enters boron removal resin for removing boron;
s8: liquid flowing out from the water producing end of the boron-removing resin enters the lithium chloride MVR device, and the lithium chloride MVR device concentrates the liquid entering the lithium chloride MVR device;
s9: and (3) enabling the lithium chloride concentrated solution obtained by concentrating the lithium chloride MVR device to enter a lithium precipitation device to react with sodium carbonate solution, generating lithium carbonate precipitate in the solution, and separating and recovering the generated lithium carbonate precipitate from the solution by the separation and recovery device.
10. The method for extracting lithium from a salt lake based on membrane separation coupling adsorption according to claim 9, wherein in the step S3, alkali is added to the liquid discharged from the water producing end of the primary nanofiltration module, and then the liquid is discharged into the secondary nanofiltration module;
in step S4, acid is added into the liquid discharged from the water producing end of the secondary nanofiltration module, and then the liquid is discharged into a carbon remover.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311274894.9A CN117305583A (en) | 2023-09-28 | 2023-09-28 | Salt lake lithium extraction system and method based on membrane separation coupling adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311274894.9A CN117305583A (en) | 2023-09-28 | 2023-09-28 | Salt lake lithium extraction system and method based on membrane separation coupling adsorption |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117305583A true CN117305583A (en) | 2023-12-29 |
Family
ID=89249463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311274894.9A Pending CN117305583A (en) | 2023-09-28 | 2023-09-28 | Salt lake lithium extraction system and method based on membrane separation coupling adsorption |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117305583A (en) |
-
2023
- 2023-09-28 CN CN202311274894.9A patent/CN117305583A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mavukkandy et al. | Brine management in desalination industry: From waste to resources generation | |
| CN104843927B (en) | Desulfurization wastewater technique of zero discharge and system | |
| US10315936B2 (en) | Forward osmosis separation processes | |
| CN105000737B (en) | A kind of Industrial sewage treatment system and sewage water treatment method | |
| CN108218087B (en) | System for treating high-salt-content wastewater based on multistage electrically-driven ionic membrane | |
| CN114105173B (en) | System and process for extracting lithium from salt lake brine | |
| CN205603386U (en) | Strong brine zero release membrane concentrator | |
| CN106277534A (en) | The processing means of a kind of low concentration brine waste and technique | |
| CN114014341A (en) | Device and method for preparing high-lithium solution from raw halogen | |
| CN109437444B (en) | Recycling treatment device and method for vanadium precipitation mother liquor and washing water | |
| CN107555542B (en) | Multi-stage nanofiltration-reverse osmosis-membrane distillation combined desalting and salt separation method | |
| CN105481160B (en) | Method and device for preparing industrial salt by strong brine with zero discharge | |
| CN204939142U (en) | A kind for the treatment of facility of desulfurization wastewater of flue gas desulphurization system discharge | |
| CN108689540A (en) | Incineration of refuse flyash wastewater zero discharge and recycling unit and treatment process | |
| CN105152405A (en) | Method and device for treating desulfurization wastewater discharged by flue gas desulfurization system | |
| CN117305583A (en) | Salt lake lithium extraction system and method based on membrane separation coupling adsorption | |
| CN205662415U (en) | High salt waste water recycling treatment facility | |
| CN205241414U (en) | Separation recovery system of chlorine root and sulfate radical in high salt waste water | |
| CN117303633A (en) | Comprehensive recovery system and method for lithium potassium sodium resources in salt lake brine | |
| CN114988438A (en) | Lithium carbonate circulation lithium extraction process | |
| CN116964247A (en) | System and method for direct production of lithium hydroxide | |
| CN103435015B (en) | Technique and device for extracting sulfuric acid (H2SO4) from acid mine water | |
| JP3045378B2 (en) | Method for combined treatment of seawater | |
| CN216426776U (en) | Lithium extraction system for salt lake brine | |
| CN114790059B (en) | Concentrating and filtering device and method for synthetic ammonia and ethylene glycol wastewater concentrated water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |