CN110004457A - A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material - Google Patents
A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material Download PDFInfo
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- CN110004457A CN110004457A CN201810852555.7A CN201810852555A CN110004457A CN 110004457 A CN110004457 A CN 110004457A CN 201810852555 A CN201810852555 A CN 201810852555A CN 110004457 A CN110004457 A CN 110004457A
- Authority
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- China
- Prior art keywords
- bipolar membrane
- lithium
- lithium hydroxide
- raw material
- outlet
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 227
- 239000012528 membrane Substances 0.000 title claims abstract description 179
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 51
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 51
- 239000002994 raw material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 230000008676 import Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 12
- WHWSEYQRQYKZGX-UHFFFAOYSA-N iridium platinum tantalum Chemical compound [Ta].[Ir].[Pt] WHWSEYQRQYKZGX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004891 communication Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 68
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 22
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 21
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 14
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 238000001471 micro-filtration Methods 0.000 claims description 9
- 229920002857 polybutadiene Polymers 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- LFIWDPYJFLBDMX-UHFFFAOYSA-N lithium;sulfuric acid Chemical compound [Li].OS(O)(=O)=O LFIWDPYJFLBDMX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 6
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 230000005611 electricity Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 120
- 238000000909 electrodialysis Methods 0.000 description 35
- 230000008569 process Effects 0.000 description 20
- 150000007519 polyprotic acids Polymers 0.000 description 18
- 238000000926 separation method Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 210000002469 basement membrane Anatomy 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 241001131796 Botaurus stellaris Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000000678 plasma activation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of bipolar membrane devices for preparing lithium hydroxide using Bipolar Membrane method using lithium carbonate as raw material.It include: anolyte import, cathode terminal, anolyte outlet, catholyte outlet；It is characterized in that, pole liquid stream guidance tape is being placed on the inside of clamping plate, it is placed with platinum tantalum iridium electrode on the inside of the liquid stream guidance tape of pole, starts inwardly to be sequentially placed the Bipolar Membrane to lithium rejection greater than 98% in platinum tantalum iridium electrode, resistance alkali anode membrane hinders the film group that sour cavity block is one group；Offer anolyte import and anolyte outlet and catholyte import and catholyte outlet respectively on the liquid stream guidance tape of pole；Liquor inlet and lithium hydroxide outlet and concentrated acid import and concentrated acid outlet are opened in two pieces of clamping plates respectively, are in communication with the outside.Due to being greater than 98% Bipolar Membrane to lithium rejection using resistance to strong acid newly developed, greatly improves the bulk life time of device and be increased to the single water hydrogen-oxygen lithium conversion energy consumption of 98% or more, one ton of every production from original 95-98% to 3 years or more, the yield of lithium hydroxide and drop to 2000 degree of electricity or less.
Description
Technical field
The invention belongs to technical field of membrane separation, and in particular to one kind is suitable for preparing lithium hydroxide by raw material of lithium carbonate
Bipolar membrane device.
Background technique
The primary raw material for producing lithium carbonate is salt lake bittern (ore method is due at high cost in global production capacity very little), rule
The enterprise of modelling production lithium carbonate must possess lithium resource reserves salt lake resources right to mine more abundant, this has the sector
Standby higher resource barrier；On the other hand, since global salt lake overwhelming majority resource is all the low lithium type of high magnesium, and from the low lithium of high magnesium
The technological difficulty of purification & isolation lithium carbonate is very big in old halogen, these technologies only rest in a small number of offshore company's hands before,
This makes lithium carbonate industry but also with technical barrier.Therefore, the global oligopoly pattern of lithium carbonate industry is created.
The whole world lithium carbonate market concentration is very high at present.Before several mega projects in China are gone into operation, the whole world is main to be produced
It can concentrate in tri- hands of SQM, FMC and Chemetall；Data is shown, although there are certain resource and skills for lithium carbonate product
Art barrier, but China have can extraction value salt lake or many, technology Salt Lake Group Company in addition to CITIC Guoan, Tibetan Mining
Breakthrough is faced, the barrier of industry just gradually weakens.
Bipolar Membrane is a kind of amberplex with specific function, and wherein interbed hydrolyzes under electric field action for it
From generation H+ and OH-ion.And this specific function is exactly combined in common electrodialysis by bipolar membrane electrodialysis technology, from
And production/regeneration of instant acid/base may be implemented, or acidification and/or alkalization.The technology can be widely applied to food and add
The fields such as work, chemical industry synthesis and environmental protection, due to its technical advance, Economic competitive and environment friendly, Bipolar Membrane electricity
Osmotic technique is known as a kind of sustainable development technology.Bipolar membrane electrodialysis technology is applied to traditional organic acid or organic base
The NaOH or HCl that in production/regenerative process, not only may be implemented the conversion of acylate or organic alkali salt, but also generate can be with
It is back in generating process.
External Bipolar membrane water splitting has just carried out industrial applications several years ago at present, and develops for different application field
A series of Bipolar Membrane product.External masking technique with Germany with Japan for representative belongs to third-generation technology, and is film-made and sets
It is most advanced that standby and support cloth production, which is with Germany, Japan, Switzerland,.Using Germany as the European countries of representative, Bipolar membrane water splitting
Industrialization level it is higher.And Japan's mainly homogeneous membrane electrodialytic membranes, industrialization level of chlor-alkali film is higher.
The application of Bipolar Membrane is mainly European countries at present, and main application is flue gas desulfurization, selexol process, sodium methoxide
Preparation, HF and HNO3Recycling, methanesulfonic acid preparation, dimethylisopropylamine regeneration, amino acid preparation, medicine intermediate prepare it is contour
The application in end field.And it is less for the application and preparation of the common organic acids such as gluconic acid, lactic acid, tartaric acid, these products he
Mainly from the import of the developing countries such as China, cost compare themselves with Bipolar Membrane produce it is cheaper.
In recent years, at home and abroad started actively using homogeneous membrane as the electrolemma technology of representative, application field is growing, special
The reverse osmosis and irreplaceable status of evaporation is not played in energy-saving and emission-reduction, resource reclaim field.At present with Chinese University of Science and Technology
Xu's copper culture and education award the studying team for representative, developed multinomial homogeneous membrane leading in the world, Bipolar Membrane, the system of diffusion dialysis film
Film theory and method.Water treatment centers rise in the eighties and begin to research Bipolar membrane water splitting, only after the nineties almost
Seize up state.In addition, thering are multiple universities and scientific research institutions all to be studied homogeneous membrane, Bipolar Membrane at present.
Preparing lithium hydroxide also using Bipolar Membrane method has numerous people to study, such as Chinese invention patent
CN201510526884 discloses Bipolar Membrane method and recycles lithium hydroxide technique from solution；Chinese invention patent
CN201610782830 discloses the electrodialysis plant that lithium hydroxide solution is prepared using soluble lithium salt solution；Chinese invention is special
Sharp CN201610794516 discloses the method for preparing lithium hydroxide and lithium carbonate using soluble lithium salt solution；Chinese invention is special
Sharp CN201680025927 discloses the preparation method and its device of lithium hydroxide and lithium carbonate；Chinese invention patent
CN201680027677 discloses the preparation method of lithium hydroxide and lithium carbonate；Chinese invention patent CN201710972445 is disclosed
A kind of LITHIUM BATTERY lithium hydroxide preparation method etc. based on UF membrane coupled method.
The above Bipolar Membrane method prepares lithium hydroxide all without the whereabouts for solving the problems, such as the diluted acid of Bipolar Membrane generation and dilute sulphur
The high problem of the turnover rate of lithium does not also solve in acid.
And Chinese invention patent CN201410124047 discloses a kind of method for extracting lithium hydroxide by salt lake bittern: first
First pass through the calcium ions and magnesium ions being added in sodium carbonate removing salt lake bittern；Obtained low Mg/Li ratio brine is concentrated by common electrodialysis
After obtain concentrated brine；Sodium carbonate deliming magnesium ion again is added into concentrated brine；Carbon is added by multiple steps of crystallization method later
Sour sodium obtains lithium carbonate；By lithium carbonate it is molten again after lithium hydroxide prepared by electrolysis-bipolar membrane electrodialysis system.
And Chinese invention patent CN201410124102 disclose it is a kind of by lithium carbonate production lithium hydroxide electrolysis-it is bis-
Pole membrane electrodialysis system and its production method: including the first alkaline chamber, the first feed compartment, sequentially arranged by side to the other side
Electrolysis-bipolar membrane electrodialysis membrane stack that two alkaline chambers, the second feed compartment and anode chamber are constituted；Each chamber passes sequentially through cationic friendship
Change film, Bipolar Membrane, cation-exchange membrane and Bipolar Membrane interval.
Although these patents, which are used, carries out bipolar film preparation lithium hydroxide by raw material of lithium carbonate, due to lithium carbonate
Solubility it is too small (less than 1.5%), the energy consumption for causing bipolar membrane process is too big, and electric current is too small, and membrane area excessively causes to invest
It is too big.
The above disadvantage all makes these patents be difficult normal commercial application.We are directed to the above status, in forefathers
On the basis of research, the particular/special requirement of lithium hydroxide is prepared for lithium carbonate, lithium sulfate, Bipolar Membrane method, has carried out series of studies
It is developed finally by many-sided experimental study using lithium carbonate as raw material with exploitation, uses dilute sulfuric acid for interior circulating carrier substance
Bipolar film preparation lithium hydroxide preparation process and device, and have developed with there is the Bipolar Membrane of high rejection to lithium, and
Form three compartment bipolar membrane device of Bipolar Membrane+anode membrane+cavity block.
Summary of the invention
The main object of the present invention is to develop a kind of pair for preparing lithium hydroxide using Bipolar Membrane method using lithium carbonate as raw material
Pole film device.Economic, environmental protection Bipolar Membrane method, which can be carried out, the object of the invention is also to provide one kind prepares lithium hydroxide
Operating parameter.
The present invention is achieved by following technical proposals:
A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material, comprising: anolyte import, cathode connection
Column, anolyte outlet, catholyte outlet；It is characterized in that, being placed with pole liquid stream guidance tape on the inside of clamping plate, in pole liquid stream
It is placed with platinum tantalum iridium electrode on the inside of guidance tape, starts inwardly to be sequentially placed to lithium rejection in platinum tantalum iridium electrode greater than 98%
Bipolar Membrane, resistance alkali anode membrane hinder the film group that sour cavity block is one group；
It offers anolyte import and anolyte outlet and catholyte import respectively on the liquid stream guidance tape of pole and catholyte goes out
Mouthful；
Liquor inlet and lithium hydroxide outlet and concentrated acid import and concentrated acid outlet are opened in two pieces of clamping plates respectively, with the external world
Connection.
The resistance alkali anode membrane is the CMB anode membrane using the production of ASTOM company.
The sour cavity block of the resistance is the AHA cavity block using the production of ASTOM company.
The clamping plate is clamped by fastening bolt.
Anode terminal and cathode terminal are connected separately on the clamping plate.
Preferably, being placed with multiple groups film between the liquid stream guidance tape of pole in a kind of above-mentioned bipolar membrane device for preparing lithium hydroxide
Group can save energy consumption and material cost.
Preferably, being greater than 98% Bipolar Membrane in a kind of above-mentioned bipolar membrane device for preparing lithium hydroxide to lithium rejection
With a thickness of 0.1-0.35 millimeters.The thickness of Bipolar Membrane is to influence one of energy consumption and the principal element of rejection.
Preferably, being greater than 98% Bipolar Membrane in a kind of above-mentioned bipolar membrane device for preparing lithium hydroxide to lithium rejection
Control film resistance is 5-8 Ω/cm2, degree of cross linking 70-90%, film thickness 0.15-0.25mm, with the energy consumption of lifting device and is cut
Stay rate.
Preferably, the Bipolar Membrane of the present invention to lithium rejection greater than 98% is to be prepared by the following method acquisition.
Raw material include: the polyethylene, polybutadiene, graphene with a thickness of 0.1-0.15 millimeters；
The preparation process is:
(A) counterdie raw material preparation
Polyethylene, polybutadiene, graphene are 100:5-50:1-10 stock according to mass ratio；
(B) counterdie is prepared
It is graphene-doped in polyethylene, polybutadiene that counterdie is prepared；
(C) Bipolar Membrane is prepared
Using impregnated with method, the sunny side layer of counterdie is subjected to carboxylated using glacial acetic acid, the back of counterdie carries out chlorine using dichloroethyl ether
Ethylize, is then carried out again with m-phenylene diamine (MPD) it is quaternary ammoniated, obtain to lithium rejection greater than 98% Bipolar Membrane；Described cuts lithium
Stay rate greater than 98% Bipolar Membrane index include: to lithium rejection be greater than 98%, control film resistance be 5-8 Ω/cm2, the degree of cross linking
For 70-90%, film thickness 0.15-0.25mm.Using Bipolar Membrane of the invention, Bipolar Membrane method is made to prepare the electric current of lithium hydroxide
Efficiency, the concentration of lithium hydroxide and purity greatly improve.And little power consumption, speed are fast, and the usable floor area of film reduces 40% or more
Preferably, the concentrate mass concentration in bipolar membrane device of the present invention enters the salt of Bipolar Membrane when reaching 10-15%
Room, light liquid mass concentration enter Bipolar Membrane acid compartment when reaching 0.05-0.5%；Alkaline chamber is water inlet with pure water, carries out bipolar film preparation hydrogen
Lithia；Bipolar membrane device pole liquid use mass concentration for 0.5% sulfuric acid+2.0% lithium sulfate；Catholyte and anolyte are distinguished
Alone cycle, flow 1.0-3.0m3/h；Salt room, acid compartment, alkaline chamber flow be 3-12m3/ h, operating pressure 0.02-
0.08MPa, operation temperature are 25-38 DEG C.Working voltage is 50-500V, running current 100-300A.
Preferably, also settable pretreatment portion in communication in a kind of above-mentioned bipolar membrane device for preparing lithium hydroxide
Part is provided with the connection outlet for the dilute sulfuric acid that bipolar membrane device itself is prepared, dilute sulfuric acid warp in pretreatment component
Connection outlet and pretreatment component connection are crossed, and it is 1.0-10% that the feed liquid in pretreatment component, which is dissolved to sulfuric acid lithium concentration, then
With 0.45 micron of micro-filtrate membrane filtration；The lithium hydroxide prepared in filtrate with device itself adjusts pH value to 9-10, then uses aperture
Microfiltration membranes for 0.01-0.1 microns are filtered, and filtrate adjusts pH to 3-6 with dilute sulfuric acid again.0.45 micron of the micro-filtration
Film is a common model of microfiltration membranes.
Bipolar membrane device of the present invention can also be with pretreatment component, electrodialysis condensation means, bipolar membrane element, single polybasic acids
Separation electrodialysis component constitutes the production system that lithium hydroxide is prepared using lithium carbonate as raw material.The wherein Bipolar Membrane of bipolar membrane element
Using the Bipolar Membrane for being greater than 98% to lithium rejection；The cavity block of single polybasic acids separation electrodialysis component is using acidproof single multivalence separation
Cavity block.Single polybasic acids separate the cavity block of electrodialysis component using conventional acidproof resistance acid cavity block as basement membrane, and surface uses etc.
Ion activation, then use electrodeposition process in film surface coating thickness for 1-5 microns of naphthalene sulfonic acids coating, and it is more to form acidproof list
Valence acid separates cavity block.Single polybasic acids separation electrodialysis component belongs to the electrodialysis concentration step before bipolar membrane device.
Bipolar membrane device of the present invention is suitable for being to prepare lithium hydroxide so that industrial level lithium carbonate (according to national standard) is raw material,
Its process is as follows: carrying out being dissolved to sulfuric acid lithium concentration being 1.0-10% by the dilute sulfuric acid for preparing bipolar membrane device itself, be used in combination
0.45 micron of micro-filtrate membrane filtration.It with itself preparing lithium hydroxide to adjust pH value to 9-10, then with aperture is 0.01- in filtrate
0.1 micron of microfiltration membranes are filtered, and filtrate adjusts pH to 3-6 with dilute sulfuric acid again.Then, dilute salt that filtrate and Bipolar Membrane come out
Liquid enters electrodialysis condensation means together, and concentrate concentration enters the salt room of Bipolar Membrane up to 10-15%, and light liquid concentration reaches 0.05-
0.5% enters Bipolar Membrane acid compartment；In bipolar membrane element, alkaline chamber is water inlet with pure water, carries out bipolar film preparation lithium hydroxide.It is double
Pole film device pole liquid uses the lithium sulfate of 0.5% sulfuric acid+2.0%；Catholyte is individually recycled with anolyte, flow 1.0-
3.0m3/h；Salt room, acid compartment, alkaline chamber flow be 3-12m3/ h, operating pressure 0.02-0.08MPa, operation temperature are 25-38 DEG C.
Working voltage is 50-500V, running current 100-300A；Locate as alkali into pre- the lithium hydroxide part that bipolar membrane element generates
It manages and carries out pH adjusting in component, remaining becomes lithium hydroxide product.
Dilute nitration mixture that bipolar membrane element comes out is separated into single polybasic acids separation electrodialysis component, a small amount of unit price separated
Discharge after heteroacid is neutralized, the dilute sulfuric acid separated continues to dissolve the lithium carbonate of next group, and so far one with dilute sulphur
Acid is that the bipolar film preparation lithium hydroxide process of circulating carrier terminates.
The bipolar membrane device has the advantage that compared with other patent bipolar membrane devices
(1) due to the Bipolar Membrane using resistance to strong acid newly developed to lithium rejection greater than 98%, mention the bulk life time of device substantially
The yield of height to 3 years or more, lithium hydroxide is increased to 98% or more, the single water hydrogen-oxygen lithium of one ton of every production from original 95-98% and turns
Change energy consumption and drops to 2000 degree of electricity or less.
(2) it due to using with dilute sulfuric acid as interior circulating carrier substance, discharges entire production process without diluted acid, avoids
The loss that lithium is discharged with diluted acid, while the conductivity of Bipolar Membrane salt room also greatly improved, increase the current efficiency and life of device
Production capacity power.
(3) the increased high-precision microfiltration membranes in the present apparatus, greatly improve the pretreatment precision of feed liquid, and it is de- to reduce resin
Hard intensity, saves energy consumption.
(4) electrodialytic process is separated due to using single polybasic acids, makes recycling with the interior circulating carrier substance of dilute sulfuric acid
Monovalent acid in the process, if hydrochloric acid, hydrofluoric acid, nitric acid isolate circulating system, thus avoid the chloride ion in material, fluorine from
The problem of accumulation of the monovalent anions such as son, nitrate anion.
(5) film size 550mm*1100mm, group number are used as the film group device of 60-240 group, greatly improves single film film group
The processing capacity of device, reduces equipment investment cost.
Detailed description of the invention
Fig. 1 is the flowage structure schematic diagram that the bipolar membrane device for preparing lithium hydroxide of the invention is realized.
Fig. 2 is Bipolar Membrane modular construction schematic diagram of the invention.
Fig. 3 is the bipolar membrane device Bipolar Membrane member principle figure for preparing lithium hydroxide of the invention.
Fig. 4 is the process route that device of the present invention is applicable in that industrial level lithium carbonate prepares lithium hydroxide.
Fig. 5 is the process route that device of the present invention is applicable in that recycling lithium carbonate prepares lithium hydroxide.
Wherein: 1, anolyte import, 2, lithium rejection is greater than 98% Bipolar Membrane, 3, the dedicated anode membrane of resistance alkali of resistance to highly basic,
4, the dedicated cavity block of resistance acid of resistance to strong acid, 5, catholyte import, 6, fastening bolt, 7, liquor inlet, 8, pole liquid stream guidance tape, 9, anode
Binding post, 10, clamping plate, 11, lithium hydroxide outlet, 12, concentrated acid outlet, 13, cathode terminal, 14, concentrated acid import, 15, platinum
Tantalum iridium electrode, 16, anolyte outlet, 17, catholyte outlet.
Specific embodiment
Embodiment 1
According to Fig. 1, Fig. 2, Fig. 3, a set of bipolar membrane device for preparing lithium hydroxide, including pretreatment component, electric osmose are installed
It analyses condensation means, bipolar membrane element, single polybasic acids and separates electrodialysis component.Wherein there is an anolyte import 1, cathode terminal 13,
Anolyte outlet 16, catholyte outlet 17；It is being placed with pole liquid stream guidance tape 8 on the inside of clamping plate 10, the liquid stream guidance tape 8 in pole
Inside is placed with platinum tantalum iridium electrode 15, starts inwardly to be sequentially placed in platinum tantalum iridium electrode 15 double greater than 98% to lithium rejection
Pole film 2, the dedicated anode membrane 3 of resistance alkali of resistance to highly basic, resistance to strong acid the dedicated cavity block 4 of resistance acid be one group film group；In two pieces of pole liquid stream road
Anolyte import 1 and anolyte outlet 16 and catholyte import 5 and catholyte outlet 17 are offered on plate 8 respectively；Feed liquid into
Mouth 7 and lithium hydroxide outlet 11 and concentrated acid import 14 and concentrated acid outlet 12 are opened in two pieces of clamping plates 10 respectively, even with the external world
It is logical；Clamping plate 10 is clamped by fastening bolt 6；Anode terminal 9 and cathode terminal 13 are connected separately on clamping plate 10.
The Bipolar Membrane 2 to lithium rejection greater than 98% of bipolar membrane element is with a thickness of 0.1 millimeter in bipolar membrane device
Graphene counterdie, proportions 100:20:5 are admixed in polyethylene and polybutadiene, then carry out Bipolar Membrane with impregnated with method
Preparation, sunny side layer carry out carboxylated using glacial acetic acid, and the back replaces common chloromethyl ether to carry out chloroethylation using dichloroethyl ether, then
Common trimethylamine is replaced to carry out the quaternary ammoniated Bipolar Membrane 2 formed to lithium rejection greater than 98%, control film electricity with m-phenylene diamine (MPD) amine
Resistance is 6 Ω/cm2, the degree of cross linking 80%, film thickness 0.15mm.Using the Bipolar Membrane of the invention having a size of 550*1100mm+
The AHA cavity block of the CMB anode membrane+ASTOM of ASTOM becomes Bipolar Membrane component for totally 120 groups.
For the cavity block of single polybasic acids separation electrodialysis component using conventional acidproof resistance acid cavity block as basement membrane, surface uses plasma
Activation, then use electrodeposition process in film surface coating thickness is 3 microns of naphthalene sulfonic acids coating, and form acidproof list polybasic acids and divide
From cavity block.
Using lithium carbonate as raw material, carries out being dissolved to sulfuric acid lithium concentration being 3% with dilute sulfuric acid prepared by device itself, be used in combination
0.45 micron of micro-filtrate membrane filtration.PH value is adjusted to 9.5 with itself preparing lithium hydroxide in filtrate, then with aperture is 0.05 micron
Microfiltration membranes be filtered, filtrate again with dilute sulfuric acid adjust pH to 4.
Enter electrodialysis condensation means together with dilute saline solution that filtrate and Bipolar Membrane come out, concentrate concentration is up to entering after 10%
The salt room of Bipolar Membrane, light liquid concentration 0.2% enter Bipolar Membrane acid compartment；In bipolar membrane element, alkaline chamber is water inlet with pure water, is carried out
Bipolar film preparation lithium hydroxide.Bipolar membrane device pole liquid uses the lithium sulfate of 0.5% sulfuric acid+2.0%；Catholyte and anolyte point
Other alone cycle, flow 1.5m3/h；Salt room, acid compartment, alkaline chamber flow be 3m3/h, operating pressure 0.04MPa, operation temperature
It is 30 DEG C.Working voltage is 200V, running current 200A；Locate as alkali into pre- the lithium hydroxide part that bipolar membrane element generates
It manages and carries out pH adjusting in component, remaining becomes lithium hydroxide product.
Dilute nitration mixture that bipolar membrane element comes out is separated into single polybasic acids separation electrodialysis component, a small amount of unit price separated
Discharge, the dilute sulfuric acid separated continue to dissolve the lithium carbonate of next group after heteroacid is neutralized.Entire bipolar membrane device
Processing current efficiency is up to 85%, and total energy consumption is monohydrate lithium hydroxide when 1800 degree of electricity/tons are.Lithium loss late 0.3%, obtained hydrogen
Lithium concentration is aoxidized up to 10%, purity is up to 99.8%.
Embodiment 2
According to Fig. 1, Fig. 2, Fig. 3, a set of bipolar membrane device for preparing lithium hydroxide structure similar to embodiment is installed, including
Pretreatment component, electrodialysis condensation means, bipolar membrane element, single polybasic acids separate electrodialysis component.It is bipolar in bipolar membrane device
The Bipolar Membrane 2 to lithium rejection greater than 98% of membrane element is to admix stone in the polyethylene and polybutadiene with a thickness of 0.1 millimeter
Black alkene counterdie, proportions 100:30:8, then the preparation of Bipolar Membrane is carried out with impregnated with method, sunny side layer is carried out using glacial acetic acid
Carboxylated, the back replaces common chloromethyl ether to carry out chloroethylation using dichloroethyl ether, then replaces common three with m-phenylene diamine (MPD) amine
Methylamine carry out it is quaternary ammoniated formed to lithium rejection be greater than 98% Bipolar Membrane 2, control film resistance be 5 Ω/cm2, the degree of cross linking 75%,
Film thickness is 0.12mm.Using the AHA of the CMB anode membrane+ASTOM of the Bipolar Membrane+ASTOM of the invention having a size of 550*1100mm
Cavity block becomes Bipolar Membrane component for totally 120 groups.
For the cavity block of single polybasic acids separation electrodialysis component using conventional acidproof resistance acid cavity block as basement membrane, surface uses plasma
Activation, then use electrodeposition process in film surface coating thickness for 2.5 microns of naphthalene sulfonic acids coating, and form acidproof list polybasic acids
Separate cavity block.
Using lithium carbonate as raw material, carries out being dissolved to sulfuric acid lithium concentration being 2% with dilute sulfuric acid prepared by device itself, be used in combination
0.45 micron of micro-filtrate membrane filtration.PH value is adjusted to 9.5 with itself preparing lithium hydroxide in filtrate, then with aperture is 0.05 micron
Microfiltration membranes be filtered, filtrate again with dilute sulfuric acid adjust pH to 4.
Filtrate enters electrodialysis condensation means together with dilute saline solution that Bipolar Membrane comes out, and concentrate concentration enters bipolar up to 8%
The salt room of film, light liquid concentration enter Bipolar Membrane acid compartment up to 0.3%；In bipolar membrane element, alkaline chamber is water inlet with pure water, is carried out double
Pole film preparation lithium hydroxide.Bipolar membrane device pole liquid uses the lithium sulfate of 0.5% sulfuric acid+2.0%；Catholyte and anolyte are distinguished
Alone cycle, flow 1.5m3/h；Salt room, acid compartment, alkaline chamber flow be 4m3/h, operating pressure 0.05MPa, operation temperature is
30℃.Working voltage is 180V, running current 180A；The lithium hydroxide part that bipolar membrane element generates is as alkali into pretreatment
PH adjusting is carried out in component, remaining becomes lithium hydroxide product.
Dilute nitration mixture that bipolar membrane element comes out is separated into single polybasic acids separation electrodialysis component, a small amount of unit price separated
Discharge, the dilute sulfuric acid separated continue to dissolve the lithium carbonate of next group after heteroacid is neutralized.Entire bipolar membrane device
Processing current efficiency is up to 86%, and total energy consumption is monohydrate lithium hydroxide when 1700 degree of electricity/tons are.Lithium loss late 0.2%, obtained hydrogen
Lithium concentration is aoxidized up to 8%, purity is up to 99.8%.
Embodiment 3
According to Fig. 1, Fig. 2, Fig. 3, a set of bipolar membrane device for preparing lithium hydroxide structure similar to embodiment is installed, including
Pretreatment component, electrodialysis condensation means, bipolar membrane element, single polybasic acids separate electrodialysis component.It is bipolar in bipolar membrane device
The Bipolar Membrane 2 to lithium rejection greater than 98% of membrane element is to admix in the polyethylene and polybutadiene with a thickness of 0.15 millimeter
Graphene counterdie, proportions 100:40:9, then carry out with impregnated with method the preparation of Bipolar Membrane, sunny side layer using glacial acetic acid into
Row carboxylated, the back replaces common chloromethyl ether to carry out chloroethylation using dichloroethyl ether, then is replaced commonly with m-phenylene diamine (MPD) amine
Trimethylamine carries out the quaternary ammoniated Bipolar Membrane 2 formed to lithium rejection greater than 98%, and control film resistance is 6 Ω/cm2, and the degree of cross linking is
75%, film thickness 0.15mm.Using the CMB anode membrane+ASTOM of the Bipolar Membrane+ASTOM of the invention having a size of 550*1100mm
AHA cavity block totally 60 groups become Bipolar Membrane component.
For the cavity block of single polybasic acids separation electrodialysis component using conventional acidproof resistance acid cavity block as basement membrane, surface uses plasma
Activation, then use electrodeposition process in film surface coating thickness for 3.5 microns of naphthalene sulfonic acids coating, and form acidproof list polybasic acids
Separate cavity block.
Using lithium carbonate as raw material, carries out being dissolved to sulfuric acid lithium concentration being 5% with dilute sulfuric acid prepared by device itself, be used in combination
0.45 micron of micro-filtrate membrane filtration.PH value is adjusted to 10 with itself preparing lithium hydroxide in filtrate, then with aperture is 0.05 micron
Microfiltration membranes be filtered, filtrate again with dilute sulfuric acid adjust pH to 4.
Filtrate enters electrodialysis condensation means together with dilute saline solution that Bipolar Membrane comes out, and concentrate concentration enters double up to 10%
The salt room of pole film, light liquid concentration enter Bipolar Membrane acid compartment up to 0.2%；In bipolar membrane element, alkaline chamber is water inlet with pure water, is carried out
Bipolar film preparation lithium hydroxide.Bipolar membrane device pole liquid uses the lithium sulfate of 0.5% sulfuric acid+2.0%；Catholyte and anolyte point
Other alone cycle, flow 1.5m3/h；Salt room, acid compartment, alkaline chamber flow be 3m3/h, operating pressure 0.04MPa, operation temperature
It is 35 DEG C.Working voltage is 100V, running current 200A；Locate as alkali into pre- the lithium hydroxide part that bipolar membrane element generates
It manages and carries out pH adjusting in component, remaining becomes lithium hydroxide product.
Dilute nitration mixture that bipolar membrane element comes out is separated into single polybasic acids separation electrodialysis component, a small amount of unit price separated
Discharge, the dilute sulfuric acid separated continue to dissolve the lithium carbonate of next group after heteroacid is neutralized.Entire bipolar membrane device
Processing current efficiency is up to 88%, and total energy consumption is monohydrate lithium hydroxide when 1900 degree of electricity/tons are.Lithium loss late 0.1%, obtained hydrogen
Lithium concentration is aoxidized up to 12%, purity is up to 99.9%.
The index of lithium carbonate used in the present invention is as follows: GB/T 11075-2013, YS/T 582-2013.
The product index that the present invention produces the lithium hydroxide obtained is as follows: GB/T 8766-2013, GB/T 26008-
2010。
Embodiment 4
Bipolar membrane device of the present invention is suitable for following two lithium carbonate and prepares lithium hydroxide process route.
The first, the lithium carbonate suitable for technical grade prepares lithium hydroxide process route.
As shown in figure 4, its process route the following steps are included:
A. the dilute sulfuric acid that mass concentration is 5% or so is added in the lithium carbonate of technical grade, and lithium sulfate solution and titanium dioxide are generated after dissolution
Carbon gas, carbon dioxide gas exclude.
B. the lithium sulfate solution that step A is obtained is concentrated by electrodialysis, obtains lithium sulfate dope.
C. the lithium sulfate dope that step B is obtained obtains refined sulfuric acid lithium solution by accurate filter, accurate filter
Effect is the impurity excluded in lithium sulfate dope.
Accurate filter can be leaf filter or ultrafilter.
D. refined sulfuric acid lithium solution step C obtained is handled by bipolar membrane electrodialysis system, and obtaining mass concentration is
The lithium hydroxide that the lithium sulfate and mass concentration that 5% or so dilute sulfuric acid, mass concentration are 8% are 5%；The dilute sulfuric acid contains Determination of Trace Sulfur
Sour lithium impurity.
Mass concentration be 5% lithium hydroxide using MVR carry out condensing crystallizing, then successively carry out demagnetization, washing and drying,
Broken and classification packaging, the lithium carbonate for completing technical grade prepare the process of lithium hydroxide.
The dilute sulfuric acid that mass concentration is 5% or so, which is back in step A, to be recycled.
The lithium sulfate that mass concentration is 8% is back in step B, is concentrated to get lithium sulfate dope by electrodialysis.
Second, lithium hydroxide process route is prepared suitable for recycling lithium carbonate.
As shown in figure 5, its process route the following steps are included:
A. recycling lithium carbonate is first washed and is filtered, and dilute sulfuric acid dissolution then is added in filter cake.It is molten that lithium sulfate is generated after dissolution
Liquid and carbon dioxide gas, carbon dioxide gas exclude.
B. the lithium sulfate solution that step a is obtained successively passes through alkali cleaning, filtering, resins exchange, essence filtering and electrodialysis concentration,
Obtain lithium sulfate dope.
C. the lithium sulfate dope that step b is obtained is handled by bipolar membrane electrodialysis system, obtains dilute sulfuric acid, lithium sulfate and hydrogen
Lithia；The dilute sulfuric acid contains micro lithium sulfate impurity.
Lithium hydroxide carries out condensing crystallizing using MVR, then successively carries out demagnetization, washing and drying, broken and classification packaging,
Complete the process that recycling lithium carbonate prepares lithium hydroxide.
Claims (9)
1. a kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material, comprising: anolyte import (1), yin
Pole binding post (13), anolyte outlet (16), catholyte outlet (17)；It is characterized in that, being put on the inside of clamping plate (10)
It is equipped with pole liquid stream guidance tape (8), platinum tantalum iridium electrode (15) is placed on the inside of pole liquid stream guidance tape (8), in platinum tantalum iridium electrode (15)
Start inwardly to be sequentially placed the Bipolar Membrane (2) to lithium rejection greater than 98%, resistance alkali anode membrane hinders the film group that sour cavity block is one group；
Offer anolyte import (1) and anolyte outlet (16) and catholyte import respectively on pole liquid stream guidance tape (8)
(5) and catholyte exports (17)；
Liquor inlet (7) and lithium hydroxide outlet (11) and concentrated acid import (14) and concentrated acid outlet (12) are opened in two respectively
Block clamping plate (10), is in communication with the outside.
2. the bipolar membrane device as described in claim 1 for being suitable for preparing lithium hydroxide using lithium carbonate as raw material, feature exist
In: the clamping plate (10) is clamped by fastening bolt (6).
3. the bipolar membrane device as described in claim 1 for being suitable for preparing lithium hydroxide using lithium carbonate as raw material, feature exist
In: anode terminal (9) and cathode terminal (13) are connected separately on the clamping plate (10).
4. the bipolar membrane device as described in claim 1 for being suitable for preparing lithium hydroxide using lithium carbonate as raw material, feature exist
In: multiple groups film group is placed between the pole liquid stream guidance tape (8).
5. the bipolar membrane device as described in claim 1 for being suitable for preparing lithium hydroxide using lithium carbonate as raw material, feature exist
In: it is described to the high rejection of lithium greater than 98% Bipolar Membrane with a thickness of 0.1-0.35 millimeters.
6. the bipolar membrane device as described in claim 1 for being suitable for preparing lithium hydroxide using lithium carbonate as raw material, feature exist
In: the control film resistance of the Bipolar Membrane to the high rejection of lithium greater than 98% is 5-8 Ω/cm2, degree of cross linking 70-90%, film thickness
Degree is 0.15-0.25mm.
7. being suitable for filling using the Bipolar Membrane that lithium carbonate prepares lithium hydroxide as raw material as of any of claims 1-6
It sets, it is characterised in that: the Bipolar Membrane to the high rejection of lithium greater than 98% is to be prepared by the following method acquisition, raw material
It include: the polyethylene, polybutadiene, graphene with a thickness of 0.1-0.15 millimeters；
The preparation process is:
X1. counterdie raw material preparation
Polyethylene, polybutadiene, graphene are 100:5-50:1-10 stock according to mass ratio；
X2. counterdie is prepared
It is graphene-doped in polyethylene, polybutadiene that counterdie is prepared；
X3. Bipolar Membrane is prepared
Using impregnated with method, the sunny side layer of counterdie is subjected to carboxylated using glacial acetic acid, the back of counterdie carries out chlorine using dichloroethyl ether
Ethylize, is then carried out again with m-phenylene diamine (MPD) it is quaternary ammoniated, obtain to lithium rejection greater than 98% Bipolar Membrane (2)；It is described to lithium
The index of Bipolar Membrane (2) of the rejection greater than 98% includes: to be greater than 98%, control film resistance to lithium rejection for 5-8 Ω/cm2, hand over
Connection degree is 70-90%, film thickness 0.15-0.25mm.
8. being suitable for filling using the Bipolar Membrane that lithium carbonate prepares lithium hydroxide as raw material as of any of claims 1-6
It sets, it is characterised in that: concentrate mass concentration enters the salt room of Bipolar Membrane when reaching 10-15%, light liquid mass concentration reaches 0.05-
Enter Bipolar Membrane acid compartment when 0.5%；Alkaline chamber is water inlet with pure water, carries out bipolar film preparation lithium hydroxide；Bipolar membrane device pole liquid is adopted
With the lithium sulfate for the sulfuric acid+2.0% that mass concentration is 0.5%；Catholyte is individually recycled with anolyte, flow 1.0-
3.0m3/h；Salt room, acid compartment, alkaline chamber flow be 3-12m3/ h, operating pressure 0.02-0.08MPa, operation temperature are 25-38 DEG C,
Working voltage is 50-500V, running current 100-300A.
9. being suitable for filling using the Bipolar Membrane that lithium carbonate prepares lithium hydroxide as raw material as of any of claims 1-6
It sets, it is characterised in that: also settable pretreatment component in communication is provided with bipolar membrane device in pretreatment component
The connection outlet for the dilute sulfuric acid itself being prepared, dilute sulfuric acid will be pre-processed by connection outlet and pretreatment component connection
It is 1.0-10% that feed liquid in component, which is dissolved to sulfuric acid lithium concentration, then with 0.45 micron of micro-filtrate membrane filtration；In filtrate certainly with device
The lithium hydroxide of body preparation adjusts pH value and is filtered to 9-10, then with the microfiltration membranes that aperture is 0.01-0.1 microns, and filtrate is again
PH to 3-6 is adjusted with dilute sulfuric acid.
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| CN114146574A (en) * | 2021-11-26 | 2022-03-08 | 中南大学 | Modified Nb2CTxNano-sheet film and preparation method thereof |
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| CN105622435A (en) * | 2016-02-16 | 2016-06-01 | 建德蓝忻环境科技有限公司 | Bipolar membrane device for preparing amino-1-propanol |
| CN107299361A (en) * | 2016-08-31 | 2017-10-27 | 江苏力泰锂能科技有限公司 | The electrodialysis plant of lithium hydroxide solution is prepared using soluble lithium salt solution |
| CN108097047A (en) * | 2017-12-14 | 2018-06-01 | 杭州水处理技术研究开发中心有限公司 | A kind of dilute sodium hydroxide electrodialysis concentrates film group device |
| CN208667866U (en) * | 2018-07-30 | 2019-03-29 | 宜宾丽博生物科技有限公司 | A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material |
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| CN105622435A (en) * | 2016-02-16 | 2016-06-01 | 建德蓝忻环境科技有限公司 | Bipolar membrane device for preparing amino-1-propanol |
| CN107299361A (en) * | 2016-08-31 | 2017-10-27 | 江苏力泰锂能科技有限公司 | The electrodialysis plant of lithium hydroxide solution is prepared using soluble lithium salt solution |
| CN108097047A (en) * | 2017-12-14 | 2018-06-01 | 杭州水处理技术研究开发中心有限公司 | A kind of dilute sodium hydroxide electrodialysis concentrates film group device |
| CN208667866U (en) * | 2018-07-30 | 2019-03-29 | 宜宾丽博生物科技有限公司 | A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114146574A (en) * | 2021-11-26 | 2022-03-08 | 中南大学 | Modified Nb2CTxNano-sheet film and preparation method thereof |
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