CN110004457B - Bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as raw material - Google Patents
Bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as raw material Download PDFInfo
- Publication number
- CN110004457B CN110004457B CN201810852555.7A CN201810852555A CN110004457B CN 110004457 B CN110004457 B CN 110004457B CN 201810852555 A CN201810852555 A CN 201810852555A CN 110004457 B CN110004457 B CN 110004457B
- Authority
- CN
- China
- Prior art keywords
- bipolar membrane
- lithium
- acid
- membrane
- lithium hydroxide
- 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.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 253
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 246
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 46
- 239000002994 raw material Substances 0.000 title claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- WHWSEYQRQYKZGX-UHFFFAOYSA-N iridium platinum tantalum Chemical compound [Ta].[Ir].[Pt] WHWSEYQRQYKZGX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 210000004379 membrane Anatomy 0.000 claims description 184
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 72
- 238000000909 electrodialysis Methods 0.000 claims description 41
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 30
- 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 30
- 238000000926 separation method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 19
- 239000002585 base Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000001471 micro-filtration Methods 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012267 brine Substances 0.000 claims description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- 238000005470 impregnation Methods 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 210000002469 basement membrane Anatomy 0.000 claims description 2
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims 1
- 230000021523 carboxylation Effects 0.000 claims 1
- 238000006473 carboxylation reaction Methods 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 10
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 abstract description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 abstract description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 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
- 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
- 229910002651 NO3 Inorganic materials 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
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation 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
- 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
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 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
- 238000000108 ultra-filtration Methods 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 bipolar membrane device for preparing lithium hydroxide by taking lithium carbonate as a raw material and adopting a bipolar membrane method. Comprising the following steps: an anolyte inlet, a cathode binding post, an anolyte outlet and a catholyte outlet; the lithium ion battery is characterized in that a polar liquid runner plate is arranged close to the inner side of the clamping plate, a platinum tantalum iridium electrode is arranged on the inner side of the polar liquid runner plate, bipolar membranes with the lithium rejection rate of more than 98% are sequentially arranged inwards from the platinum tantalum iridium electrode, and an alkali-resistant anode membrane and an acid-resistant cathode membrane are a group of membrane groups; an anolyte inlet and an anolyte outlet, and a catholyte inlet and a catholyte outlet are respectively arranged on the anolyte channel plate; the feed liquid inlet and the lithium hydroxide outlet, and the concentrated acid inlet and the concentrated acid outlet are respectively arranged on the two clamping plates and are communicated with the outside. Because the newly developed bipolar membrane with strong acid resistance and lithium rejection rate of more than 98% is adopted, the whole service life of the device is greatly prolonged to more than 3 years, the yield of lithium hydroxide is increased to more than 98% from the original 95-98%, and the conversion energy consumption of lithium hydroxide monohydrate per ton is reduced to less than 2000 ℃.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as a raw material.
Background
The main raw material for producing lithium carbonate is salt lake brine (the ore method has low global productivity due to high cost), so enterprises for producing lithium carbonate in large scale must have the salt lake resource exploitation rights with rich lithium resource reserves, which makes the industry have high resource barriers; on the other hand, most of the resources of the global salt lake are high-magnesium low-lithium, and the technical difficulty of the process for purifying and separating lithium carbonate from high-magnesium low-lithium old brine is great, and the technologies are only mastered in a few foreign companies before, so that the lithium carbonate industry has technical barriers. Thus, a global oligopolistic pattern of the lithium carbonate industry is created.
The current global lithium carbonate market concentration is very high. Before the delivery of several large projects in China, the global main productivity is concentrated in three hands of SQM, FMC and Chemetall; the data show that although the lithium carbonate product has certain resources and technical barriers, the salt lake with the exploitation value in China is not few, the technology is also in breakthrough in salt lake groups outside the national security and the Tibetan mining industry, and the barriers of the industry are gradually weakened.
The bipolar membrane is an ion exchange membrane with special functions, and the bipolar membrane is subjected to water dissociation in the middle under the action of an electric field to generate H+ and OH-ions. The bipolar membrane electrodialysis technology combines the special function into common electrodialysis, so that the production/regeneration of instant acid/alkali or acidification and/or alkalization can be realized. The technology can be widely applied to the fields of food processing, chemical synthesis, environmental protection and the like, and the bipolar membrane electrodialysis technology is known as a sustainable development technology due to technical advancement, economic competitiveness and environmental friendliness. The bipolar membrane electrodialysis technology is applied to the production/regeneration process of the traditional organic acid or organic alkali, so that not only can the conversion of the organic acid salt or the organic alkali salt be realized, but also the generated NaOH or HCl can be recycled in the generation process.
At present, the foreign bipolar membrane technology is industrially applied for a few years, and a series of bipolar membrane products are developed aiming at different application fields. Foreign film forming technologies represented by germany and japan are the third generation technologies, and the production of film forming equipment and support cloth is the most advanced in germany, japan, and swiss. The bipolar membrane technology is industrialized to a high degree in european countries, typified by germany. The industrialization degree of the homogeneous membrane electrodialysis membrane and the chlor-alkali membrane is higher in japan.
The application of the bipolar membrane is mainly in European countries, and the main applications are flue gas desulfurization, natural gas desulfurization, sodium methoxide preparation, HF and HNO 3 Is applied to the high-end fields such as recovery, methanesulfonic acid preparation, dimethyl isopropylamine regeneration, amino acid preparation, medicine intermediate preparation and the like. The common organic acids such as gluconic acid, lactic acid, tartaric acid and the like are less in preparation and application, and the products are mainly imported from developing countries such as China, and the cost of the products is cheaper than that of the products produced by the products by the bipolar membranes.
In recent years, the membrane technology represented by homogeneous membranes is active at home and abroad, the application field is increasingly expanded, and the membrane technology plays an irreplaceable role in the fields of energy conservation, emission reduction and resource recovery, namely, the reverse osmosis and evaporation method. At present, research teams represented by Xu Tongwen teaching of China university of science and technology develop a plurality of international leading membrane-making theories and methods of homogeneous membranes, bipolar membranes and diffusion dialysis membranes. Water treatment centers began to study bipolar membrane technology since the eighties, but were almost at rest after the nineties. In addition, many universities and scientific institutions currently have studied homogeneous membranes and bipolar membranes.
Numerous studies have been made on the preparation of lithium hydroxide by bipolar membrane process, such as chinese patent No. CN201510526884, which discloses a process for recovering lithium hydroxide from solution by bipolar membrane process; chinese patent No. CN201610782830 discloses an electrodialysis device for preparing lithium hydroxide solution from soluble lithium salt solution; chinese patent No. CN201610794516 discloses a method for preparing lithium hydroxide and lithium carbonate using a soluble lithium salt solution; chinese patent No. CN201680025927 discloses a method and apparatus for preparing lithium hydroxide and lithium carbonate; chinese patent No. CN201680027677 discloses a method for preparing lithium hydroxide and lithium carbonate; chinese patent No. CN201710972445 discloses a method for preparing battery-grade lithium hydroxide based on membrane separation coupling method.
The problem of the forward direction of dilute acid generated by the bipolar membrane and the problem of high loss rate of lithium in dilute sulfuric acid are not solved in the preparation of lithium hydroxide by the bipolar membrane method.
Chinese patent No. CN201410124047 discloses a method for extracting lithium hydroxide from salt lake brine: firstly, removing calcium and magnesium ions in salt lake brine by adding sodium carbonate; concentrating the obtained brine with low magnesium-lithium ratio through common electrodialysis to obtain concentrated brine; adding sodium carbonate into the concentrated brine to remove calcium and magnesium ions again; adding sodium carbonate into the mixture by a multi-step crystallization method to obtain lithium carbonate; and re-dissolving lithium carbonate, and preparing lithium hydroxide by an electrolysis-bipolar membrane electrodialysis system.
And chinese patent No. CN201410124102 discloses an electrolytic-bipolar membrane electrodialysis system for producing lithium hydroxide from lithium carbonate and a production method thereof: comprises an electrolysis-bipolar membrane electrodialysis membrane stack formed by a first alkali chamber, a first feed liquid chamber, a second alkali chamber, a second feed liquid chamber and an anode chamber which are sequentially arranged from one side to the other side; each chamber sequentially passes through a cation exchange membrane, a bipolar membrane, a cation exchange membrane and a bipolar membrane.
Although the patents adopt the lithium carbonate as the raw material to prepare the lithium hydroxide by using the bipolar membrane, the solubility of the lithium carbonate is too small (less than 1.5%), so that the energy consumption of the bipolar membrane process is too large, the current is too small, and the investment is too large due to the excessive membrane area.
These drawbacks make it difficult to properly industrialize the patent. Aiming at the current situation, on the basis of the previous research and aiming at the special requirements of lithium carbonate, lithium sulfate and a bipolar membrane method for preparing lithium hydroxide, a series of experimental researches and developments are carried out, and finally a preparation process and a device for preparing lithium hydroxide by using lithium carbonate as a raw material and adopting dilute sulfuric acid as an internal circulation carrier substance are developed, and a three-compartment bipolar membrane device with high rejection rate for lithium and bipolar membrane+positive membrane+negative membrane is developed.
Disclosure of Invention
The invention mainly aims to develop a bipolar membrane device for preparing lithium hydroxide by taking lithium carbonate as a raw material and adopting a bipolar membrane method. The invention also aims to provide an operating parameter for preparing lithium hydroxide by an economic and environment-friendly bipolar membrane method.
The invention is realized by the following technical scheme:
a bipolar membrane device suitable for preparing lithium hydroxide from lithium carbonate, comprising: an anolyte inlet, a cathode binding post, an anolyte outlet and a catholyte outlet; the lithium ion battery is characterized in that a polar liquid runner plate is arranged close to the inner side of the clamping plate, a platinum tantalum iridium electrode is arranged on the inner side of the polar liquid runner plate, bipolar membranes with the lithium rejection rate of more than 98% are sequentially arranged inwards from the platinum tantalum iridium electrode, and an alkali-resistant anode membrane and an acid-resistant cathode membrane are a group of membrane groups;
an anolyte inlet and an anolyte outlet, and a catholyte inlet and a catholyte outlet are respectively arranged on the anolyte channel plate;
the feed liquid inlet and the lithium hydroxide outlet, and the concentrated acid inlet and the concentrated acid outlet are respectively arranged on the two clamping plates and are communicated with the outside.
The alkali-resistant positive film is CMB positive film produced by ASTOM company.
The acid-resistant negative film is an AHA negative film produced by ASTOM company.
The clamping plate is clamped by the fastening bolt.
The clamping plate is respectively connected with an anode binding post and a cathode binding post.
Preferably, a plurality of groups of membrane groups are arranged between the polar liquid flow passage plates in the bipolar membrane device for preparing lithium hydroxide, so that energy consumption and material cost can be saved.
Preferably, the bipolar membrane device for preparing lithium hydroxide has a thickness of 0.1-0.35 mm for a bipolar membrane with a lithium rejection rate of more than 98%. The thickness of bipolar membranes is one of the main factors affecting energy consumption and rejection rate.
Preferably, in the bipolar membrane device for preparing lithium hydroxide, the bipolar membrane with the lithium rejection rate of more than 98% controls the membrane resistance to be 5-8 omega/cm < 2 >, the crosslinking degree to be 70-90% and the membrane thickness to be 0.15-0.25mm so as to improve the energy consumption and rejection rate of the device.
Preferably, the bipolar membrane with a lithium retention rate of more than 98% according to the present invention is prepared by the following method. The raw materials comprise: polyethylene, polybutadiene and graphene with the thickness of 0.1-0.15 mm;
the preparation process comprises the following steps:
(A) Preparation of base film raw material
Polyethylene, polybutadiene and graphene are mixed according to the mass ratio of 100:5-50:1-10, preparing materials;
(B) Preparation of a base film
Preparing a basement membrane by doping graphene into polyethylene and polybutadiene;
(C) Preparation of bipolar membranes
Carboxylating a positive surface layer of a bottom film by glacial acetic acid by adopting an impregnation method, chloroethylating a negative surface of the bottom film by adopting chlorodiethyl ether, and then quaternizing by using m-phenylenediamine to obtain a bipolar film with the lithium rejection rate of more than 98%; the indexes of the bipolar membrane with the lithium rejection rate being more than 98 percent comprise: the retention rate of lithium is more than 98%, the membrane resistance is controlled to be 5-8 omega/cm < 2 >, the crosslinking degree is 70-90%, and the membrane thickness is 0.15-0.25mm. The bipolar membrane of the invention greatly improves the current efficiency of preparing lithium hydroxide by a bipolar membrane method, and the concentration and purity of lithium hydroxide. And the power consumption is low, the speed is high, and the use area of the film is reduced by more than 40 percent
Preferably, the concentrated solution in the bipolar membrane device enters a salt chamber of the bipolar membrane when the mass concentration reaches 10-15%, and enters an acid chamber of the bipolar membrane when the mass concentration of the dilute solution reaches 0.05-0.5%; the alkali chamber takes pure water as water inlet, and bipolar membrane is carried out to prepare lithium hydroxide; the polar liquid of the bipolar membrane device adopts sulfuric acid with the mass concentration of 0.5 percent and lithium sulfate with the mass concentration of 2.0 percent; the catholyte and the anolyte are respectively and independently circulated, and the flow is 1.0-3.0m 3 /h; the flow rates of the salt chamber, the acid chamber and the alkali chamber are 3-12m 3 And/h, the operating pressure is 0.02-0.08MPa, and the operating temperature is 25-38 ℃. The operating voltage is 50-500V and the operating current is 100-300A.
Preferably, a pretreatment component communicated with the bipolar membrane device for preparing lithium hydroxide can be further arranged in the bipolar membrane device, a connection outlet of dilute sulfuric acid prepared by the bipolar membrane device is arranged in the pretreatment component, the dilute sulfuric acid is communicated with the pretreatment component through the connection outlet, and feed liquid in the pretreatment component is dissolved to the concentration of 1.0-10% of lithium sulfate and then filtered by a microfiltration membrane with the concentration of 0.45 micrometers; the pH value of the filtrate is regulated to 9-10 by lithium hydroxide prepared by the device, the filtrate is filtered by a microfiltration membrane with the aperture of 0.01-0.1 micron, and the pH value of the filtrate is regulated to 3-6 by dilute sulfuric acid. The 0.45 micron microfiltration membrane is a common model of microfiltration membrane.
The bipolar membrane device can also form a production system for preparing lithium hydroxide by taking lithium carbonate as a raw material together with a pretreatment component, an electrodialysis concentration component, a bipolar membrane component and a single multivalent acid separation electrodialysis component. Wherein the bipolar membrane of the bipolar membrane component adopts a bipolar membrane with the lithium rejection rate of more than 98 percent; the membrane of the single multivalent acid separation electrodialysis unit adopts an acid-resistant single multivalent separation membrane. The membrane of the single multivalent acid separation electrodialysis component takes a conventional acid-resistant membrane as a base membrane, the surface of the membrane is activated by plasma, and then a naphthalene sulfonic acid coating with the thickness of 1-5 microns is coated on the surface of the membrane by an electrodeposition method, so that the acid-resistant single multivalent acid separation membrane is formed. The single multivalent acid separation electrodialysis unit belongs to the electrodialysis concentration step prior to the bipolar membrane device.
The bipolar membrane device is suitable for preparing lithium hydroxide by taking industrial grade lithium carbonate (according to national standard) as a raw material, and comprises the following steps: the dilute sulfuric acid prepared by the bipolar membrane device itself is dissolved to a lithium sulfate concentration of 1.0-10% and filtered with a microfiltration membrane of 0.45 μm. The filtrate is prepared by self to adjust the pH value to 9-10 by lithium hydroxide, then is filtered by a microfiltration membrane with the pore diameter of 0.01-0.1 micron, and the pH value of the filtrate is adjusted to 3-6 by dilute sulfuric acid. Then, the filtrate and dilute salt solution from the bipolar membrane enter an electrodialysis concentration part together, the concentration of the concentrated solution reaches 10-15% and enters a salt chamber of the bipolar membrane, and the concentration of the dilute solution reaches 0.05-0.5% and enters an acid chamber of the bipolar membrane; in the bipolar membrane component, the alkali chamber takes pure water as water for preparing lithium hydroxide by using the bipolar membrane. The polar liquid of the bipolar membrane device adopts 0.5 percent sulfuric acid and 2.0 percent lithium sulfate; the catholyte and the anolyte are respectively and independently circulated, and the flow is 1.0-3.0m 3 /h; the flow rates of the salt chamber, the acid chamber and the alkali chamber are 3-12m 3 And/h, the operating pressure is 0.02-0.08MPa, and the operating temperature is 25-38 ℃. The running voltage is 50-500V, and the running current is 100-300A; and taking part of lithium hydroxide generated by the bipolar membrane component as alkali to enter the pretreatment component for pH adjustment, and the rest of lithium hydroxide is the lithium hydroxide product.
The diluted mixed acid from the bipolar membrane part enters a single multivalent acid separation electrodialysis part for separation, a small amount of separated monovalent mixed acid is discharged after neutralization, and the separated diluted sulfuric acid continuously dissolves the next batch of lithium carbonate until the process of preparing lithium hydroxide by using the bipolar membrane with the diluted sulfuric acid as a circulating carrier is finished.
Compared with bipolar membrane devices of other patents, the bipolar membrane device has the following advantages:
(1) Because the newly developed bipolar membrane with strong acid resistance and lithium rejection rate of more than 98% is adopted, the whole service life of the device is greatly prolonged to more than 3 years, the yield of lithium hydroxide is increased to more than 98% from the original 95-98%, and the conversion energy consumption of lithium hydroxide monohydrate per ton is reduced to less than 2000 ℃.
(2) Because dilute sulfuric acid is adopted as an internal circulation carrier substance, the whole production process has no dilute acid emission, the loss of lithium along with the dilute acid emission is avoided, the conductivity of the bipolar membrane salt chamber is greatly improved, and the current efficiency and the production capacity of the device are increased.
(3) The high-precision micro-filtration membrane added in the device greatly improves the pretreatment precision of the feed liquid, reduces the strength of resin hardening off and saves energy consumption.
(4) The electrodialysis process is carried out by separating mono-multivalent acid, so that the monovalent acid such as hydrochloric acid, hydrofluoric acid and nitric acid in the circulation process is separated from the dilute sulfuric acid as an internal circulation carrier substance, thereby avoiding the problem of accumulation of monovalent anions such as chloride ions, fluoride ions and nitrate ions in the material.
(5) The membrane group device with the membrane size of 550mm and 1100mm and the group number of 60-240 groups is adopted, so that the processing capacity of a single membrane group device is greatly improved, and the equipment investment cost is reduced.
Drawings
Fig. 1 is a schematic flow chart of the implementation of a bipolar membrane device for preparing lithium hydroxide.
Fig. 2 is a schematic view of a bipolar membrane assembly according to the present invention.
Fig. 3 is a schematic diagram of bipolar membrane components of a bipolar membrane device for preparing lithium hydroxide according to the present invention.
FIG. 4 shows a process route for preparing lithium hydroxide by using the device of the invention for preparing industrial grade lithium carbonate.
FIG. 5 is a schematic diagram of a process route for preparing lithium hydroxide by recycling lithium carbonate using the apparatus of the present invention.
Wherein: 1. the anode liquid inlet, 2, a bipolar membrane with the retention rate of lithium being more than 98%, 3, a strong alkali resistant anode membrane special for alkali resistance, 4, a strong acid resistant cathode membrane special for acid resistance, 5, a catholyte inlet, 6, a fastening bolt, 7, a feed liquid inlet, 8, a polar liquid runner plate, 9, an anode binding post, 10, a clamping plate, 11, a lithium hydroxide outlet, 12, a concentrated acid outlet, 13, a cathode binding post, 14, a concentrated acid inlet, 15, a platinum tantalum iridium electrode, 16, an anolyte outlet, 17 and a catholyte outlet.
Detailed Description
Example 1
According to the figures 1, 2 and 3, a bipolar membrane device for preparing lithium hydroxide is arranged, and comprises a pretreatment component, an electrodialysis concentration component, a bipolar membrane component and a single multivalent acid separation electrodialysis component. The anode liquid inlet 1, the cathode binding post 13, the anode liquid outlet 16 and the cathode liquid outlet 17 are arranged in the anode liquid tank; a polar liquid flow channel plate 8 is arranged near the inner side of the clamping plate 10, a platinum tantalum iridium electrode 15 is arranged at the inner side of the polar liquid flow channel plate 8, and a bipolar membrane 2 with a lithium rejection rate of more than 98%, a strong alkali resistant special anode membrane 3 and a strong acid resistant special cathode membrane 4 which are a group of membrane groups are sequentially arranged inwards from the platinum tantalum iridium electrode 15; an anolyte inlet 1 and an anolyte outlet 16, and a catholyte inlet 5 and a catholyte outlet 17 are respectively arranged on the two polar liquid runner plates 8; the feed liquid inlet 7 and the lithium hydroxide outlet 11, and the concentrated acid inlet 14 and the concentrated acid outlet 12 are respectively arranged on the two clamping plates 10 and are communicated with the outside; the clamping plate 10 is clamped by the fastening bolt 6; the clamping plate 10 is connected to the anode terminal 9 and the cathode terminal 13, respectively.
The bipolar membrane 2 with the lithium rejection rate of more than 98% of the bipolar membrane component in the bipolar membrane device is prepared by mixing polyethylene with polybutadiene with the thickness of 0.1 mm with a graphene base membrane, and the ratio of the polyethylene to the polybutadiene base membrane to the graphene base membrane is 100:20:5, preparing a bipolar membrane by using an impregnation method, carboxylating a positive surface layer by using glacial acetic acid, chloroethylating a negative surface layer by using chlorodiethyl ether to replace common chloromethyl ether, and quaternizing by using m-phenylenediamine to replace common trimethylamine to form the bipolar membrane 2 with the lithium rejection rate of more than 98%, wherein the membrane resistance is controlled to be 6 omega/cm < 2 >, the crosslinking degree is 80%, and the membrane thickness is 0.15mm. The bipolar membrane component is composed of the bipolar membrane of the invention with a size of 550 x 1100mm and the CMB Yang Mo of ASTOM and the AHA cathode membrane of ASTOM.
The membrane of the single multivalent acid separation electrodialysis component takes a conventional acid-resistant membrane as a base membrane, the surface is activated by plasma, and then a naphthalene sulfonic acid coating with the thickness of 3 micrometers is coated on the surface of the membrane by an electrodeposition method, so that the acid-resistant single multivalent acid separation membrane is formed.
Lithium carbonate is used as a raw material, diluted sulfuric acid prepared by the device is used for dissolving until the concentration of the lithium sulfate is 3%, and a microfiltration membrane of 0.45 micrometers is used for filtering. The filtrate was adjusted to pH 9.5 with self-prepared lithium hydroxide, filtered with a microfiltration membrane having a pore size of 0.05 μm, and the filtrate was adjusted to pH 4 with dilute sulfuric acid.
The filtrate and dilute salt solution from the bipolar membrane enter an electrodialysis concentration part, the concentration of the concentrated solution reaches 10 percent, then the concentrated solution enters a salt chamber of the bipolar membrane, and the concentration of the dilute solution is 0.2 percent, and then the concentrated solution enters an acid chamber of the bipolar membrane; in the bipolar membrane component, the alkali chamber takes pure water as water for preparing lithium hydroxide by using the bipolar membrane. The polar liquid of the bipolar membrane device adopts 0.5 percent sulfuric acid and 2.0 percent lithium sulfate; the catholyte and the anolyte are respectively and independently circulated, and the flow is 1.5m3/h; the flow rates of the salt chamber, the acid chamber and the alkali chamber are 3m3/h, the operating pressure is 0.04MPa, and the operating temperature is 30 ℃. The operating voltage is 200V and the operating current is 200A; and taking part of lithium hydroxide generated by the bipolar membrane component as alkali to enter the pretreatment component for pH adjustment, and the rest of lithium hydroxide products.
The diluted mixed acid from the bipolar membrane part enters a single multivalent acid separation electrodialysis part for separation, a small amount of separated monovalent mixed acid is discharged after neutralization, and the separated diluted sulfuric acid continuously dissolves the lithium carbonate of the next batch. The current treatment efficiency of the whole bipolar membrane device is as high as 85%, and the total energy consumption is 1800 DEG electricity/ton time lithium hydroxide monohydrate. The lithium loss rate is 0.3%, the concentration of the obtained lithium hydroxide reaches 10%, and the purity reaches 99.8%.
Example 2
According to the figures 1, 2 and 3, a bipolar membrane device for preparing lithium hydroxide is arranged, and has a similar structure as the embodiment, and comprises a pretreatment part, an electrodialysis concentration part, a bipolar membrane part and a single multivalent acid separation electrodialysis part. The bipolar membrane 2 with the lithium rejection rate of more than 98% of the bipolar membrane component in the bipolar membrane device is prepared by mixing polyethylene with polybutadiene with the thickness of 0.1 mm with a graphene base membrane, and the ratio of the polyethylene to the polybutadiene base membrane to the graphene base membrane is 100:30:8, preparing a bipolar membrane by using an impregnation method, carboxylating a positive surface layer by using glacial acetic acid, chloroethylating a negative surface layer by using chlorodiethyl ether to replace common chloromethyl ether, and quaternizing by using m-phenylenediamine to replace common trimethylamine to form the bipolar membrane 2 with the lithium rejection rate of more than 98%, wherein the membrane resistance is controlled to be 5 omega/cm < 2 >, the crosslinking degree is 75%, and the membrane thickness is 0.12mm. The bipolar membrane component is composed of the bipolar membrane of the invention with a size of 550 x 1100mm and the CMB Yang Mo of ASTOM and the AHA cathode membrane of ASTOM.
The membrane of the single multivalent acid separation electrodialysis component takes a conventional acid-resistant membrane as a base membrane, the surface is activated by plasma, and then a naphthalene sulfonic acid coating with the thickness of 2.5 micrometers is coated on the surface of the membrane by an electrodeposition method, so that the acid-resistant single multivalent acid separation membrane is formed.
Lithium carbonate is used as a raw material, diluted sulfuric acid prepared by the device is used for dissolving until the concentration of the lithium sulfate is 2%, and a microfiltration membrane of 0.45 micrometers is used for filtering. The filtrate was adjusted to pH 9.5 with self-prepared lithium hydroxide, filtered with a microfiltration membrane having a pore size of 0.05 μm, and the filtrate was adjusted to pH 4 with dilute sulfuric acid.
The filtrate and dilute salt solution from the bipolar membrane enter an electrodialysis concentration part, the concentration of the concentrated solution reaches 8 percent, the concentrated solution enters a salt chamber of the bipolar membrane, and the concentration of the dilute solution reaches 0.3 percent, and the concentrated solution enters an acid chamber of the bipolar membrane; in the bipolar membrane component, the alkali chamber takes pure water as water for preparing lithium hydroxide by using the bipolar membrane. The polar liquid of the bipolar membrane device adopts 0.5 percent sulfuric acid and 2.0 percent lithium sulfate; the catholyte and the anolyte are respectively and independently circulated, and the flow is 1.5m3/h; the flow rates of the salt chamber, the acid chamber and the alkali chamber are 4m3/h, the operating pressure is 0.05MPa, and the operating temperature is 30 ℃. The operating voltage is 180V and the operating current is 180A; and taking part of lithium hydroxide generated by the bipolar membrane component as alkali to enter the pretreatment component for pH adjustment, and the rest of lithium hydroxide products.
The diluted mixed acid from the bipolar membrane part enters a single multivalent acid separation electrodialysis part for separation, a small amount of separated monovalent mixed acid is discharged after neutralization, and the separated diluted sulfuric acid continuously dissolves the lithium carbonate of the next batch. The current treatment efficiency of the whole bipolar membrane device is up to 86%, and the total energy consumption is 1700 ℃ electricity/ton. The lithium loss rate is 0.2%, the concentration of the obtained lithium hydroxide reaches 8%, and the purity reaches 99.8%.
Example 3
According to the figures 1, 2 and 3, a bipolar membrane device for preparing lithium hydroxide is arranged, and has a similar structure as the embodiment, and comprises a pretreatment part, an electrodialysis concentration part, a bipolar membrane part and a single multivalent acid separation electrodialysis part. The bipolar membrane 2 with the lithium rejection rate of more than 98% of the bipolar membrane component in the bipolar membrane device is prepared by mixing polyethylene with polybutadiene with the thickness of 0.15mm with a graphene base membrane, and the ratio of the polyethylene to the polybutadiene base membrane to the graphene base membrane is 100:40:9, preparing a bipolar membrane by using an impregnation method, carboxylating a positive surface layer by using glacial acetic acid, chloroethylating a negative surface layer by using chlorodiethyl ether to replace common chloromethyl ether, and quaternizing by using m-phenylenediamine to replace common trimethylamine to form the bipolar membrane 2 with the lithium rejection rate of more than 98%, wherein the membrane resistance is controlled to be 6 omega/cm < 2 >, the crosslinking degree is 75%, and the membrane thickness is 0.15mm. The bipolar membrane component is composed of 60 parts of the bipolar membrane of the invention with 550 x 1100mm of CMB Yang Mo +ASTOM and AHA cathode membrane of ASTOM.
The membrane of the single multivalent acid separation electrodialysis component takes a conventional acid-resistant membrane as a base membrane, the surface is activated by plasma, and then a naphthalene sulfonic acid coating with the thickness of 3.5 micrometers is coated on the surface of the membrane by an electrodeposition method, so that the acid-resistant single multivalent acid separation membrane is formed.
Lithium carbonate is used as a raw material, diluted sulfuric acid prepared by the device is used for dissolving until the concentration of the lithium sulfate is 5%, and a microfiltration membrane of 0.45 micrometers is used for filtering. The filtrate is subjected to self-preparation of lithium hydroxide to adjust the pH value to 10, and then is filtered by a microfiltration membrane with the pore diameter of 0.05 micron, and the pH value of the filtrate is adjusted to 4 by dilute sulfuric acid.
The filtrate and dilute salt solution from the bipolar membrane enter an electrodialysis concentration part, the concentration of the concentrated solution reaches 10 percent, the concentrated solution enters a salt chamber of the bipolar membrane, and the concentration of the dilute solution reaches 0.2 percent, and the concentrated solution enters an acid chamber of the bipolar membrane; in the bipolar membrane component, the alkali chamber takes pure water as water for preparing lithium hydroxide by using the bipolar membrane. The polar liquid of the bipolar membrane device adopts 0.5 percent sulfuric acid and 2.0 percent lithium sulfate; the catholyte and the anolyte are respectively and independently circulated, and the flow is 1.5m3/h; the flow rates of the salt chamber, the acid chamber and the alkali chamber are 3m3/h, the operating pressure is 0.04MPa, and the operating temperature is 35 ℃. The operating voltage is 100V and the operating current is 200A; and taking part of lithium hydroxide generated by the bipolar membrane component as alkali to enter the pretreatment component for pH adjustment, and the rest of lithium hydroxide products.
The diluted mixed acid from the bipolar membrane part enters a single multivalent acid separation electrodialysis part for separation, a small amount of separated monovalent mixed acid is discharged after neutralization, and the separated diluted sulfuric acid continuously dissolves the lithium carbonate of the next batch. The current treatment efficiency of the whole bipolar membrane device is up to 88%, and the total energy consumption is 1900 ℃ electricity/ton time lithium hydroxide monohydrate. The lithium loss rate is 0.1%, the concentration of the obtained lithium hydroxide reaches 12%, and the purity reaches 99.9%.
The index of lithium carbonate used in the present invention is as follows: GB/T11075-2013, YS/T582-2013.
The product indexes of the lithium hydroxide produced by the invention are as follows: GB/T8766-2013, GB/T26008-2010.
Example 4
The bipolar membrane device is suitable for the following two technological routes for preparing lithium hydroxide from lithium carbonate.
The first is applicable to the technical route for preparing lithium hydroxide from industrial grade lithium carbonate.
As shown in fig. 4, the process route comprises the following steps:
A. adding dilute sulfuric acid with mass concentration of about 5% into industrial grade lithium carbonate, dissolving to generate lithium sulfate solution and carbon dioxide gas, and removing the carbon dioxide gas.
B. And D, concentrating the lithium sulfate solution obtained in the step A through electrodialysis to obtain lithium sulfate concentrate.
C. And B, the lithium sulfate concentrate obtained in the step B is subjected to a precision filter to obtain a refined lithium sulfate solution, and the precision filter has the function of removing impurities in the lithium sulfate concentrate.
The precision filter may be a plate filter or an ultrafiltration filter.
D. C, treating the refined lithium sulfate solution obtained in the step C through a bipolar membrane electrodialysis system to obtain dilute sulfuric acid with the mass concentration of about 5%, lithium sulfate with the mass concentration of 8% and lithium hydroxide with the mass concentration of 5%; the dilute sulfuric acid contains trace lithium sulfate impurities.
Concentrating and crystallizing lithium hydroxide with the mass concentration of 5% by using MVR, and then sequentially demagnetizing, washing, drying, crushing and grading packaging to finish the technical treatment of preparing lithium hydroxide from industrial-grade lithium carbonate.
And (3) returning the dilute sulfuric acid with the mass concentration of about 5% to the step A for recycling.
And (3) returning the lithium sulfate with the mass concentration of 8% to the step (B), and carrying out electrodialysis concentration to obtain lithium sulfate concentrate.
The second is suitable for the process route for preparing lithium hydroxide by recycling lithium carbonate.
As shown in fig. 5, the process route comprises the following steps:
a. the recovered lithium carbonate is washed with water and filtered, and then the filter cake is dissolved by adding dilute sulfuric acid. After dissolution, lithium sulfate solution and carbon dioxide gas are generated, and the carbon dioxide gas is removed.
b. And c, sequentially performing alkali washing, filtering, resin exchange, fine filtering and electrodialysis concentration on the lithium sulfate solution obtained in the step a to obtain lithium sulfate concentrate.
c. B, treating the lithium sulfate concentrate obtained in the step b through a bipolar membrane electrodialysis system to obtain dilute sulfuric acid, lithium sulfate and lithium hydroxide; the dilute sulfuric acid contains trace lithium sulfate impurities.
Concentrating and crystallizing lithium hydroxide by using MVR, and then sequentially carrying out degaussing, washing, drying, crushing and grading packaging to finish the process treatment of preparing lithium hydroxide by recycling lithium carbonate.
Claims (2)
1. The method for preparing the lithium hydroxide by taking the lithium carbonate as the raw material based on the bipolar membrane device is characterized by comprising the following steps of:
a. dissolving lithium carbonate serving as a raw material with dilute sulfuric acid prepared by a bipolar membrane device until the concentration of the lithium sulfate is 1.0-10%, filtering with a microfiltration membrane of 0.45 micrometers, and taking filtrate;
b. preparing lithium hydroxide by a bipolar membrane device, regulating the pH value in filtrate to 9-10, filtering by a microfiltration membrane with the aperture of 0.01-0.1 micron, and regulating the pH value of the filtrate to 3-6 by dilute sulfuric acid;
c. the filtrate enters an electrodialysis concentration part together with the dilute brine from the bipolar membrane deviceThe concentration of the concentrated solution reaches 10-15% and enters a salt chamber of the bipolar membrane device, and the concentration of the dilute solution reaches 0.05-0.5% and enters a bipolar membrane acid chamber; in the bipolar membrane device, the alkali chamber takes pure water as water for preparing lithium hydroxide by using a bipolar membrane, and the polar liquid of the bipolar membrane device adopts 0.5% sulfuric acid and 2.0% lithium sulfate; the catholyte and the anolyte are respectively and independently circulated, and the flow is 1.0-3.0m 3 /h; the flow rates of the salt chamber, the acid chamber and the alkali chamber are 3-12m 3 And/h, the operating pressure is 0.02-0.08MPa, the operating temperature is 25-38 ℃, the operating voltage of the bipolar membrane device is 50-500V, and the operating current is 100-300A; taking part of lithium hydroxide generated by the bipolar membrane device as alkali to enter a pretreatment component for pH adjustment, and the rest of lithium hydroxide products;
d. the diluted mixed acid from the bipolar membrane device in the step c enters a single multivalent acid separation electrodialysis component for separation, a small amount of separated monovalent mixed acid is discharged after neutralization, and the separated diluted sulfuric acid continuously dissolves the lithium carbonate of the next batch;
the bipolar membrane device comprises: an anolyte inlet (1), a cathode binding post (13), an anolyte outlet (16) and a catholyte outlet (17); a polar liquid runner plate (8) is arranged near the inner side of the clamping plate (10), a platinum tantalum iridium electrode (15) is arranged at the inner side of the polar liquid runner plate (8), bipolar membranes (2) with the lithium rejection rate of more than 98% are sequentially arranged inwards from the platinum tantalum iridium electrode (15), and the control membrane resistance of the bipolar membranes is 5-8 omega/cm 2 The crosslinking degree is 70-90%, the film thickness is 0.15-0.25mm, the alkali-resistant positive film and the acid-resistant negative film are a group of film groups, and a plurality of groups of film groups are arranged between the polar liquid runner plates (8);
an anode liquid inlet (1) and an anode liquid outlet (16), a cathode liquid inlet (5) and a cathode liquid outlet (17) are respectively arranged on the anode liquid channel plate (8); the feed liquid inlet (7) and the lithium hydroxide outlet (11), and the concentrated acid inlet (14) and the concentrated acid outlet (12) are respectively arranged on the two clamping plates (10) and are communicated with the outside; the clamping plate (10) is respectively connected with an anode binding post (9) and a cathode binding post (13);
the bipolar membrane (2) is prepared by the following method, and the raw materials comprise: polyethylene, polybutadiene, graphene; the preparation process comprises the following steps:
x1. preparation of base film raw material
Polyethylene, polybutadiene and graphene are mixed according to the mass ratio of 100:5-50:1-10, preparing materials;
x2. preparation of a base film
Preparing a basement membrane by doping graphene into polyethylene and polybutadiene;
x3. preparation of bipolar membranes
Carboxylation is carried out on the positive surface layer of the bottom film by glacial acetic acid by adopting an impregnation method, chloroethylation is carried out on the negative surface of the bottom film by adopting chloroethyl ether, and then quaternization is carried out by using m-phenylenediamine, so that the bipolar film (2) is obtained.
2. The method for preparing lithium hydroxide by using lithium carbonate as a raw material based on a bipolar membrane device according to claim 1, wherein the method comprises the following steps: the clamping plate (10) is clamped by the fastening bolt (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810852555.7A CN110004457B (en) | 2018-07-30 | 2018-07-30 | Bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810852555.7A CN110004457B (en) | 2018-07-30 | 2018-07-30 | Bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110004457A CN110004457A (en) | 2019-07-12 |
| CN110004457B true CN110004457B (en) | 2023-12-29 |
Family
ID=67164764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810852555.7A Active CN110004457B (en) | 2018-07-30 | 2018-07-30 | Bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110004457B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146574A (en) * | 2021-11-26 | 2022-03-08 | 中南大学 | Modified Nb2CTxNano-sheet film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-07-30 CN CN201810852555.7A patent/CN110004457B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110004457A (en) | 2019-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101711854B1 (en) | Method for manufacturing lithium hydroxide and lithium carbonate | |
| KR101700684B1 (en) | Method and apparatus for manufacturing lithium hydroxide, and lithium carbonate | |
| Xu | Development of bipolar membrane-based processes | |
| CN110065958B (en) | Method for preparing lithium hydroxide by treating salt lake brine through integrated selective electrodialysis and selective bipolar membrane electrodialysis | |
| CN110002476B (en) | Preparation method of lithium hydroxide | |
| CN108997141B (en) | Preparation method of 1, 5-pentanediamine | |
| CN106629786B (en) | A kind of highly selective salt lake bittern puies forward lithium method | |
| CN109231623A (en) | A kind of new process of high salt high rigidity waste water reclaiming recycling soda acid | |
| CN106365183A (en) | Recovery method of electrode discharge solution in high-magnesium solution electrodialysis lithium extraction process | |
| CN103388198A (en) | Method for preparing acid base from waste liquid of viscose sodium sulphate by bipolar membrane electrodialysis method | |
| CN110451707A (en) | A kind of waste water of mine Zero discharge treatment method | |
| CN103341320A (en) | Novel process for recycling acid and base from viscose sodium sulfate waste liquid by using a bipolar membrane electrodialysis method | |
| CN105622435B (en) | Bipolar membrane device for preparing amino-1-propanol | |
| CN208667866U (en) | A kind of bipolar membrane device suitable for preparing lithium hydroxide using lithium carbonate as raw material | |
| CN110004457B (en) | Bipolar membrane device suitable for preparing lithium hydroxide by taking lithium carbonate as raw material | |
| CN109134317B (en) | Method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis | |
| CN103341321A (en) | Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method | |
| CN111607802A (en) | Method for preparing acid and alkali from by-product sodium sulfate | |
| CN107602394A (en) | Method for preparing N, N, N-trimethyl-1-adamantyl ammonium hydroxide by bipolar membrane electrodialysis | |
| CN113694733A (en) | Lithium separation method based on bipolar membrane electrodialysis device | |
| CN102839383B (en) | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane | |
| CN113830740B (en) | Method for preparing acid and alkali by bipolar membrane based on electrodialysis technology | |
| WO2023168896A1 (en) | Bipolar membrane system for efficiently removing magnesium ions in salt lake brine by means of in-situ alkali production | |
| CN109136971A (en) | A kind of technique of electroosmose process production lithium hydroxide | |
| CN103343403B (en) | Viscose sodium sulfate waste liquor acid and alkali recycling technology by virtue of bipolar membrane electrodialysis method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |