CN116143145A - Salt lake lithium extraction, boron removal and boric acid recovery device - Google Patents
Salt lake lithium extraction, boron removal and boric acid recovery device Download PDFInfo
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- CN116143145A CN116143145A CN202211596573.6A CN202211596573A CN116143145A CN 116143145 A CN116143145 A CN 116143145A CN 202211596573 A CN202211596573 A CN 202211596573A CN 116143145 A CN116143145 A CN 116143145A
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000004327 boric acid Substances 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- 238000000605 extraction Methods 0.000 title description 9
- 239000012528 membrane Substances 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 74
- 238000000909 electrodialysis Methods 0.000 claims abstract description 42
- 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 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 235000010724 Wisteria floribunda Nutrition 0.000 claims abstract description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 24
- 239000013505 freshwater Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005271 boronizing Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical class CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C25B1/14—Alkali metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the technical field of water treatment, and particularly discloses a device for extracting lithium from a salt lake, removing boron and recycling boric acid. The invention comprises a boron removal electrodialysis component, a flat plate reverse osmosis component, a high-pressure reverse osmosis component and a sodium removal bipolar membrane component, wherein each component is sequentially connected, the cathode and anode membranes of the boron removal electrodialysis component adopt a high-power concentration membrane type-12 membrane of Fuji Japan to improve drainage property, the flat plate reverse osmosis component adopts a plate frame structure, and the sodium removal bipolar membrane component adopts a conventional two-compartment sodium removal bipolar membrane device; the invention has the advantages of lithium recovery rate of more than 99.5 percent, low cost, and capability of recovering boron in the lithium recovery rate and forming byproducts in the form of high-purity boric acid crystals.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a device for extracting lithium, removing boron and recycling boric acid from a salt lake.
Background
Lithium is an important strategic resource substance, and is widely applied to the emerging fields of batteries, ceramics, glass, aluminum, lubricants, refrigerants, nuclear industry and the like, and is an important raw material indispensable for modern high-tech products. The development and production of lithium products directly affect the development of new industrial technologies to some extent, and the consumption of lithium products marks the development level of a national high-tech industry. In particular, the lithium battery industry has grown rapidly in recent years, with the market demand for lithium growing rapidly at a rate of 10% per year. The lithium resource reserves in China are rich and are mainly distributed in salt lakes of Qinghai and Tibet. The mineral resources (especially the salt lake resources) of the Qidamu basin on the Qinghai-Tibet plateau are very abundantly known as "cornucopia", the lithium reserves in the salt lake are about 2447.38 ten thousand tons (calculated by lithium chloride), accounting for 83% of the total lithium resources in China and accounting for 1/3 of the total lithium resources in the world. Because of the limitation of weak foundation of geographical environment and industry, the development of the lithium resource of the Tibetan salt lake is difficult, so the Qinghai salt lake is an important foundation for the lithium resource supply of China. The lithium mineral sites which are in charge of mineral reserves in the Qinghai salt lake resource are 10 in total, but are mainly distributed in 6 mining areas of the Nardostat salt lake Nardostat mining areas, nardostat salt lake, dongtai Ji salt lake, west Tai Ji salt lake and Yi Li salt lake. Wherein the Nalge salt lake and the Billen beach mining area are 2 oversized mineral deposits, and the West and east Geranial salt lake and the Yili mining area are 3 oversized mineral deposits.
The extraction of lithium from the salt lake refers to the extraction of lithium ore from the salt lake. Besides salt, the salt lake is rich in precious resources such as potassium, sodium, magnesium, lithium, boron and the like, and the lithium extraction technology of the salt lake is to extract potassium salt from salt lake brine to form lithium-containing brine, and the lithium carbonate, lithium chloride, lithium hydroxide and other products can be obtained after impurities are removed.
The principle of electrodialysis is a process in which ions migrate through a selective ion exchange membrane under the action of a direct current electric field, thereby partially separating electrolyte ions from a solution.
Electrodialysis technology is one of the membrane separation technologies that was developed earlier and achieved significant industrial success. Initial studies could be traced back to two centuries ago. Most historical reports began with the first observation by the french schner a. Noller of 1748 that water can naturally diffuse through the bladder membrane into an ethanol solution. This experiment found and confirmed the osmotic phenomenon of water through animal membranes. Dialysis was found by Graham in 1854. In 1863 Dubranfout, the first membrane dialyzer was made to successfully separate sugar from salts. In 1903 Morse and Pierce placed the two electrodes in solution inside and outside the dialysis bag, respectively, and found that charged impurities could be removed from the gel more rapidly. Pauli in 1924 adopts the principle of chemical design, improves the test device of Morse, and attempts to lighten polarization and increase mass transfer rate. Although they all employ non-permselective membranes, these pioneering efforts have produced a enlightening effect for the later development of utility electrodialysis. Meyer and Strauss in 1940 proposed the concept of a multi-compartment electrodialysis unit of practical interest. Particularly, after Juda and McRae in 1950 succeed in developing a cation exchange membrane and an anion exchange membrane with high selective permeability, a practical foundation of electrodialysis technology is laid.
The first electrodialysis device in the world was manufactured by Ionics company in the united states in 1952 for brackish water desalination, and then put into commercial production. Then, the bitter salty water is desalted by an electrodialysis device to prepare drinking water and industrial water, and the drinking water and industrial water are sequentially conveyed to other countries. The development of this technology was focused on the last 50 th century in japan, and the main research direction was in the concentration of seawater to produce salt. The successful research of monovalent ion selective permeation membranes with excellent performance and the exquisite process technology keep the Japanese in the advanced position in the aspect of electrodialysis sea water concentration salt production technology, and the annual production of salt is 160 ten thousand t. After 1970, japan also used electrodialysis for brackish water desalination. In 1974, a sea water desalination device for daily drinking water 120t was built in the wild island. In 1972, the Ionics company in the United states introduced a frequent reverse pole electrodialysis device, and the polarity of the electrode was changed once every 10-15min, so that the operation stability of the device was improved. In recent years, ionpuretechnology corporation of America has produced a continuous deionization electrodialysis apparatus in which ion exchange resins or ion exchange fibers are filled in an electrodialysis desalination compartment, and high purity water is directly and continuously produced without regenerating the resins.
The bipolar membrane is a novel ion exchange composite membrane, which is usually formed by compositing a cation exchange layer (N-type membrane), an interface hydrophilic layer (catalytic layer) and an anion exchange layer (P-type membrane), and is a reaction membrane in the real sense. Under the action of a direct current electric field, the bipolar membrane can dissociate water to obtain hydrogen ions and hydroxyl ions on two sides of the membrane respectively. By utilizing the characteristics, the bipolar membrane electrodialysis system formed by combining the bipolar membrane with other anion-cation exchange membranes can convert salts in aqueous solution into corresponding acids and bases without introducing new components, and the method is called a bipolar membrane electrodialysis method. The bipolar membrane electrodialysis method is not only used for preparing acid and alkali, but also can realize multiple functions and can be used in multiple fields if the bipolar membrane electrodialysis method is skillfully combined with a monopolar membrane.
At present, the boron-removing part of the lithium extracted from the salt lake adopts methods such as reverse osmosis, electrodialysis, resin and the like, and the methods have the defects of high cost, low lithium recovery rate, no recovery of boron resources and the like. Based on the technology of the former, the method has the advantages that the recovery rate of lithium is more than 99.5 percent, the cost is low, the boron in the method can be recovered, and byproducts are formed in the form of high-purity boric acid crystals.
Disclosure of Invention
The invention mainly aims to develop a device for extracting lithium, removing boron and recycling boric acid from a salt lake.
The invention is realized by the following technical scheme:
the device comprises a boron-removing electrodialysis component, a flat reverse osmosis component, a high-pressure reverse osmosis component and a sodium-removing bipolar membrane;
the cathode and anode membranes of the boron-removing electrodialysis component are modified by adopting a high-concentration membrane type-12 type membrane of Fuji Japan to improve drainage; the specific method of the transformation adopts a radiation grafting method to perform surface activation, then performs impregnation by impregnating styrene and methyl silicone oil, and performs introduction of silicon base at the temperature of 90-130 ℃, controls the introduction amount of silicon to be 0.1-0.5mmol/g, and then washes with water for 2-5 times. Soaking into 8% methanol solution for 1-5 hr, and processing. After treatment, the contact angle between water and the surface of the film is improved to 30-60 degrees;
the flat plate reverse osmosis component adopts a plate frame structure, and the acyl chloride of the acid-resistant reverse osmosis membrane adopts 1, 3-diacetyl chloride-5-methoxybenzene to represent trimesic acid chloride (TMC). The acid-resistant reverse osmosis membrane is formed by stacking acid-resistant reverse osmosis membrane and water distribution partition plates at intervals, and the sealing surface of the overlapped part is formed by hydraulically locking after being bonded by acid-resistant silica gel under the pressure of 15-30 MPa;
the sodium-removing bipolar membrane component adopts a conventional two-compartment sodium-removing bipolar membrane device, and an alkali-resistant positive membrane therein adopts an ED-C-C alkali-resistant special positive membrane wetted by Beijing;
the device for extracting lithium, removing boron and recycling boric acid from salt lake is characterized in that: the raw material is the regenerated liquid after eluting the lithium-extracted adsorbent in the salt lake: the lithium content is 100-500mg/L, the sodium ion content is 20-300mg/L, the boron content is 5-50mg/L, after 5-20 times of high-pressure reverse osmosis concentration, the solution enters the boron-containing lithium chloride solution inlet of the treatment device, enters the boron-removing electrodialysis component, and water enters the boron-removing electrodialysis component from the water inlet, so that the lithium concentration and boron removal processes are continuously carried out. After being treated by the boron-removing electrodialysis component, the concentrated water is discharged from a lithium chloride concentrated solution outlet, and the fresh water is discharged from a boron-containing lithium chloride dilute solution outlet and enters a flat plate reverse osmosis water inlet. After being treated by the flat plate reverse osmosis component, the generated concentrated water returns to the boron-containing lithium chloride solution inlet of the boron-removing electrodialysis component for recycling after coming out from the lithium chloride reverse osmosis concentrated water outlet; the fresh water generated by the flat plate reverse osmosis component enters a high-pressure reverse osmosis inlet of the high-pressure reverse osmosis component after exiting from a boron-containing reverse osmosis water outlet, and after being treated by the high-pressure reverse osmosis component, enters a water utilization system from a pure water outlet and enters a bipolar membrane alkaline chamber water inlet of the sodium removal bipolar membrane component partially; the produced concentrated water enters the bipolar membrane salt chamber inlet of the sodium removal bipolar membrane component after coming out of the sodium borate concentrated liquid outlet; after being treated by the sodium-removing bipolar membrane component, boric acid is produced from a boric acid outlet, and sodium hydroxide is produced from a sodium hydroxide outlet and returned to a pH adjusting point for recycling.
Preferably, the operation pressure of the flat plate reverse osmosis component of the salt lake lithium extraction, boron removal and boric acid recovery device is 2.0-6.0MPa, the water yield is controlled to be 50-90%, the concentrated water circulation ratio is controlled to be 0-60%, and the water temperature is controlled to be 15-40 ℃.
Preferably, the average operation power of each pair of membranes of the sodium removal bipolar membrane component of the salt lake lithium extraction and boron removal and boric acid recovery device is 1.0-1.5V, the linear flow rate is controlled to be 2-5cm/s, and the current density is controlled to be 500-1000A/m2. The direct current adopts unidirectional pulse, the duty ratio is 10-50%, and the frequency is 0.1-10Hz.
Preferably, the fresh water generated by the flat plate reverse osmosis component of the salt lake lithium extraction, boron removal and boric acid recovery device is discharged from a boron-containing reverse osmosis water outlet, the pH value is adjusted to 9-10 through a pH adjusting point, and then the fresh water enters the high-pressure reverse osmosis component.
Preferably, sodium hydroxide generated by a sodium removal bipolar membrane component of a salt lake lithium extraction and boron removal and boric acid recovery device is produced from a sodium hydroxide outlet and returned to a fresh water generated by a flat plate reverse osmosis component, and the produced fresh water is subjected to pH adjustment at a boron-containing reverse osmosis produced water outlet.
The beneficial effects are that: the device has the advantages of lithium recovery rate of more than 99.5 percent, low cost, and capability of recovering boron and forming byproducts in the form of high-purity boric acid crystals.
Drawings
FIG. 1 is a schematic flow chart of a process for extracting lithium from a salt lake and removing boron and recovering boric acid
FIG. 2 recovery device for extracting lithium, removing boron and boric acid from salt lake
A boronizing electrodialysis unit (1); a flat plate reverse osmosis member (2); a high pressure reverse osmosis component (3); a sodium-removing bipolar membrane (4); a water inlet (5); a boron-containing lithium chloride solution inlet (6); a lithium chloride concentrated solution outlet (7); a boron-containing lithium chloride dilute solution outlet (8); a flat plate reverse osmosis water inlet (9); a lithium chloride reverse osmosis concentrated water outlet (10); a boron-containing reverse osmosis produced water outlet (11); a high pressure reverse osmosis inlet (12); a pure water outlet (13); a sodium borate concentrate outlet (14); a bipolar membrane alkaline compartment water inlet (15); a bipolar membrane salt compartment inlet (16); a boric acid outlet (17); a sodium hydroxide outlet (18); a pH adjustment point (19);
Detailed Description
The invention is described in detail below with reference to the attached drawings:
example 1
The method comprises the steps of adopting a high-concentration film type-12 type negative and positive film of Fuji Japan as a raw material film, adopting an irradiation grafting method to perform surface activation, then performing impregnation by impregnating styrene and methyl silicone oil, introducing silicon base at the temperature of 100 ℃, controlling the introduction amount of silicon to be 0.2mmol/g, and then cleaning with water for 5 times. The mixture was further immersed in an 8% methanol solution for 5 hours, and the treatment was completed. The contact angle of water with the film surface is increased to 40 degrees after treatment. And then the modified membrane is used for assembling the boron-removing electrodialysis component 1.
The acid chloride of the acid-resistant reverse osmosis membrane adopts 1, 3-diacetyl chloride-5-methoxybenzene and m-phenylenediamine to produce the reverse osmosis membrane by adopting an interfacial polymerization method. The plate reverse osmosis component 2 is formed by overlapping acid-resistant reverse osmosis membranes and water distribution partition boards at intervals, and the sealing surface of the overlapped part is formed by hydraulically locking acid-resistant silica gel after being bonded with the pressure of 30 MPa.
The raw material is the regenerated liquid after eluting the lithium-extracted adsorbent in the salt lake: the lithium content is 200mg/L, the sodium ion content is 50mg/L, the boron content is 10mg/L, the solution enters the boron-containing lithium chloride solution inlet 6 of the treatment device of the invention to enter the boron-removing electrodialysis part 1 after being concentrated by 10 times by high-pressure reverse osmosis, and the water enters the boron-removing electrodialysis part 1 from the water inlet 5 to continue the lithium concentration and boron removal processes. After being treated by the boron-removing electrodialysis component 1, the concentrated water is discharged from a lithium chloride concentrated solution outlet 7, and the fresh water is discharged from a boron-containing lithium chloride dilute solution outlet 8 and enters a flat plate reverse osmosis water inlet 9. After being treated by the flat plate reverse osmosis component 2, the generated concentrated water is returned to the boron-containing lithium chloride solution inlet 6 of the boron-removing electrodialysis component 1 for recycling after coming out of the lithium chloride reverse osmosis concentrated water outlet 10. The fresh water generated by the parts of the flat plate reverse osmosis part 2 flows out from the boron-containing reverse osmosis water outlet 11, the pH value is adjusted to 9-10 through the pH value adjusting point 19, the fresh water enters the high-pressure reverse osmosis inlet 12 of the high-pressure reverse osmosis part 3, the fresh water after being treated by the high-pressure reverse osmosis part 3 enters the water utilization system from the pure water outlet 13 and part of the fresh water enters the bipolar membrane alkaline chamber water inlet 15 of the sodium-removing bipolar membrane part 4. The produced concentrated water passes out of the sodium borate concentrated liquid outlet 14 and enters the bipolar membrane salt chamber inlet 16 of the sodium removal bipolar membrane component 4. After being treated by the sodium removal bipolar membrane component 4, boric acid is produced from the boric acid outlet 17, and sodium hydroxide is produced from the sodium hydroxide outlet 18 and returned to the pH adjustment point 19 for recycling.
The operation pressure of the flat reverse osmosis part 2 was 4.0MPa, the recovery rate of produced water was controlled to 70%, the circulation rate of concentrated water was controlled to 50%, and the water temperature was controlled to 30 ℃.
The average operating power of each pair of membranes of the sodium removal bipolar membrane component 4 is 1.5V, the linear flow rate is controlled to be 2cm/s, and the current density is controlled to be 800A/m 2 . The direct current adopts unidirectional pulse, the duty ratio is 20%, and the frequency is 0.2Hz.
After the treatment process, the obtained lithium chloride is concentrated to 140g/L, the boric acid is concentrated to 120g/L, and the recovery rate of the lithium reaches 99.5 percent.
Example 2
The method comprises the steps of adopting a high-concentration film type-12 type negative and positive film of Fuji Japan as a raw material film, adopting an irradiation grafting method to perform surface activation, then performing impregnation by impregnating styrene and methyl silicone oil, introducing silicon base at the temperature of 120 ℃, controlling the introduction amount of silicon to be 0.5mmol/g, and then cleaning with water for 2 times. The treatment was completed by immersing in 8% methanol solution for another 4 hours. The contact angle of water with the film surface is increased to 50 degrees after treatment. And then the modified membrane is used for assembling the boron-removing electrodialysis component 1.
The raw material is the regenerated liquid after eluting the lithium-extracted adsorbent in the salt lake: the lithium content is 300mg/L, the sodium ion content is 150mg/L, the boron content is 30mg/L, the solution enters the boron-containing lithium chloride solution inlet 6 of the treatment device of the invention to enter the boron-removing electrodialysis part 1 after being concentrated by 10 times by high-pressure reverse osmosis, and the water enters the boron-removing electrodialysis part 1 from the water inlet 5 to continue the lithium concentration and boron removal processes. After being treated by the boron-removing electrodialysis component 1, the concentrated water is discharged from a lithium chloride concentrated solution outlet 7, and the fresh water is discharged from a boron-containing lithium chloride dilute solution outlet 8 and enters a flat plate reverse osmosis water inlet 9. After being treated by the flat plate reverse osmosis component 2, the generated concentrated water is returned to the boron-containing lithium chloride solution inlet 6 of the boron-removing electrodialysis component 1 for recycling after coming out of the lithium chloride reverse osmosis concentrated water outlet 10. The fresh water generated by the parts of the flat plate reverse osmosis part 2 flows out from the boron-containing reverse osmosis water outlet 11, the pH value is adjusted to 9-10 through the pH value adjusting point 19, the fresh water enters the high-pressure reverse osmosis inlet 12 of the high-pressure reverse osmosis part 3, the fresh water after being treated by the high-pressure reverse osmosis part 3 enters the water utilization system from the pure water outlet 13 and part of the fresh water enters the bipolar membrane alkaline chamber water inlet 15 of the sodium-removing bipolar membrane part 4. The produced concentrated water passes out of the sodium borate concentrated liquid outlet 14 and enters the bipolar membrane salt chamber inlet 16 of the sodium removal bipolar membrane component 4. After being treated by the sodium removal bipolar membrane component 4, boric acid is produced from the boric acid outlet 17, and sodium hydroxide is produced from the sodium hydroxide outlet 18 and returned to the pH adjustment point 19 for recycling.
The operation pressure of the flat reverse osmosis part 2 is 5.0MPa, the recovery rate of produced water is controlled to be 80%, the circulation rate of concentrated water is controlled to be 60%, and the water temperature is controlled to be 25 ℃.
The average operating power of each pair of membranes of the sodium removal bipolar membrane component 4 is 1.4V, the linear flow rate is controlled to be 3cm/s, and the current density is controlled to be 600A/m 2 . The direct current adopts unidirectional pulse, the duty ratio is 15%, and the frequency is 0.5Hz.
After the treatment process, the obtained lithium chloride is concentrated to 140g/L, the boric acid is concentrated to 100g/L, and the recovery rate of the lithium reaches 99.6 percent.
Claims (5)
1. The utility model provides a salt lake draws lithium to remove boron and boric acid recovery unit, includes that boron removal electrodialysis part (1), dull and stereotyped reverse osmosis part (2), high pressure reverse osmosis part (3), desorptive bipolar membrane part (4), its characterized in that:
the negative and positive membranes of the boron removal electrodialysis component (1) are modified by adopting a high-concentration membrane type-12 membrane of Fuji Japan, and the modification mode is as follows: performing surface activation by adopting an irradiation grafting method, soaking styrene and methyl silicone oil, introducing silicon base at the temperature of 90-130 ℃, controlling the introducing amount of silicon to be 0.1-0.5mmol/g, washing with water, soaking in 8% methanol solution for 1-5 hours, and finishing the treatment;
the flat plate reverse osmosis component (2) adopts a plate frame structure; the water distribution device is formed by stacking acid-resistant reverse osmosis membranes at intervals, and sealing surfaces of overlapped parts are formed by hydraulic locking after acid-resistant silica gel is bonded;
the sodium removal bipolar membrane component (4) adopts a two-compartment sodium removal bipolar membrane device, wherein an alkali-resistant positive membrane adopts an ED-C-C alkali-resistant special positive membrane wetted by Beijing;
the device is characterized in that a solution to be treated enters the boronizing electrodialysis component (1) from an inlet (6), and water enters the boronizing electrodialysis component (1) from an inlet (5); the concentrated water produced by the boron-removing electrodialysis component (1) is discharged from a lithium chloride concentrated solution outlet (7), and the fresh water is discharged from a boron-containing lithium chloride dilute solution outlet (8) and enters a flat plate reverse osmosis water inlet (9); the concentrated water generated by the flat plate reverse osmosis component (2) returns to the boron-containing lithium chloride solution inlet (6) of the boron-removing electrodialysis component (1) for recycling after coming out of the lithium chloride reverse osmosis concentrated water outlet (10); fresh water generated by the flat plate reverse osmosis component (2) flows out from the boron-containing reverse osmosis produced water outlet (11) and enters the high-pressure reverse osmosis inlet (12) of the high-pressure reverse osmosis component (3); fresh water generated by the high-pressure reverse osmosis component (3) enters a water utilization system from a pure water outlet (13) and partially enters a bipolar membrane alkaline chamber water inlet (15) of the sodium removal bipolar membrane component (4), and concentrated water generated by the high-pressure reverse osmosis component (3) enters a bipolar membrane salt chamber inlet (16) of the sodium removal bipolar membrane component (4) after exiting from a sodium borate concentrated solution outlet (14); boric acid generated by the sodium removal bipolar membrane component (4) is output from a boric acid outlet (17), and generated sodium hydroxide is output from a sodium hydroxide outlet (18).
2. The device for extracting lithium from salt lake, removing boron and boric acid according to claim 1, wherein the operation pressure of the flat plate reverse osmosis component (2) is 2.0-6.0MPa, the recovery rate of produced water is controlled to be 50-90%, the circulation rate of concentrated water is controlled to be 0-60%, and the water temperature is controlled to be 15-40 ℃.
3. The device for extracting lithium, removing boron and recycling boric acid from salt lakes according to claim 1, wherein the average running electricity of each pair of membranes of the sodium removing bipolar membrane component (4) is 1.0-1.5V, the linear flow rate is controlled to be 2-5cm/s, and the current density is controlled to be 500-1000A/m2; the direct current adopts unidirectional pulse, the duty ratio is 10-50%, and the frequency is 0.1-10Hz.
4. The device for extracting lithium, removing boron and recycling boric acid from salt lakes according to claim 1, wherein the fresh water generated by the flat plate reverse osmosis component (2) is discharged from the boron-containing reverse osmosis water outlet (11), is adjusted to pH 9-10 by a pH adjusting point (19), and then enters the high-pressure reverse osmosis component (3).
5. The device for extracting lithium from salt lake, removing boron and recycling boric acid according to claim 1, wherein sodium hydroxide generated by the sodium removing bipolar membrane component (4) is produced from a sodium hydroxide outlet (18) and returned to the flat plate reverse osmosis component (2), and the produced fresh water is subjected to pH adjustment at a boron-containing reverse osmosis water production outlet (11).
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| US20030187142A1 (en) * | 2002-03-26 | 2003-10-02 | Mark Hellums | Polymer grafted support polymers |
| CN207375760U (en) * | 2017-08-17 | 2018-05-18 | 江苏久吾高科技股份有限公司 | A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio |
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| US20030187142A1 (en) * | 2002-03-26 | 2003-10-02 | Mark Hellums | Polymer grafted support polymers |
| CN111226293A (en) * | 2017-04-12 | 2020-06-02 | 原子能股份公司 | Method for controlling and treating waste liquid of nuclear power station by using boron |
| CN207375760U (en) * | 2017-08-17 | 2018-05-18 | 江苏久吾高科技股份有限公司 | A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio |
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