CN106276988B - A kind of method that battery-level lithium carbonate is prepared using potassium carbonate as precipitating reagent - Google Patents
A kind of method that battery-level lithium carbonate is prepared using potassium carbonate as precipitating reagent Download PDFInfo
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 title claims abstract description 72
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910000027 potassium carbonate Inorganic materials 0.000 title claims abstract description 36
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 title claims abstract description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 229910052744 lithium Inorganic materials 0.000 claims description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 11
- 241001131796 Botaurus stellaris Species 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 230000029087 digestion Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 2
- 230000005611 electricity Effects 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract description 6
- 238000002604 ultrasonography Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000012452 mother liquor Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000001103 potassium chloride Substances 0.000 abstract description 2
- 235000011164 potassium chloride Nutrition 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 235000017550 sodium carbonate Nutrition 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000012267 brine Substances 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000007630 basic procedure Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 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 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 241000219780 Pueraria Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- XIXYJCCQFKSBHG-UHFFFAOYSA-L lithium sodium hydrogen carbonate Chemical compound C([O-])([O-])=O.[Na+].C(O)(O)=O.[Li+] XIXYJCCQFKSBHG-UHFFFAOYSA-L 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
A kind of method that battery-level lithium carbonate is prepared using potassium carbonate as precipitating reagent, is related to chemical technology field, there is following steps completion, Alkali liquid compounding → removal of impurities → ion exchange → evaporation and concentration → reaction aging → filtration washing → drying → finished product；The beneficial effects of the present invention are：The present invention is reacted using potassium carbonate as precipitating reagent with lithium chloride prepares lithium carbonate, and the mother liquor finally obtained the Klorvess Liquid higher for purity, the mother liquor can be directly used for production potassium chloride or potassium carbonate, and no waste generates；Solves the problems, such as viscous wall more serious in reaction process with reaction temperature cooperation using crystal seed is added in；Using the problem of crystal seed, reaction temperature, mixing speed, combination of ultrasound avoid lithium carbonate crystal accumulation, size distribution is wide.
Description
First, technical field
The present invention relates to chemical technology fields, and battery-level lithium carbonate is prepared by precipitating reagent of potassium carbonate more particularly to one kind
Method.
2nd, background technology
Lithium carbonate is most basic lithium salts in lithium compound, is the primary raw material for preparing other lithium compounds and lithium alloy.
In recent years, as lithium carbonate is in the high-technology fields such as new energy and new material, especially electric vehicle field is shown up prominently, table
Reveal tempting application prospect.
China possesses abundant saline lake lithium resource.Salt has been gradually formed under the joint efforts of scientific worker and business circles
The complete lithium industrial chain that lake lithium resource exploitation, lithium battery material production, lithium battery manufacture, pure electric automobile are assembled into one.
In recent years, Qinghai Salt Lake Industry Co., Ltd., Qinghai CITIC Guoan Science and Technology Development Co., Ltd. and Qinghai lithium industry are limited
The salt lakes enterprise such as company is respectively adopted absorption method, calcination method and ion selection transfer method and realizes that salt lake brine with high magnesium-lithium ratio puies forward lithium skill
Art industrializes, using the lithium chloride solution and sodium carbonate extracted（Soda ash）Reaction precipitation（Crystallization）Produce lithium carbonate.
Current battery level lithium carbonate preparation method mainly has sulfuric acid process, carbonizatin method and electroosmose process etc..
Sulfuric acid process is mainly used for extracting lithium from the lithium ores such as spodumene, lepidolite, and basic procedure is as follows:First by lithium essence
Ore deposit carries out transition roasting, acidizing fired, then is converted into lithium sulfate solution with sulfuric acid to leach, through further detaching metal impurities ion
Afterwards, it adds in sodium carbonate to be precipitated, battery-level lithium carbonate is made（Xu Longquan, Zeng Zuliang, Liang Hu, Tu Mingjiang, meter Mao Long, sulfuric acid
Method produces battery-level lithium carbonate, CN1267636；Yang Chunhui, Wang Yunxu, Zhao Jiang, Zhang Xiaohong, Li Chaohong, a kind of LITHIUM BATTERY carbonic acid
The clean method for producing of lithium, CN103086405A；Yao Kailin, Jinpeng, Huo Liming, Huang Chunlian, Tu Mingjiang, Liangping is military, Zhang Ping
Member, Zhao Wei, the method CN101125668 of producing low-magnesium battery-stage lithium carbonate from lithium sulfate solution）, there are high-quality lithium essences for sulfuric acid process
Ore deposit relies on the problems such as import, production process high energy consumption, difficult, seriously polluted tailing and waste water.Since nineteen ninety-six, salt lake
Brine carries lithium gradually becomes the leading of global lithium industry, 80% is at present from salt lake bittern in the lithium carbonate product of worldwide production
Extraction.
The raw materials used lithium carbonate containing certain impurity for being mainly derived from the production of salt lake enterprise of carbonizatin method, basic procedure is such as
Under：Lithium carbonate and water are configured to suspension first, then pass to carbon dioxide by the lithium carbonate of indissoluble be converted into solubility compared with
Big lithium bicarbonate, the methods of being filtered to remove indissoluble impurity, then passing through ion exchange, removes soluble impurity, then passes through heat point
Battery-level lithium carbonate is made in solution reaction or addition Lithium hydroxide（Peng Qiuhua, Dai Yang, Xu Zhongji, depth carbonizatin method processing carbon
Hydrochlorate type lithium concentrate produces battery-level lithium carbonate technique, CN102502720A；Su Kang, Du Hongwen, eastwards, a kind of production LITHIUM BATTERY
The industrial method of lithium carbonate or pure Lithium Carbonate, CN102583453A；Tan Xiumin, Zhang Lizhen, Zhang Xiufeng, Li Qi, Zhao Hengqin,
The method that battery-level lithium carbonate or pure Lithium Carbonate are prepared using industrial level lithium carbonate, CN103539169A；Li Weida, Yuan Ai
Force, Zhou Guiyue, Zhang Junmei, a kind of method from lithium concentrate production battery-level lithium carbonate, CN103708505A）, carbonizatin method can prolong
Long technological process increases equipment investment, increases considerably production cost, and also there is the problems such as engineering is difficult.
Electroosmose process is to detach Li+ and Mg2+ by electrodialysis with salt lake bittern to obtain lithium chloride, then precipitated with sodium carbonate
Lithium carbonate is obtained, basic procedure is as follows：Using salt lake bittern as raw material, using ion selectivity separator, under electric field action
The magnesium ion in raw brine, lithium ion are migrated, when raw brine is by selective seperation film, lithium, sodium
Waiting monovalent ions, the divalent ions such as magnesium, calcium are isolated, and the rich lithium brine of low Mg/Li ratio has been obtained after separation, to low magnesium by film
Lithium than rich lithium brine carry out depth except Ca2+, Mg2, K+, S042-+etc. impurity, and carry out the purification of auxiliary material soda ash solution, it is deep
Rich lithium brine tune acid after degree removal of impurities carries out three-effect evaporation and condensation after neutralizing, and the rich lithium brine after concentration carries out at a certain temperature
Add sodium carbonate sinker, then carry out press filtration, wash and starch, centrifuge washing, be finally dried and cool down up to LITHIUM BATTERY carbonic acid
Lithium finished product（Ma Peihua, Li Zengrong, Li Jian, Zhou Xiaojun, Liu Guowang, Zhao Ying, Tang Faman, Ma Jun, it is a kind of to be produced using salt lake bittern
The method that LITHIUM BATTERY carbonic acid buries, CN102976367；Ma Peihua, Guo Yongnan directly produce battery from salt lake brine with high magnesium-lithium ratio
The method of level lithium carbonate, CN105540619A）, electroosmose process technological process is long, the water consumption and power consumption of multistage electrodialysis
Higher, production cost is excessively high.
Also document report prepares battery-level lithium carbonate using lithium chloride as raw material, with the sodium carbonate precipitation method（Li Liangbin, it is recklessly resistance to
Root, yellow-study is military, Pueraria lobota button Wei, Zhu Shigui, Xiong Xunman, Ma Zhenqian, a kind of side that battery-level lithium carbonate is prepared using lithium chloride solution
Method, CN101609888；Ma Jin, Ma Aijun, Xu Zhongji, He Guocai, Yi Chao, Lu Xingwu, Cheng Liang, Li Yuliang, Ji Wuren, tribute are big
Thunder, Shao Chuanbing, Li Shourong, Zhang Enyu, Li Yu, Xue Yingying, a kind of preparation process of battery-level lithium carbonate, CN103351010A）,
The method shortcoming is very high to material purity requirement, can not be handled containing miscellaneous lithium carbonate raw material.
In short, in terms of battery-level lithium carbonate preparation, more than patent uses sodium carbonate（Soda ash）As precipitating reagent.But
Be, using sodium carbonate as precipitating reagent there are size distribution it is wide the problems such as（See Fig. 1）, the quality requirement with battery-level lithium carbonate
Often there is a certain distance.In addition, production is produced in the mother liquor obtained after lithium carbonate by the use of sodium carbonate as precipitating reagent containing highly concentrated
The sodium chloride of degree, recovery value are little（Qinghai Salt Lake possesses abundant high-quality sodium chloride resource）, salt will be influenced by such as returning to salt lake
The element balance in lake is unfavorable for the sustainable development of salt lake enterprise.
3rd, invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides one kind LITHIUM BATTERY is prepared by precipitating reagent of potassium carbonate
The method of lithium carbonate, it is characterised in that：It has a following steps completion, and Alkali liquid compounding → removal of impurities → ion exchange → evaporation and concentration →
Reaction aging → filtration washing → drying → finished product；The processing step of Alkali liquid compounding process：It is 10~35% to prepare mass percent
Potassium hydroxide solution, compound concentration is the solution of potassium carbonate of 1~3mol/L, and potassium hydroxide in mass ratio：Potassium carbonate is
10~50：1 by two kinds of solution mixing for standby use；
The processing step for the process that cleans：Salt lake bittern is taken to be placed in reactor and add in potassium hydroxide and potassium carbonate mixing it is molten
The pH of salt lake bittern is adjusted to 10 ~ 14, and stir by liquid, 10 ~ 200 turns/min of mixing speed, reacts 0.5 ~ 3h, solution reaction temperature
Degree is maintained at 10~90 DEG C, and the magnesium ion in salt lake bittern reacts generation magnesium hydrate precipitate, calcium ion and carbon with potassium hydroxide
Sour nak response generates precipitation of calcium carbonate, is detached magnesium hydroxide and precipitation of calcium carbonate with lithium chloride by filtering, lithium chloride solution
It is spare；
The processing step of ion-exchange process：Spare lithium chloride solution is continued through and is filled with cation exchange resin
It is spare to obtain refined lithium chloride solution for ion exchange column；
It is concentrated by evaporation the processing step of process：Lithium chloride solution after will be refined is concentrated by evaporation, the concentration control of lithium ion
In 1.5 ~ 3.5mol/L, it is spare that lithium chloride solution is concentrated by evaporation cooling；
The processing step of reaction aging process：Lithium carbonate crystal seed is added in spare lithium chloride solution, lithium carbonate crystal seed adds
Enter amount to add 1.0~30g in every liter of lithium chloride solution, be then slowly added into the solution of potassium carbonate of a concentration of 1~3mol/L, carbonic acid
Potassium charging rate 1mL/min~200mL/min, at 10 DEG C~95 DEG C, speed of agitator is controlled in 100 turns/min for reaction temperature control
~ 1000 turns/min, Vltrasonic device, ultrasonic power 5W~2000W/L solution, supersonic frequency are opened while solution of potassium carbonate is added in
Rate 50kHZ~1MHZ, 0~2h of ultrasonic time；
After the completion of solution of potassium carbonate charging, the ageing of carbonic acid crystalline lithium, 0 ~ 2h of digestion time are carried out；Lithium carbonate suspension is old
It is spare after change；
The processing step of filter and cleaning process：The spare lithium carbonate suspension of above-mentioned ageing is used into Medium speed filter paper at room temperature
Filtering, the filter cake being obtained by filtration with 70 DEG C~90 DEG C deionized waters wash 3 times or more it is spare；
The processing step of drying process：Above-mentioned spare filter cake is dried in an oven, drying temperature is 50 DEG C~120
DEG C, drying time is 4h~16h, and battery-level lithium carbonate finished product is obtained after dry.The storage of battery-level lithium carbonate finished product should be noted that
It avoids direct sunlight, avoid storing under conditions of high humidity.
The beneficial effects of the present invention are：The present invention is reacted using potassium carbonate as precipitating reagent with lithium chloride prepares lithium carbonate,
The mother liquor finally obtained the Klorvess Liquid higher for purity, which can be directly used for production potassium chloride or potassium carbonate, without useless
Object generates；Solves the problems, such as viscous wall more serious in reaction process with reaction temperature cooperation using crystal seed is added in；Using crystal seed,
Reaction temperature, mixing speed, combination of ultrasound avoid that lithium carbonate crystal accumulation, size distribution are wide etc. to influence battery-level lithium carbonate production
The problem of quality.The lithium carbonate crystal morphology obtained under this condition is preferable, and product quality is stablized.
4th, Figure of description
Fig. 1 is to use particle size distribution figure of the sodium carbonate for the lithium carbonate of precipitating reagent（Without ultrasound）
Fig. 2 is to use particle size distribution figure of the potassium carbonate for the lithium carbonate of precipitating reagent（Without ultrasound）
Fig. 3 is to be schemed using carbonic acid crystalline lithium SEM prepared by conventional method（Without ultrasound）
Fig. 4 is to be schemed using carbonic acid crystalline lithium SEM prepared by this method（There is ultrasound）
5th, specific embodiment
Case 1
Take 1000mL lithium chloride solutions, wherein containing 2.16 mol of lithium ion/L, containing 0.09 mol of magnesium ion/L, calcic from
Son 0.012 mol/L, containing 0.076 mol of potassium ion, containing 0.26 mol of sodium ion/L, add in 30% potassium hydroxide solution by pH
Be adjusted to 12, control temperature 70 C, mixing speed 100 turns/min, reaction time 2h, obtain after filtering separation magnesium ion and calcium from
The lithium chloride solution of son.Lithium chloride solution is crossed equipped with D751 chelating ion exchange resins, the lithium chloride solution after absorption into
Row concentration, final lithium ion content are 3.01mol/L.LiCl solution 350mL is taken to be added in the reaction kettle of 1000mL, adds in carbon
Then sour lithium crystal seed 2g adds in 1.5mol/L solution of potassium carbonate, charging rate 10mL/min, 90 DEG C of reaction temperature, mixing speed
300 turns/min.Open Vltrasonic device, ultrasonic power 1000W solution, ultrasonic time 35min.After the completion of solution of potassium carbonate charging,
Carry out the ageing of carbonic acid crystalline lithium, digestion time 1h.Then lithium carbonate suspension is filtered, and with pure water 3 times.Most
Afterwards, it is dried at 70 DEG C.
Case 2
Take 1000mL lithium chloride solutions, wherein containing 2.16 mol of lithium ion/L, containing 0.09 mol of magnesium ion/L, calcic from
Son 0.012 mol/L, containing 0.076 mol of potassium ion, containing 0.26 mol of sodium ion/L, add in 30% potassium hydroxide solution by pH
11 are adjusted to, controls temperature 70 C, reaction time 2h, 200 turns/min of mixing speed obtain the chlorination of separation magnesium ion after filtering
Lithium solution.Lithium chloride solution is crossed equipped with D751 chelating ion exchange resins, and the lithium chloride solution after absorption is concentrated, most
Whole lithium ion content is 3.01mol/L.LiCl solution 350mL is taken to be added in the reaction kettle of 1000mL, adds in lithium carbonate crystal seed
2g, then add in 1.5mol/L solution of potassium carbonate, charging rate 10mL/min, 80 DEG C of reaction temperature, 400 turns of mixing speed/
min.Open Vltrasonic device, ultrasonic power 800W solution, ultrasonic time 35min.After the completion of solution of potassium carbonate charging, carbonic acid is carried out
The ageing of crystalline lithium, digestion time 1h.Then lithium carbonate suspension is filtered, and with pure water 3 times.Finally, 70
It is dried at DEG C.
Case 3
Take 1000mL lithium chloride solutions, wherein containing 2.16 mol of lithium ion/L, containing 0.09 mol of magnesium ion/L, calcic from
Son 0.012 mol/L, containing 0.076 mol of potassium ion, containing 0.26 mol of sodium ion/L, add in 30% potassium hydroxide solution by pH
11 are adjusted to, controls temperature 70 C, reaction time 2h, 200 turns/min of mixing speed obtain the chlorination of separation magnesium ion after filtering
Lithium solution.Lithium chloride solution is crossed equipped with D751 chelating ion exchange resins, and the lithium chloride solution after absorption is concentrated, most
Whole lithium ion content is 3.01mol/L.LiCl solution 350mL is taken to be added in the reaction kettle of 1000mL, adds in lithium carbonate crystal seed
3g, then add in 1.5mol/L solution of potassium carbonate, charging rate 20mL/min, 80 DEG C of reaction temperature, 400 turns of mixing speed/
min.Open Vltrasonic device, ultrasonic power 800W solution, ultrasonic time 25min.After the completion of solution of potassium carbonate charging, carbonic acid is carried out
The ageing of crystalline lithium, digestion time 2h.Then lithium carbonate suspension is filtered, and with pure water 3 times.Finally, 70
It is dried at DEG C.
Claim：
（1）Magnesium ion and calcium ion in lithium chloride solution are removed using potassium hydroxide and carbonic acid nak response precipitation, hydrogen-oxygen
The ratio for changing potassium and potassium carbonate is mass ratio 10 ~ 50：1.
（2）Potassium hydroxide solution is added in lithium chloride solution, pH is adjusted to 10 ~ 14,0.5 ~ 3h is reacted at 10 DEG C ~ 90 DEG C,
PH is adjusted to 11, controls temperature 70 C, reaction time 2h by 10 ~ 200 turns/min of mixing speed.
（3）It is controlled using potassium carbonate as the precipitating reagent of lithium chloride solution, concentration of potassium carbonate in 1mol/L ~ 3mol/L.
（4）Lithium carbonate crystal seed is added in lithium chloride solution, Seed charge is 1.0 ~ 30g/L lithium chloride solutions.
（5）Charging rate 1mL/min ~ 200mL/min of solution of potassium carbonate, reaction temperature are controlled at 10 DEG C ~ 95 DEG C, are stirred
Mix rotating speed is controlled in 100 turns/min ~ 1000 turn/min.
（6）Vltrasonic device, ultrasonic power 5W ~ 2000W/L solution, supersonic frequency are opened while solution of potassium carbonate is added in
50kHZ ~ 1MHZ, 0 ~ 2h of ultrasonic time.
（7）After the completion of solution of potassium carbonate charging, the ageing of carbonic acid crystalline lithium, 0 ~ 2h of digestion time are carried out.
Claims (1)
- A kind of 1. method that battery-level lithium carbonate is prepared using potassium carbonate as precipitating reagent, it is characterised in that：It has following steps completion, Alkali liquid compounding → removal of impurities → ion exchange → evaporation and concentration → reaction aging → filtration washing → drying → finished product；Alkali liquid compounding work The processing step of sequence：The potassium hydroxide solution that mass percent is 10~35% is prepared, compound concentration is the carbonic acid of 1~3mol/L Potassium solution, and potassium hydroxide in mass ratio：Potassium carbonate is 10 ~ 50：1 by two kinds of solution mixing for standby use；The processing step for the process that cleans：Salt lake bittern is taken to be placed in reactor and adds in potassium hydroxide and potassium carbonate mixed solution, The pH of salt lake bittern is adjusted to 10 ~ 14, and stir, 10 ~ 200 turns/min of mixing speed reacts 0.5 ~ 3h, and solution reaction temperature is protected It holds at 10~90 DEG C, the magnesium ion in salt lake bittern reacts generation magnesium hydrate precipitate, calcium ion and potassium carbonate with potassium hydroxide Reaction generation precipitation of calcium carbonate, is detached magnesium hydroxide and precipitation of calcium carbonate with lithium chloride by filtering, lithium chloride solution is spare；The processing step of ion-exchange process：Spare lithium chloride solution is continued through to the ion for being filled with cation exchange resin It is spare to obtain refined lithium chloride solution for exchange column；It is concentrated by evaporation the processing step of process：Lithium chloride solution after will be refined is concentrated by evaporation, and the concentration of lithium ion is controlled 1.5 ~ 3.5mol/L, it is spare that lithium chloride solution is concentrated by evaporation cooling；The processing step of reaction aging process：Lithium carbonate crystal seed, lithium carbonate Seed charge are added in spare lithium chloride solution To add 1.0~30g in every liter of lithium chloride solution, the solution of potassium carbonate of a concentration of 1~3mol/L is then slowly added into, potassium carbonate adds Expect speed 1mL/min~200mL/min, reaction temperature control at 10 DEG C~95 DEG C, speed of agitator control 100 turns/min ~ 1000 turns/min, Vltrasonic device, ultrasonic power 5W~2000W/L solution, supersonic frequency are opened while solution of potassium carbonate is added in Rate 50kHz~1MHz, ultrasonic time 25min~2h；After the completion of solution of potassium carbonate charging, the ageing of carbonic acid crystalline lithium, 1 ~ 2h of digestion time are carried out；After the ageing of lithium carbonate suspension It is spare；The processing step of filter and cleaning process：By the spare lithium carbonate suspension of above-mentioned ageing at room temperature with Medium speed filter paper mistake Filter, the filter cake being obtained by filtration with 70 DEG C~90 DEG C deionized waters wash 3 times or more it is spare；The processing step of drying process：Drying temperature is 50 DEG C~120 DEG C, and drying time is 4h~16h, and electricity is obtained after dry Pond level lithium carbonate finished product, the storage of battery-level lithium carbonate finished product is it should be noted that avoiding direct sunlight, avoiding storing under conditions of high humidity.
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| CN106882822A (en) * | 2017-03-15 | 2017-06-23 | 江苏容汇通用锂业股份有限公司 | A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor |
| CN107963643A (en) * | 2017-12-19 | 2018-04-27 | 唐朝辉 | A kind of method for preparing battery-level lithium carbonate |
| CN110817908A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | System and method for preparing high-purity lithium carbonate by using lithium-containing waste material |
| CN108840354B (en) * | 2018-08-16 | 2020-12-15 | 湖北上和化学有限公司 | Deep impurity removal method for battery-grade lithium chloride |
| US20220048783A1 (en) * | 2018-12-20 | 2022-02-17 | Lanxess Deutschland Gmbh | Production of High Purity Lithium Carbonate from Brines |
| CN110563009A (en) * | 2019-09-29 | 2019-12-13 | 华东理工大学 | Method for preparing battery-grade lithium carbonate from fly ash by carbonization decomposition method |
| CN113120924A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Recovery method of alkali activator for preparing activated carbon |
| CN112875731B (en) * | 2021-04-19 | 2023-12-08 | 青海盐湖工业股份有限公司 | Preparation method of lithium carbonate |
| CN113955776A (en) * | 2021-12-02 | 2022-01-21 | 江苏容汇通用锂业股份有限公司 | Preparation method of lithium carbonate |
| WO2023208742A1 (en) | 2022-04-29 | 2023-11-02 | Hte Gmbh The High Throughput Experimentation Company | Device and method for producing solid particles |
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| CN115448332B (en) * | 2022-11-11 | 2023-03-21 | 山东海化集团有限公司 | Method for preparing potassium carbonate by continuous ion exchange of fixed bed |
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| CN100528753C (en) * | 2007-01-30 | 2009-08-19 | 西部矿业集团有限公司 | Method for combined extracting boron, magnesium and lithium from salt lake bittern |
| CN101609888B (en) * | 2009-07-10 | 2011-06-22 | 江西赣锋锂业股份有限公司 | Method for preparing battery level lithium carbonate by using lithium chloride solution |
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Effective date of registration: 20231226 Address after: 338000 Jiangxi Dongpeng New Materials Co., Ltd., south of Sunshine Avenue and east of Quanzhou Avenue, High-tech Development Zone, Xinyu City, Jiangxi Province Patentee after: Jiangxi Chunpeng Lithium Industry Co.,Ltd. Address before: 1628 suzhao Road, Minhang District, Shanghai 201100 Patentee before: Shanghai Jiugui Information Technology Co.,Ltd. Effective date of registration: 20231226 Address after: 1628 suzhao Road, Minhang District, Shanghai 201100 Patentee after: Shanghai Jiugui Information Technology Co.,Ltd. Address before: 810016 No. 251 Ningda Road, Chengbei District, Xining City, Qinghai Province Patentee before: Qinghai University |