CN107285345A - The system for preparing monohydrate lithium hydroxide - Google Patents
The system for preparing monohydrate lithium hydroxide Download PDFInfo
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- CN107285345A CN107285345A CN201710582949.0A CN201710582949A CN107285345A CN 107285345 A CN107285345 A CN 107285345A CN 201710582949 A CN201710582949 A CN 201710582949A CN 107285345 A CN107285345 A CN 107285345A
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- Prior art keywords
- lithium hydroxide
- entrance
- outlet
- lithium
- crude product
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- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 title claims abstract description 52
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 189
- 239000012043 crude product Substances 0.000 claims abstract description 48
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 39
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 31
- NKIZTEHKKBVIBS-UHFFFAOYSA-L [Li+].C([O-])([O-])=O.[Ca+2] Chemical compound [Li+].C([O-])([O-])=O.[Ca+2] NKIZTEHKKBVIBS-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 230000002000 scavenging effect Effects 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- 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 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 description 31
- 238000012545 processing Methods 0.000 description 17
- 239000011575 calcium Substances 0.000 description 13
- 229910052791 calcium Inorganic materials 0.000 description 12
- 229960004424 carbon dioxide Drugs 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 4
- 238000009993 causticizing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000008901 benefit Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- UMJRTMJPXLIFPH-UHFFFAOYSA-J [Li+].[OH-].[Ce+3].[OH-].[OH-].[OH-] Chemical compound [Li+].[OH-].[Ce+3].[OH-].[OH-].[OH-] UMJRTMJPXLIFPH-UHFFFAOYSA-J 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 battery industry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 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 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- C01D15/02—Oxides; Hydroxides
Abstract
The invention discloses the system for preparing monohydrate lithium hydroxide, including：Be carbonized knot screen, and it has lithium carbonate crude product entrance, water inlet, carbon dioxide entrance, EDTA entrances and the outlet of prepared calcium carbonate lithium；Causticization device, there is prepared calcium carbonate lithium entrance, milk of lime entrance and lithium hydroxide to complete liquid outlet for it；Ion interchange unit, there is lithium hydroxide to complete liquid entrance and the outlet of refined lithium hydroxide scavenging solution for it；Evaporated crystallization device, it has refined lithium hydroxide scavenging solution entrance and the wet crude product outlet of monohydrate lithium hydroxide, and the refined lithium hydroxide scavenging solution entrance is connected with the refined lithium hydroxide scavenging solution outlet；After-treatment device, it has the wet crude product entrance of monohydrate lithium hydroxide and monohydrate lithium hydroxide outlet, and the wet crude product entrance of monohydrate lithium hydroxide is connected with the outlet of the lithium hydroxide wet crude product.The system can prepare high-purity monohydrate lithium hydroxide using technical grade or secondary industrial level lithium carbonate crude product, and industrial flow is stable, and product quality is stably and controllable, high income.
Description
Technical field
The present invention relates to battery material field, specifically, the present invention relates to the system for preparing monohydrate lithium hydroxide.
Background technology
Lithium hydroxide is mainly used in terms of industrial chemicals, battery industry, chemicals, space flight, atomic energy.With new
Energy automobile industry Rapid Expansion, drives the fast development of battery industry and battery material industry.Tesla's system, new negative pole
The thriving demand of material of lithium titanate and nickelic ternary material to lithium hydroxide so that battery material market is to lithium hydroxide demand
In explosive growth.Requirement of the early stage lithium battery material to lithium hydroxide be mainly manifested in that physical appearance is uniform, chemical impurity is low,
Lot stability is good.But with the development of the electric industry of lithium, aspect of performance above-mentioned to lithium hydroxide product requires stricter, to height
The demand of pure cerium hydroxide lithium is more vigorous.
Lithium hydroxide is mainly purified by spodumene and prepared, and spodumene concentrate sulfuric acid leaching obtains lithium sulfate solution, then leads to
Freezeout sodium-deep impurity-removing-recrystallization process is subcooled and obtains lithium hydroxide product.The method is primarily present problems with：
(1) product purity is relatively low, and product impurity component fluctuation situation is big, and quality is difficult to control.Generally require repeatedly crystallization
Purifying can just obtain qualified battery-stage monohydrate lithium hydroxide product, want to obtain high-purity monohydrate lithium hydroxide product difficulty more
Greatly；
(2) freezing analysis sodium and multiple evaporation and crystal process can cause a large amount of losses of lithium, and lithium yield is low.
Therefore, the means for preparing high-purity monohydrate lithium hydroxide could be improved.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is the system that proposition prepares monohydrate lithium hydroxide.The system can be thick using technical grade or secondary industrial level lithium carbonate
Product effectively prepare high-purity monohydrate lithium hydroxide product, and industrial flow is stable, and product quality is stably and controllable, high income.
In one aspect of the invention, the present invention proposes a kind of system for preparing monohydrate lithium hydroxide.According to the present invention
Embodiment, the system includes：Be carbonized knot screen, and the carbonization knot screen has lithium carbonate crude product entrance, water inlet, two
Carbonoxide entrance, EDTA entrances and the outlet of prepared calcium carbonate lithium；Causticization device, the causticization device have prepared calcium carbonate lithium entrance,
Milk of lime entrance and lithium hydroxide complete liquid outlet, and the prepared calcium carbonate lithium entrance is connected with prepared calcium carbonate lithium outlet；From
There is sub- switch, the ion interchange unit lithium hydroxide to complete liquid entrance and the outlet of refined lithium hydroxide scavenging solution, institute
Lithium hydroxide completion liquid entrance is stated with the outlet of lithium hydroxide completion liquid to be connected；Evaporated crystallization device, the evaporative crystallization dress
Put with refined lithium hydroxide scavenging solution entrance and the wet crude product outlet of monohydrate lithium hydroxide, the refined lithium hydroxide scavenging solution enters
Mouth is connected with the refined lithium hydroxide scavenging solution outlet；After-treatment device, the after-treatment device has monohydrate lithium hydroxide
Wet crude product entrance and monohydrate lithium hydroxide outlet, the wet crude product entrance of monohydrate lithium hydroxide goes out with the wet crude product of the lithium hydroxide
Mouth is connected.
Thus, the system for preparing monohydrate lithium hydroxide according to embodiments of the present invention can use technical grade or secondary technical grade
Lithium carbonate crude product effectively prepares high-purity monohydrate lithium hydroxide product, and industrial flow is stable, product quality is stably and controllable,
High income.
In addition, the system according to the above embodiment of the present invention for preparing monohydrate lithium hydroxide can also have what is added as follows
Technical characteristic：
In some embodiments of the invention, the carbonization knot screen further comprises：Batch mixing unit, the batch mixing list
Member has lithium carbonate crude product entrance, water inlet and slurry outlet；Precipitation unit, the precipitation unit has slurry inlet, dioxy
Change carbon entrance, EDTA entrances and mixture export, the slurry inlet is connected with the slurry outlet；Filter element, the mistake
Filter unit has entry to mixed solution, sludge outlet and filtrate (liquid, and the entry to mixed solution is connected with the mixture export；Heat
Solve unit, the pyrolysis unit has filtrate inlet, carbon dioxide outlet and a refined lithium hydroxide, the filtrate inlet with it is described
Filtrate (liquid is connected.
In some embodiments of the invention, the carbonization knot screen is closed mechanic whirl-nett reaction kettle.
In some embodiments of the invention, the causticization device is the mechanic whirl-nett reaction kettle with heated for controlling temperature.
In some embodiments of the invention, the ion interchange unit is pillar ion exchange pot.
In some embodiments of the invention, the ion exchange resin used in the ion interchange unit include D401,
D732 or IRC747.
In some embodiments of the invention, the evaporated crystallization device is vacuum type crystallizer or mechanical agitation cooled
Crystallizer.
In some embodiments of the invention, the after-treatment device is rotary scrubber and vacuum drying chamber.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the system structure diagram according to an embodiment of the invention for preparing monohydrate lithium hydroxide；
Fig. 2 is the system structure diagram for preparing monohydrate lithium hydroxide according to further embodiment of the present invention.
Embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art
Offer described technology or condition or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument,
For can be by the conventional products of acquisition purchased in market.
In one aspect of the invention, the present invention proposes a kind of system for preparing monohydrate lithium hydroxide.According to the present invention
Embodiment, with reference to Fig. 1~2, the system includes：Be carbonized knot screen 100, causticization device 200, ion interchange unit 300, steaming
Send out crystallization apparatus 400 and after-treatment device 500.
It is described in detail below with reference to Fig. 1~2 pair system for preparing monohydrate lithium hydroxide according to embodiments of the present invention：
Embodiments in accordance with the present invention, carbonization knot screen 100 has lithium carbonate crude product entrance 101, water inlet 102, two
Carbonoxide entrance 103, EDTA entrances 104 and prepared calcium carbonate lithium outlet 105, carbonization knot screen 100 are suitable to lithium carbonate crude product
Carbonization removal of impurities processing is carried out, to remove the impurity such as soluble K, Na in lithium carbonate crude product, prepared calcium carbonate lithium is obtained.Inventor
Found in research process, simple mode of washing is only capable of removing the soluble impurity of lithium carbonate crude product adsorption, and big portion
The impurity such as point solubility K, Na are entrained in lithium carbonate intercrystalline, are difficult to remove by washing, so inventor's discovery by using
Be carbonized removal of impurities processing, can effectively remove the impurity such as most solubility K, Na in lithium carbonate crude product.
Embodiments in accordance with the present invention, carbonization knot screen can be closed mechanic whirl-nett reaction kettle.
Specifically, embodiments in accordance with the present invention, with reference to Fig. 2, carbonization knot screen further comprises：Batch mixing unit 110,
Precipitation unit 120, filter element 130 and pyrolysis unit 140.
There is embodiments in accordance with the present invention, batch mixing unit 110 lithium carbonate crude product entrance 101, water inlet 102 and slurry to go out
Mouth 111, batch mixing unit 110 is mixed suitable for lithium carbonate crude product with water, to obtain slurry.
The proportioning of embodiments in accordance with the present invention, lithium carbonate crude product and water is not particularly restricted, those skilled in the art
It can be selected according to actual needs, according to a particular embodiment of the invention, can be by lithium carbonate crude product and water according to quality
Than 1:(20~22) are mixed.Inventor has found, when lithium carbonate crude product quality is fixed, with the increase of rate of water added, although carbon
Sour lithium slurry and CO2The time of contact is longer, contact area increase, reacts more complete；But due to dissolving a certain amount of lithium carbonate
Water needed for crude product is fixed, and water exceedes reaction rate after certain limit and will not continue to increase, can conversely cause follow-up
The increase of lithia water pyrolytic process power consumption.
According to the specific embodiment of the present invention, slurry outlet 111 can pass through centrifugal pump and post precipitation unit 120
In slurry inlet 121 be connected, thus, it is possible to further improve material transfer efficiency.
There is embodiments in accordance with the present invention, precipitation unit 120 slurry inlet 121, carbon dioxide entrance 103, EDTA to enter
Mouth 104 and mixture export 122, slurry inlet 121 are connected with slurry outlet 111, and precipitation unit 120 is suitable to batch mixing unit
Carbon dioxide is passed through in the slurry obtained in 110, until the solid lithium carbonate in slurry all dissolves, to be mixed
Liquid.Specifically, by being passed through carbon dioxide into slurry, solid lithium carbonate can be converted into the form of lithium bicarbonate,
Li is entered liquid phase, realize the separation of the impurity such as Li and slightly solubility Ca, Mg.
According to a particular embodiment of the invention, carbon dioxide can be passed through into slurry under 20~30 degrees Celsius.
Inventor has found, in certain temperature range, and rise temperature is conducive to improving reaction rate, but due to Li2CO3And CO2Solubility
Reduce with the rise of temperature, rise temperature slows down reaction rate on the contrary.In addition, temperature is too high to also result in lithium carbonate crude product
In impurity Ca, Mg dissolve in the carbonized in liquid, with subsequent evaporation decomposable process again entrance purifying lithium carbonate, cause impurity
Being difficult to of Ca, Mg separates.
Embodiments in accordance with the present invention, filter element 130 has entry to mixed solution 131, sludge outlet 132 and filtrate (liquid
133, entry to mixed solution 131 is connected with mixture export 122, and filter element 130 is suitable to the mixing that will be obtained in precipitation unit 120
Liquid is mixed with EDTA, to precipitate the impurity such as slightly solubility Ca, Mg in mixed liquor using EDTA, and then uses churned mechanically side
Formula is filtered to remove slightly solubility impurity, and collects filtrate, so as to realize the separation of the impurity such as Li and slightly solubility Ca, Mg.
Embodiments in accordance with the present invention, mixed liquor and EDTA proportioning are not particularly restricted, and those skilled in the art can
To be selected according to actual needs, according to a particular embodiment of the invention, EDTA quality can be carbonic acid in step of sizing mixing
The 0.1~0.5% of lithium crude product quality.Inventor has found that EDTA addition has with impurity Ca, Mg contents in lithium carbonate crude product
Close, removal of impurity can be improved by suitably improving addition multiple, can then cause cost of supplementary product to increase and introduce impurity too much.
According to the specific embodiment of the present invention, it is preferred to use plate and frame filter press carries out above-mentioned filtering, thus, it is possible to enter
One step improves filter efficiency and the Li rate of recovery.
Embodiments in accordance with the present invention, pyrolysis unit 140 has filtrate inlet 141, carbon dioxide outlet 142 and refining carbon
Sour lithium outlet 105, filtrate inlet 141 is connected with filtrate (liquid 133, and pyrolysis unit 140 in filter element 130 suitable for will obtain
Filtrate carries out pyrolysis processing, to obtain prepared calcium carbonate lithium.Specifically, by pyrolysis processing, it can make to be dissolved in liquid phase
Lithium bicarbonate is decomposed into lithium carbonate and carbon dioxide, and then lithium carbonate is separated, you can obtain prepared calcium carbonate lithium.In addition, in heat
Reaction solution should persistently be stirred in solution processing procedure, to help other discharges of carbon dioxide, prevent reaction solution from emitting groove.
Embodiments in accordance with the present invention, the condition of pyrolysis processing is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, pyrolysis processing can be completed under 85~90 degrees Celsius.Hair
A person of good sense has found that heat decomposition temperature is too low, prepared calcium carbonate lithium low yield, and as temperature is raised, yield is gradually stepped up, this mainly by
In LiHCO3Decomposition be an absorbing reaction, Li in addition2CO3Solubility with temperature rise and reduce, temperature gets over Gao Yueyou
Beneficial to Li2CO3The increase of yield, but temperature is too high can cause the rise of impurity concentration in prepared calcium carbonate lithium, while temperature is more than 90
It DEG C can cause abnormal reaction acutely, release substantial amounts of CO2Gas, emits groove accident.
According to the specific embodiment of the present invention, prepared calcium carbonate lithium outlet 105 can pass through centrifuge and follow-up causticization
The prepared calcium carbonate lithium entrance 201 of device 200 is connected, thus, it is possible to the moisture in separation and purification lithium carbonate, so as to further remove
Soluble impurity in prepared calcium carbonate lithium.
Embodiments in accordance with the present invention, causticization device 200 has prepared calcium carbonate lithium entrance 201, milk of lime entrance 202 and hydrogen
Lithia completes liquid outlet 203, and prepared calcium carbonate lithium entrance 201 is connected with prepared calcium carbonate lithium outlet 105, and causticization device 200 is suitable to
Prepared calcium carbonate lithium is subjected to causticization processing, to obtain lithium hydroxide solution.Specifically, inventor has found, for causticization processing
The milk of lime preparation that should be added water using fresh quick lime obtain, it is possible thereby to significantly improve the activity of milk of lime, improve reactivity,
So as to further improve the Li rate of recovery.
Embodiments in accordance with the present invention, causticization device can be the mechanic whirl-nett reaction kettle with heated for controlling temperature.According to this hair
A bright specific embodiment, the lithium hydroxide slurry that can be obtained causticization processing by centrifuge and the carbonic acid being wherein mixed with
Calcium slag carries out solid-liquor separation, obtains lithium hydroxide and completes liquid.
Embodiments in accordance with the present invention, the condition of causticization processing is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, causticization processing can be completed under 90~95 degrees Celsius.Hair
A person of good sense has found that higher temperature is conducive to the progress of causticizing reaction, improves the conversion ratio of lithium carbonate, therefore, causticizing reaction is suitable
Carried out more than 90 DEG C, or even under the conditions of boiling.
According to a particular embodiment of the invention, causticization processing is to carry out 0.5~2h under conditions of pH value is 14~14.5
Complete.Inventor has found, by controlling reacting liquid pH value and reaction time to significantly improve the reactivity that causticization is handled, and
The content of Li in carbonic acid calcium impurities is reduced, so as to further improve the Li rate of recovery.
There is embodiments in accordance with the present invention, ion interchange unit 300 lithium hydroxide to complete liquid entrance 301 and refined hydrogen-oxygen
Change lithium scavenging solution outlet 302, lithium hydroxide completes liquid entrance 301 and is connected with lithium hydroxide completion liquid outlet 203, ion exchange dress
Put 300 to be suitable to lithium hydroxide is completed into liquid progress removal of impurities using cationic ion-exchange resin, to remove Ca, Mg in lithium hydroxide
Deng impurity, refined lithium hydroxide scavenging solution is obtained.
Embodiments in accordance with the present invention, ion interchange unit can be pillar ion exchange pot.
The species of the ion exchange resin used in embodiments in accordance with the present invention, ion interchange unit is not limited especially
System, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, cation exchange tree
Fat can include D401, D732 or IRC747.Thus, it is possible to further improve the clearance of the impurity such as Ca, Mg.After testing, obtain
To refined lithium hydroxide solution in impurity Ca, Mg content be not higher than 1mg/L.
Embodiments in accordance with the present invention, evaporated crystallization device 400 has refined lithium hydroxide scavenging solution entrance 401 and Dan Shui
The wet crude product outlet 402 of lithium hydroxide, refines lithium hydroxide scavenging solution entrance 401 and exports 302 phases with refined lithium hydroxide scavenging solution
Even, evaporated crystallization device 400 is suitable to refined lithium hydroxide solution being evaporated crystallization treatment, to obtain monohydrate lithium hydroxide
Wet crude product.
Embodiments in accordance with the present invention, evaporated crystallization device can be that vacuum type crystallizer or mechanical agitation cooled are crystallized
Device.
According to the specific embodiment of the present invention, after refined lithium hydroxide solution is evaporated into concentration, crystallization point
From being preferred to use centrifugal separator or the wet crude product of the isolated monohydrate lithium hydroxide of vacuum band-type filter machine.
Embodiments in accordance with the present invention, after-treatment device 500 has the wet crude product entrance 501 of monohydrate lithium hydroxide and single water hydrogen
Lithia outlet 502, the wet crude product entrance 501 of monohydrate lithium hydroxide is connected with lithium hydroxide wet crude product outlet 402, after-treatment device
500 suitable for the wet crude product of monohydrate lithium hydroxide is washed, drying and processing, to obtain monohydrate lithium hydroxide.
Embodiments in accordance with the present invention, after-treatment device can be rotary scrubber and vacuum drying chamber.
Embodiments in accordance with the present invention, the condition of drying and processing is not particularly restricted, and those skilled in the art can root
Selected according to being actually needed, according to a particular embodiment of the invention, drying and processing can 50~70 degrees Celsius temperature with
And completed under -0.09~-0.07MPa vacuum.Inventor has found, by being dried under -0.09~-0.07MPa vacuum
The dry wet crude product of monohydrate lithium hydroxide, can avoid the change of the crystallization water in monohydrate lithium hydroxide product, so as to further improve single
The quality of water lithium hydroxide product, drying temperature is too low and the too low meeting of vacuum make it that product residue water evaporation is excessively slow, conversely, then
The monohydrate lithium hydroxide product crystallization water can be caused to lose.
Thus, the system for preparing monohydrate lithium hydroxide according to embodiments of the present invention is by the way that lithium carbonate crude product is carbonized
Removal of impurities is handled, and obtains prepared calcium carbonate lithium, and then prepared calcium carbonate lithium is carried out into causticization processing, and will be severe using cationic ion-exchange resin
The lithium hydroxide solution that change processing is obtained carries out removal of impurities, refined lithium hydroxide solution is obtained, subsequently by refined lithium hydroxide solution
Crystallization treatment is evaporated, to obtain the wet crude product of monohydrate lithium hydroxide, then the wet crude product of monohydrate lithium hydroxide is washed, is dried
Dry-cure, obtains monohydrate lithium hydroxide product.The system, can be effective by using technical grade or secondary industrial level lithium carbonate crude product
Ground prepares high-purity monohydrate lithium hydroxide product, and industrial flow is stable, and product quality is stably and controllable, high income.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only description
Property, without limiting the present invention in any way.
Embodiment 1
Using carbonization knot screen, 200g technical pure lithium carbonate (main content 97wt%) is added in 2L pure water, stirred
Mix, be passed through carbon dioxide, until lithium carbonate all dissolves, stop ventilation.Thereto add 0.2g EDTA, stirring and dissolving,
It is filtrated to get clear liquid.Clear liquid is heated to 90 DEG C again, heated while stirring, it is seen that has white solid precipitation, is filtrated to get refined
Lithium carbonate, main content 99wt%.The prepared calcium carbonate lithium of preparation and freshly prepared calcium hydroxide are supplied to enter into causticization device
Row causticizing reaction, 95 DEG C of reaction temperature, reaction time 1h, through being filtrated to get lithium hydroxide solution after reaction.Lithium hydroxide is molten
Liquid is supplied into ion interchange unit, by being mounted with large aperture cationic ion-exchange resin D401 reaction tower, obtain impurity Ca,
Mg contents are less than 1mg/L refined lithium hydroxide solution.Refined lithium hydroxide solution is put into cold boiler, depressurized
It is concentrated by evaporation to a small amount of crystal when separating out and stops heating, is cooled to 40 DEG C, crystallization obtains monohydrate lithium hydroxide crude product.With a small amount of pure
Vacuum drying chamber drying is placed into after water washing monohydrate lithium hydroxide crude product and obtains high-purity monohydrate lithium hydroxide, product LiOH
H2O purity is not less than 98wt%, major impurity K, Na, Ca, Mg, CO3 2-、Cl-、SO4 2-Content be respectively 0.001wt%,
0.001wt%, 0.002wt%, 0.002wt%, 0.6wt%, 0.001wt%, 0.008wt%.Indices are superior to GB/T
Requirements of the 26008-2010 to impurity content.
Embodiment 2
Using carbonization knot screen, 200g technical pure lithium carbonate (main content 97wt%) is added in 4.4L pure water,
Stirring, is passed through carbon dioxide, until lithium carbonate all dissolves, stops ventilation.0.3g EDTA are added thereto, are stirred molten
Solution, is filtrated to get clear liquid.Clear liquid is heated to 85 DEG C again, heated while stirring, it is seen that has white solid precipitation, is filtrated to get essence
Lithium carbonate processed, main content 99wt%.The prepared calcium carbonate lithium of preparation and freshly prepared calcium hydroxide are supplied into causticization device
Carry out causticizing reaction, 95 DEG C of reaction temperature, reaction time 0.5h, through being filtrated to get lithium hydroxide solution after reaction.By hydroxide
Lithium solution is supplied into ion interchange unit, by being mounted with large aperture cationic ion-exchange resin D401 reaction tower, obtains miscellaneous
Matter Ca, Mg content is less than 1mg/L refined lithium hydroxide solution.Refined lithium hydroxide solution is put into cold boiler, entered
Row reduction vaporization, which is concentrated into when a small amount of crystal is separated out, stops heating, is cooled to 40 DEG C, crystallization obtains monohydrate lithium hydroxide crude product.With
Vacuum drying chamber drying is placed into after a small amount of pure water monohydrate lithium hydroxide crude product and obtains high-purity monohydrate lithium hydroxide, product
LiOH·H2O purity is not less than 98wt%, major impurity K, Na, Ca, Mg, CO3 2-、Cl-、SO4 2-Content be respectively 0.001wt%,
0.001wt%, 0.001wt%, 0.001wt%, 0.5wt%, 0.001wt%, 0.007wt%.Indices are superior to GB/T
Requirements of the 26008-2010 to impurity content.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (8)
1. a kind of system for preparing monohydrate lithium hydroxide, it is characterised in that including：
Be carbonized knot screen, and the carbonization knot screen has lithium carbonate crude product entrance, water inlet, carbon dioxide entrance, EDTA
Entrance and the outlet of prepared calcium carbonate lithium；
There is causticization device, the causticization device prepared calcium carbonate lithium entrance, milk of lime entrance and lithium hydroxide to complete liquid outlet, institute
Prepared calcium carbonate lithium entrance is stated with prepared calcium carbonate lithium outlet to be connected；
There is ion interchange unit, the ion interchange unit lithium hydroxide completion liquid entrance and refined lithium hydroxide scavenging solution to go out
Mouthful, the lithium hydroxide completes liquid entrance and is connected with the outlet of lithium hydroxide completion liquid；
Evaporated crystallization device, the evaporated crystallization device has refined lithium hydroxide scavenging solution entrance and monohydrate lithium hydroxide wet thick
Product are exported, and the refined lithium hydroxide scavenging solution entrance is connected with the refined lithium hydroxide scavenging solution outlet；
After-treatment device, the after-treatment device has the wet crude product entrance of monohydrate lithium hydroxide and monohydrate lithium hydroxide outlet, institute
The wet crude product entrance of monohydrate lithium hydroxide is stated with the outlet of the lithium hydroxide wet crude product to be connected.
2. system according to claim 1, it is characterised in that the carbonization knot screen further comprises：
Batch mixing unit, the batch mixing unit has lithium carbonate crude product entrance, water inlet and slurry outlet；
Precipitation unit, the precipitation unit has slurry inlet, carbon dioxide entrance, EDTA entrances and mixture export, described
Slurry inlet is connected with the slurry outlet；
Filter element, the filter element has entry to mixed solution, sludge outlet and filtrate (liquid, the entry to mixed solution and institute
Mixture export is stated to be connected；
Pyrolysis unit, the pyrolysis unit has filtrate inlet, carbon dioxide outlet and the outlet of refined lithium hydroxide scavenging solution, institute
Filtrate inlet is stated with the filtrate (liquid to be connected.
3. system according to claim 1, it is characterised in that the carbonization knot screen is closed mechanic whirl-nett reaction
Kettle.
4. system according to claim 1, it is characterised in that the causticization device is that the mechanical agitation with heated for controlling temperature is anti-
Answer kettle.
5. system according to claim 1, it is characterised in that the ion interchange unit is pillar ion exchange pot.
6. system according to claim 5, it is characterised in that the ion exchange resin used in the ion interchange unit
Including D401, D732 or IRC747.
7. system according to claim 1, it is characterised in that the evaporated crystallization device is vacuum type crystallizer or machinery
Stir cooled crystallizer.
8. system according to claim 1, it is characterised in that the after-treatment device is rotary scrubber and vacuum drying
Case.
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| CN109502611A (en) * | 2018-11-16 | 2019-03-22 | 湖南众德新材料科技有限公司 | A kind of device preparing lithium hydroxide micro nano powder |
| CN110467204A (en) * | 2019-08-19 | 2019-11-19 | 浙江华美新能源科技有限公司 | A kind of lithium hydroxide preparation system and technique |
| CN112919505A (en) * | 2021-03-03 | 2021-06-08 | 中国恩菲工程技术有限公司 | Device and method for continuously producing lithium hydroxide from salt lake lithium-rich brine |
| CN113634014A (en) * | 2021-08-17 | 2021-11-12 | 新乡赛普瑞特环保科技有限公司 | System and method for separating potassium ions in lithium solution |
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Application publication date: 20171024 |