CN102826576A

CN102826576A - Method for industrially producing industrial, cell-grade or high-purity lithium hydroxide monohydrate

Info

Publication number: CN102826576A
Application number: CN201210345099XA
Authority: CN
Inventors: 苏康; 杜洪文; 向东
Original assignee: SICHUAN CHANGHEHUALI TECHNOLOGY Co Ltd
Current assignee: SICHUAN CHANGHEHUALI TECHNOLOGY Co Ltd
Priority date: 2011-09-19
Filing date: 2012-09-17
Publication date: 2012-12-19
Also published as: CN202482081U

Abstract

The invention provides a method for industrially producing an industrial, cell-grade or high-purity lithium hydroxide monohydrate, which comprises the following steps of: (1) grinding; (2) removing impurities by a thermal precipitation method; (3) causticizing; and (4) removing impurities, crystallizing, washing, separating and drying. The invention also provides a method for preparing high-purity lithium carbonate. After causticizing reaction equipment and a reaction method which are provided by the invention are utilized, the feeding amount of the single causticizing production can be greatly improved and the large-scale industrial continuous production of the industrial and cell-grade lithium hydroxide monohydrate and the high-purity lithium carbonate is implemented; the consumption of water resources and energy can be effectively reduced and in the reaction, only a cheap precipitating agent or a cheap complexing agent needs to be used, so that the production cost is reduced; and the reaction is simple and convenient to operate and, the environment pollution is small, the obtained product has high quality and yield, the quality of the obtained product is stable and the product has wide industrial application prospect.

Description

The method of a kind of suitability for industrialized production technical grade, cell-grade or high-purity monohydrate lithium hydroxide

Technical field

The present invention relates to a kind of method with lithium ore deposit industriallization manufacture level, cell-grade or high-purity monohydrate lithium hydroxide.

Background technology

Lithium is at present known the lightest, the minimum silvery white basic metal of nuclear radius, and because of lithium and compound thereof have many distinctive premium propertiess, they are widely used in fields such as glass, pottery, lubricated, electronics, metallurgy, medicine, refrigeration, aerospace.Surging along with the clean energy demand, the lithium energy maybe the deep effect human lives, and it also is known as " energy upstart of 21 century ".Monohydrate lithium hydroxide is one of most important lithium salts.Being widely used in industries such as industrial chemicals, chemical reagent, lithium ion battery, oil, metallurgy, glass, pottery, also is the Chinese medicine material of national defense industry, nuclear industry and space industry simultaneously.Lithium Hydroxide MonoHydrate is mainly used in electrolytic solution and the lithium bromide refrigerator absorption liquid of producing lithium soap grease, Edison battery at present, can also be as the raw material of producing other lithium salts goods.

The method of traditional preparation process Lithium Hydroxide MonoHydrate is to be raw material with the lithium ore, and along with the lithium ore reduces day by day, the main mode of production that lithium becomes Lithium Hydroxide MonoHydrate is put forward in the salt lake.At present, be that the method for feedstock production Lithium Hydroxide MonoHydrate mainly contains Quilonum Retard causticizing process, ion-exchange membrane electrolysis, the aluminate precipitator method and calcination method with bittern.Yet existing industrial process Lithium Hydroxide MonoHydrate yield is not high, and heat utilization efficiency is low, and energy consumption is high, and a large amount of discharging of waste liquid are arranged, and the environmental friendliness degree is low; Simultaneously, because the restriction of production unit at present causes the suitability for industrialized production amount of Lithium Hydroxide MonoHydrate lower, can't satisfy the current market requirement to monohydrate lithium hydroxide.

Along with rapid increase to the Lithium Hydroxide MonoHydrate demand; It is reasonable to explore a kind of technological process of production; Production cost is low, and environmental pollution is little, and the method for product quality height, stay in grade, ability heavy industrialization continuous production cell-grade Lithium Hydroxide MonoHydrate has important economy, environment and social effect.

Summary of the invention

In order to address the above problem, the invention provides a kind of method of new suitability for industrialized production technical grade, cell-grade or high-purity monohydrate lithium hydroxide.

At first, the invention provides a kind of method with lithium ore deposit industriallization manufacture level, cell-grade or high-purity monohydrate lithium hydroxide, it comprises the steps:

(1) grinds: get the lithium ore deposit, be milled to particle diameter less than 80 μ m;

(2) thermal precipitator method removal of impurities:

1. sinker for the first time: with the lithium ore deposit add pure water or the waste liquid that recycles in, heated and stirred, spinning must contain lithium deposition one;

2. sinker for the second time: will contain lithium deposition one and be dissolved in the pure water, heating, spinning must contain lithium deposition two, and waste liquid is used for step and 1. recycles;

(3) causticization: the lithium deposition two that contains that step (two) obtains is carried out causticizing reaction, get lithium hydroxide solution;

(4) removal of impurities, crystallization: handle lithium hydroxide solution with precipitation agent or complexing agent, evaporation concentration, Crystallization Separation get the wet bullion of Lithium Hydroxide MonoHydrate;

Washing separates: with the wet bullion of pure water washing Lithium Hydroxide MonoHydrate, get the wet elaboration of Lithium Hydroxide MonoHydrate;

Dry: as, promptly to get technical grade, cell-grade or High Purity Hydrogen Lithium Oxide 98min with the wet elaboration oven dry of Lithium Hydroxide MonoHydrate.

Wherein, the said method of grinding of step () is:

A, thick broken: get salt lake type lithium ore deposit, be crushed to particle diameter less than 5mm;

B, oven dry: bake out temperature is less than 350 ℃, dry to material moisture less than 3%;

C, fine grinding: be finely ground to material particular diameter less than 50 μ m.

Further, said salt lake type lithium ore deposit is carbonate type lithium ore deposit, wherein contains the lithium amount with Li ₂O counts 5.0～40.3%w/w.

Wherein, step (two) the said first time of sinker with the concrete operations step of sinker for the second time is:

Getting the solid-liquid mass volume ratio is 1:2～5, is heated to 80～100 ℃, and constant temperature stirs 20～30min, and stirring velocity is 80～150r/min, after stirring is accomplished, and spinning again.

Further, the solid-liquid mass volume ratio is 1:2, and Heating temperature is 90 ℃.

Further, said causticizing reaction carries out in causticizing reaction equipment; Causticizing reaction equipment comprises causticizing tank, fore-warmer tank and tank;

Opening for feed one, circulation tube one and steam are set on the causticizing tank pipe one, discharge port one, recycle pump one and heating chamber one are set on the circulation tube one, steam inlet one and vapour outlet one are set on the heating chamber one;

Opening for feed two, circulation tube two and steam are set on the fore-warmer tank pipe two, discharge port two, recycle pump two and heating chamber two are set on the circulation tube two, steam inlet two and vapour outlet two are set on the heating chamber two;

Outlet is set on the tank;

The steam inlet two that steam on the causticizing tank goes out on the Guan Yiyu fore-warmer tank links to each other, and the steam on the fore-warmer tank goes out pipe two ends and is positioned at tank inside.

Wherein, the said causticizing reaction of step (three) carries out in the causticizing tank of causticizing reaction device, and pressure is 0～0.5MPa in the causticizing tank, and temperature of reaction is 85～135 ℃, and the flow velocity in the causticizing tank in the circulation tube one is 2～8m/s.

Further, pressure is 0.05～0.44MPa in the causticizing tank, and temperature is 95～135 ℃.

Wherein, the concrete operation method of step (four) is:

Get step (threes') lithium hydroxide solution; A mother liquor that adds pure water or recycle is handled lithium hydroxide solution, evaporation concentration, Crystallization Separation with precipitation agent or complexing agent; Get the once wet bullion of Lithium Hydroxide MonoHydrate and a mother liquor, one time mother liquor is used to recycle; With the once wet bullion of pure water washing Lithium Hydroxide MonoHydrate, get the once wet elaboration of Lithium Hydroxide MonoHydrate; With the once wet elaboration vacuum-drying of Lithium Hydroxide MonoHydrate, promptly get industrial 1 stage monohydrate lithium hydroxide.

Further, in the step (four), the final concentration of evaporation concentration is with LiO ₂Count 100～130g/L (solidliquid mixture).

Wherein, the concrete operation method of step (four) is:

A, get step (threes') lithium hydroxide solution; A mother liquor that adds pure water or recycle is handled lithium hydroxide solution, evaporation concentration, Crystallization Separation with precipitation agent or complexing agent; Get the once wet bullion of Lithium Hydroxide MonoHydrate and a mother liquor, one time mother liquor is used to recycle;

B, the once wet bullion of Lithium Hydroxide MonoHydrate is dissolved with pure water, secondary mother liquid, wash water or its mixed solution again, handles with precipitation agent or complexing agent again, evaporation concentration, Crystallization Separation, the Lithium Hydroxide MonoHydrate secondary bullion that wets; With the wet bullion of pure water washing Lithium Hydroxide MonoHydrate secondary, get the wet elaboration of Lithium Hydroxide MonoHydrate secondary; With the wet elaboration vacuum-drying of Lithium Hydroxide MonoHydrate secondary, promptly get battery-stage monohydrate lithium hydroxide.

Further, in the steps A, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 100～130g/L (solidliquid mixture); Among the step B, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 110～130g/L (solidliquid mixture).

Wherein, the concrete operation method of step (four) is:

B, the once wet bullion of Lithium Hydroxide MonoHydrate is dissolved with pure water, secondary mother liquid, wash water or its mixed solution again, handles with precipitation agent or complexing agent again, evaporation concentration, Crystallization Separation, the Lithium Hydroxide MonoHydrate secondary bullion that wets;

C, the wet bullion of Lithium Hydroxide MonoHydrate secondary is dissolved with pure water, three mother liquors, wash water or its mixed solutions again, handle lithium hydroxide solution with precipitation agent or complexing agent, evaporation concentration, Crystallization Separation must three wet bullions of Lithium Hydroxide MonoHydrate; With three wet bullions of pure water washing Lithium Hydroxide MonoHydrate, get three wet elaboration of Lithium Hydroxide MonoHydrate; With three wet elaboration vacuum-drying of Lithium Hydroxide MonoHydrate, promptly get the High Purity Hydrogen Lithium Oxide 98min.

Further, among the step a, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 100～130g/L (solidliquid mixture); Among the step b, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 110～130g/L (solidliquid mixture); Among the step c, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 110～120g/L (solidliquid mixture).

Further, said precipitation agent is Na ₂S, thioacetic acid amine, oxalic acid, lithium oxalate, sodium oxalate, phosphoric acid, Trilithium phosphate, sodium phosphate, monometallic or SODIUM PHOSPHATE, MONOBASIC, said complexing agent are YD 30, YD 30 lithium salts or disodium edta; The crystalline temperature is below 40 ℃.

The present invention also provides a kind of Preparation of High Pure Lithium Carbonate method, comprises the steps:

I, get three wet elaboration of the described Lithium Hydroxide MonoHydrate of above-mentioned steps c, add the pure water dissolving;

II, handle lithium hydroxide solution, filter, must filtrate with precipitation agent or complexing agent;

In III, the importing sealed reaction vessel of will filtrating, in container, feed carbonic acid gas, after question response was complete, filtering separation got the wet bullion of pure Lithium Carbonate;

IV, use the wet bullion of pure Lithium Carbonate added the pure water agitator treating, after the spinning, the wet elaboration of Quilonum Retard;

V, the wet elaboration of Quilonum Retard is dried to water cut less than 0.05%, promptly gets pure Lithium Carbonate.

Further, precipitation agent described in the step II is Na ₂S, thioacetic acid amine, oxalic acid, lithium oxalate, sodium oxalate, phosphoric acid, Trilithium phosphate, sodium phosphate, monometallic or SODIUM PHOSPHATE, MONOBASIC, said complexing agent are YD 30, YD 30 lithium salts or disodium edta;

In the step III, the pressure of carbonic acid gas is at 0.01～0.1MPa in the container;

In the step IV, the mass volume ratio of wet bullion of pure Lithium Carbonate and pure water is 1:2～5, and whipping temp is 90～120 ℃, and the agitator treating time is 10～30min.

Utilize causticizing reaction equipment provided by the invention and reaction method, can significantly improve the feeding quantity that the single causticization is produced, realized heavy industrialization continuous production technical grade, battery-stage monohydrate lithium hydroxide and pure Lithium Carbonate; Can effectively reduce the consumption of water resources and energy, and only need use cheap precipitation agent or complexing agent in the reaction, reduce production cost; This operation is easy, and environmental pollution is little, and products obtained therefrom quality and yield are all higher, and stay in grade has favorable industrial application prospect.

Obviously, according to foregoing of the present invention,,, can also make modification, replacement or the change of other various ways not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite according to the ordinary skill knowledge and the customary means of this area.

Below, foregoing of the present invention is remake further detailed description through the embodiment of embodiment form.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following instance.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.

Description of drawings

Fig. 1 the present invention prepares the process flow sheet of cell-grade Lithium Hydroxide MonoHydrate and pure Lithium Carbonate;

Fig. 2 the present invention prepares the process flow sheet of technical grade, cell-grade, High Purity Hydrogen Lithium Oxide 98min and pure Lithium Carbonate;

Fig. 3 causticization equipment of the present invention; Wherein, 1 is causticizing tank, and 2 is fore-warmer tank, and 3 is tank, and 4 is that opening for feed one, 5 is a circulation tube one; 6 is that discharge port one, 8 is that recycle pump one, 9 is that heating chamber one, 10 is a steam inlet one for steam goes out pipe one, 7; 11 is that vapour outlet one, 12 is that opening for feed two, 13 is that circulation tube two, 14 is a discharge port two for steam goes out pipe two, 15; 16 is that recycle pump two, 17 is that heating chamber two, 18 is that steam inlet two, 19 is that vapour outlet two, 20 is outlet.

Embodiment

Embodiment 1 the present invention prepares the method for cell-grade Lithium Hydroxide MonoHydrate

According to technical process as shown in Figure 1, the preparation pure Lithium Carbonate:

(1), grinds

1. get salt lake type lithium ore deposit, be lithium ore deposit, Zha Buye salt lake (Li ₂O:5.0～40.3%)

2. thick broken with the direct broken particle diameter＜50mm of material

3. dry bake out temperature and be controlled in 350 ℃ material moisture content＜3%

4. ultra-fine micropowder grind materials particle diameter＜50 μ m are adopted in fine grinding

(2), thermal precipitator method removal of impurities

5. with material 4. or contain sodium liquid and 10. in reaction kettle, be heated to 90 ℃ of heat with solid-liquid mass volume ratio 1:2 and stir and wash lithium sodium separate, and separates drying after the constant temperature 20～30 minutes with whizzer, must contain the lithium solid and contain sodium liquid

6. contain the lithium solid and after drying, contain 5. material moisture content＜8% of lithium solid

Chemical Composition: Li ₂O:28～31% Na ⁺: 1.5～3.5%

K ⁺：0.1～0.4% Cl ^-：1.2～2.0%

7. containing sodium liquid does not circulate and directly is used to prepare Na ₂CO ₃And NaCl

Chemical Composition: Li ₂O:2.5～5g/L Na ⁺: 50～80g/L K ⁺: 8～11g/L

CO ₃ ^2-：90～110g/L Cl ^-：35～55g/L ?SO ₄ ^2-：6～12g/L

Ca ²⁺：0.002～0.05g/L Mg ²⁺：0.03～0.07g/L

8. the material after the secondary lithium sodium separation activation removal of impurities: pure water=1:2 is heated to 90 ℃, and constant temperature stirs washes 20～30 minutes, dries to separate.

9. contain lithium solid materials moisture content≤8%

Chemical Composition: Li ₂O:28～33%

10. contain sodium liquid

Chemical Composition: Li ₂O:2.5～3.5g/L Na ⁺: 5～7g/L K ⁺: 0.4～0.7g/L

CO ₃ ^2-：8～12g/L Cl ^-：2～4g/L SO ₄ ^2-：0.2～0.16g/L

Ca ²⁺：0.002～0.05g/L Mg ²⁺：0.03～0.07g/L

(3) causticization will contain the lithium solid 9., lime and causticization water place the causticizing tank 1 of causticizing reaction equipment, feeds steam heating, carries out causticization, the causticizing reaction condition is following:

over-temp and over-pressure causticization pressure: 0.05～0.44MPa temperature: 95～135 ℃

Flow velocity in the causticizing tank 1 in the circulation tube 5 is 2～8m/s

Lime is effective: CaO＞80% particle diameter＜50 μ m

Constant temperature 20min

Filtering separation causticization slag contains H ₂O＜15% Li ₂O＜0.1%

The LiOH limpid Li that filtrates ₂O:18～25g/L

(4) removal of impurities, crystallization

Add oxalic acid and remove heavy metal Pb ²⁺, Ba ²⁺Deng with metallic impurity Ca ²⁺, Mg ²⁺Deng impurity

slag

Filtrating Li ₂O:18～25g/L Pb ²⁺＜0.001～0.005g/L, Ba ²⁺＜0.001～0.05g/L, Ca ²⁺＜0.0015～0.05g/L

Filtrating is evaporated to Li ₂O:100～130g/L (solidliquid mixture)

Crystallization Separation cools below 40 ℃, separates with whizzer

Once wet bullion LiOHH ₂The external free moisture content of O>=91.0%＜6%

To once wet dissolving crude product in pure water, return solution Li ₂O:50～90g/L

Removal of impurities adds auxiliary agent EDTA lithium salts and removes Ca ²⁺, Fe ³⁺, Mg ²⁺Deng impurity

It is as clear as crystal to filtrate, Li ₂O:50～80g/L

Evaporation concentration will

Evaporation concentration is to Li ₂O content is 120g/L (solidliquid mixture)

The cooling of

Crystallization Separation is cooled to below 40 ℃ spinning

The LiOH secondary bullion LiOHH that wets ₂The external free moisture content of O＞93.0%＜5%

Return to dissolve the wet bullion of secondary is added the pure water dissolving, return strength of solution Li ₂O:50～80g/L

Removal of impurities adds EDTA and further removes Ca ²⁺, Fe ³⁺, Mg ²⁺Deng impurity

It is as clear as crystal to filtrate, Li ₂O:50～80g/L

Evaporation concentration liquid concentrator Li ₂O:100～120g/L

Crystallization Separation cools below 40 ℃ spinning

Three wet bullion LiOHH of LiOH ₂The external free moisture content of O＞94.5%＜3%

(5) washing separates

washing separates use pure water, adopts drip washing or stirs and wash also spinning

Three wet elaboration LiOHH of LiOH ₂The external free moisture content of O＞94.5%＜3%

(6) drying

vacuum-drying vacuum tightness: 60～90 ℃ of oven dry of 0.001～0.01MPa temperature, 1～3h

25kg or the two-layer inner membrance of 20kg; The outer bag of one deck, quantitative package.

Through measuring, in the product of dry back, the content of monohydrate lithium hydroxide is greater than LiOHH ₂O=98.6%; , meet GB/T 26008-2010.

Embodiment 2 Preparation of High Pure Lithium Carbonate

Three wet elaboration of LiOH of preparation among the embodiment 1 are dissolved in the pure water solution Li ₂O:60～90g/L

Add EDTA and further remove Ca ²⁺, Fe ³⁺, Mg ²⁺, Si ⁴⁺, B ³⁺Deng impurity, and filter

It is as clear as crystal to filtrate, Li ₂O:60～90g/L

Feed high-purity CO ₂In the sealing carbonating tower, control CO ₂Flow velocity

Control pressure is at 0.01～0.1MPa

The high-purity Li of spinning ₂CO ₃Wet bullion moisture content＜8%

With Li ₂CO ₃Wet bullion adds pure water, stirs at 90～120 ℃ of following constant temperature with 1:2～5 solid-to-liquid ratios and washes 10～30min

spinning

pure Lithium Carbonate elaboration moisture content＜8% that wets

dried moisture content＜0.05% under 200～500 ℃ of temperature

pure Lithium Carbonate master's content>=99.99%, standard YS/T-2008

Embodiment 3 the present invention prepare the method for lithium hydroxide in industrial grade

According to technical process as shown in Figure 2, the preparation pure Lithium Carbonate:

(1), grinds

1. get carbonate type lithium concentrate (Li ₂O:5.0～40.3% is like lithium ore deposit, Zha Buye salt lake);

2. slightly broken: that this lithium concentrate is crushed to particle diameter≤5mm;

3. oven dry: bake out temperature≤350 ℃, dry to material moisture≤3%;

4. fine grinding: adopt the superfine grinding, be finely ground to material particular diameter≤80 μ m.

(2), thermal precipitator method removal of impurities

5. a lithium sodium separates 4. material is perhaps contained sodium liquid 10. with the drying of solid-liquid mass separation, must contain the lithium solid and contain sodium liquid; Volume ratio 1:2 is heated to 90 ℃ of heat and stirs and wash in reaction kettle, constant temperature is used whizzer after 20～30 minutes

6. contain the lithium solid and after drying, contain 5. material moisture content＜8% of lithium solid;

Chemical Composition: Li ₂O:28～31% Na ⁺: 1.5～3.5%

K ⁺：0.1～0.4% Cl ^-：1.2～2.0%

7. containing sodium liquid does not circulate and directly is used to prepare Na ₂CO ₃And NaCl;

Chemical Composition: Li ₂O:2.5～5.0g/L Na ⁺: 50～80g/L K ⁺: 8～11g/L

CO ₃ ^2-：90～110g/L Cl ^-：35～55g/L ?SO ₄ ^2-:6～12g/L

Ca ²⁺：0.002～0.05g/L Mg ²⁺：0.03～0.07g/L

9. contain lithium solid materials moisture content≤8%

Chemical Composition: Li ₂O:28～33%

10. contain sodium liquid

Chemical Composition: Li ₂O:2.5～3.5g/L Na ⁺: 5～7g/L K ⁺: 0.4～0.7g/L

CO ₃ ^2-：8～12g/L Cl ^-：2～4g/L SO ₄ ^2-:0.2～0.16g/L

Ca ²⁺：0.002～0.05g/L Mg ²⁺：0.03～0.07g/L

over-temp and over-pressure causticization pressure: 0～0.5MPa temperature: 85～135 ℃

Flow velocity in the causticizing tank 1 in the circulation tube 5 is 2～8m/s

The effective calcium of lime: CaO＞80% particle diameter＜50 μ m

Constant temperature 20min

Filtering separation causticization slag contains H ₂O＜15% Li ₂O＜0.1%

The LiOH limpid Li that filtrates ₂O:18～25g/L

(4) removal of impurities, crystallization

Add oxalic acid and remove heavy metal Pb ²⁺, Ba ²⁺Deng with metal Ca ²⁺, Mg ²⁺Deng foreign ion;

slag

Filtrating Li ₂O:18～25g/L, Pb ²⁺＜0.001～0.005g/L, Ba ²⁺＜0.001～0.05g/L, Ca ²⁺＜0.0015～0.05g/L

Filtrating is evaporated to Li ₂O:100～130g/L (solidliquid mixture);

Crystallization Separation cools below 40 ℃, separates with whizzer;

Once wet bullion: the LiOHH of LiOH ₂The external free moisture content of O>=91.0%＜6%;

(5) washing separates

washing separates with pure water with drip washing or stir the mode of washing and wash also spinning;

(6) drying

vacuum-drying vacuum tightness: 60～90 ℃ of oven dry of 0.001～0.01MPa temperature, 1～3h.

Prepare industrial 1 stage monohydrate lithium hydroxide 25kg or 50kg, two-layer inner membrance, the outer bag of one deck, quantitative package; Standard GB/T 8766-2002: product index: LiOHH ₂O:98.8%; Na ⁺: 0.07%; K ⁺: 0.05%; Fe:0.0005%; Ca ²⁺: 0.02%; CO ₂: 0.35%; Cl ^-: 0.001%; SO ₄ ² ^-: 0.012%; Hydrochloric acid insoluble substance: 0.08%; Water-insoluble: 0.01%; Through measuring, yield is more than 95%.

Embodiment 4 the present invention prepare the method for cell-grade Lithium Hydroxide MonoHydrate

The LiOH of embodiment 3 preparations is once wet dissolving crude product in pure water, return solution Li ₂O:50～90g/L;

Removal of impurities adds auxiliary agent EDTA, removes Ca ²⁺, Fe ³⁺, Mg ²⁺Deng impurity;

It is as clear as crystal to filtrate, Li ₂O:50～80g/L;

Evaporation concentration will

Evaporation concentration is to Li ₂O content is (solidliquid mixture) about 120g/L;

The cooling of Crystallization Separation is cooled to below 40 ℃ spinning;

LiOH secondary bullion: the LiOHH that wets ₂The external free moisture content of O＞93.0%＜5%;

(5) washing separates

Three wet elaboration: LiOHH of LiOH ₂O＞94.5%, external free moisture content＜3%;

(6) drying

vacuum-drying vacuum tightness: 60～90 ℃ of oven dry of 0.001～0.01MPa temperature, 1～3h;

Prepare

Battery-stage monohydrate lithium hydroxide is used two-layer inner membrance, polyethylene plastic bag vacuum seal packing, and every bag net weight 3 ± 0.03kg, one of 4 bag, fiber board bucket (or cardboard boxes) is adopted in outer packaging; Standard GB/T 26008-2010; Product index: LiOHH ₂O=99.0%; Na ⁺: 0.002%; K ⁺: 0.001%; Fe ³⁺: 0.0007%; Ca ²⁺: 0.002%; CO ₂: 0.30%; Cl ^-: 0.001%; SO ₄ ² ^-: 0.008%; Hydrochloric acid insoluble substance: 0.002%; Through measuring, yield is more than 90%.

Embodiment 5 the present invention prepare the method for high-purity grade of Lithium Hydroxide MonoHydrate

Return the wet bullion of LiOH secondary that dissolves preparation among the embodiment 4 and add the pure water dissolving, return strength of solution Li ₂O:50～80g/L;

Removal of impurities adds EDTA and further removes Ca ²⁺, Fe ³⁺, Mg ²⁺Deng impurity;

It is as clear as crystal to filtrate, Li ₂O:50～80g/L;

Evaporation concentration liquid concentrator Li ₂O:100～120g/L (solidliquid mixture);

Crystallization Separation cools below 40 ℃ spinning;

Three wet bullion: LiOH＞94.5% of

LiOH, external free moisture content＜3%;

(5) washing separates

Three wet elaboration: LiOH＞94.5% of

LiOH, external free moisture content＜3%;

(6) drying

Prepare

The High Purity Hydrogen Lithium Oxide 98min is used two-layer inner membrance, polyethylene plastic bag vacuum seal packing, and every bag net weight 3 ± 0.03kg, one of 4 bag, fiber board bucket (or cardboard boxes) is adopted in outer packaging; Company standard; Product index: LiOHH ₂O=99.2%; Na ⁺: 0.0005%; K ⁺: 0.0002%; Fe ³⁺: 0.0003%; Ca ²⁺: 0.0008%; CO ₂: 0.30%; Cl ^-: 0.001%; SO ₄ ^2-: 0.002%; Hydrochloric acid insoluble substance: 0.001%; Through measuring, yield is more than 88%.

Through adjusting, the present invention is in the whole process of high-purity grade of Lithium Hydroxide MonoHydrate of preparation, and water consumption and energy consumption have reduced more than 10%, have significantly improved water and rate of energy.

The Lithium Oxide 98min of High Purity Hydrogen described in the present invention, essence are meant highly purified cell-grade Lithium Hydroxide MonoHydrate, and its purity is higher, are referred to as the High Purity Hydrogen Lithium Oxide 98min in the industry, and the enterprises standard is only arranged at present.

Embodiment 6 Preparation of High Pure Lithium Carbonate

Three wet elaboration of LiOH are dissolved in the pure water solution Li ₂O:60～90g/L;

Removal of impurities adds EDTA and further removes Ca ²⁺, Fe ³⁺, Mg ²⁺, Si ⁴⁺, B ³⁺Deng impurity;

It is as clear as crystal to filtrate, Li ₂O:60～90g/L;

Feed high-purity CO ₂In the sealing carbonating tower, control CO ₂Flow velocity, control pressure is at 0.01～0.1MPa;

The high-purity Li of spinning ₂CO ₃Wet bullion moisture content＜8%;

With Li ₂CO ₃Wet bullion adds pure water, stirs at 90～120 ℃ of following constant temperature with the solid-to-liquid ratio of 1:2～5 and washes 10～30min;

spinning;

pure Lithium Carbonate elaboration moisture content＜8% that wets;

dried moisture content＜0.05% under 200～500 ℃ of temperature;

pure Lithium Carbonate master's content>=99.99%, standard YS/T 546-2008;

Product index: Li ₂CO ₃: 99.99%; Na ⁺: 0.0008%; K ⁺: 0.0005%; Fe ³⁺: 0.0002%; Ca ²⁺: 0.0005%; Mg ²⁺: 0.0001%.

Embodiment 7 causticizing reaction equipment of the present invention

Producing the causticization mode of Lithium Hydroxide MonoHydrate at present, all is to adopt common response still alr mode to carry out causticization to handle, if the reaction kettle capacity is excessive; Charging capacity is too much, then can cause stirring inhomogeneous, therefore; Because the restriction of alr mode makes most reaction kettles can only be designed to 1～5m ³Stowage space, maximum also can only reach 10m ³, in the big production of industry, the limitation of reaction vessel causes when the industrial production Lithium Hydroxide MonoHydrate, needs more duplication of labour time of cost and energy consumption, can satisfy the production in enormous quantities of Lithium Hydroxide MonoHydrate.

As shown in Figure 3, the invention provides a kind of causticization equipment, it comprises causticizing tank 1, fore-warmer tank 2 and tank 3;

Opening for feed 1, circulation tube 1 and steam are set on the causticizing tank 1 pipe 1, discharge port 1, recycle pump 1 and heating chamber 1 are set on the circulation tube 1, steam inlet 1 and vapour outlet 1 are set on the heating chamber 1;

Opening for feed 2 12, circulation tube 2 13 and steam are set on the fore-warmer tank 2 pipe 2 14, discharge port 2 15, recycle pump 2 16 and heating chamber 2 17 are set on the circulation tube 2 13, steam inlet 2 18 and vapour outlet 2 19 are set on the heating chamber 2 17;

Outlet 20 is set on the tank 3;

Steam on the causticizing tank 1 goes out pipe 1 and links to each other with steam inlet 2 18 on the fore-warmer tank 2, and the steam on the fore-warmer tank 2 goes out to manage 2 14 end and is positioned at tank 3 inside.

During use; Earlier the causticization water is placed fore-warmer tank 2, the steam in the causticizing tank 1 goes out pipe 1 through steam and arrives in the fore-warmer tank 2, and the causticization water is carried out preheating; Not only utilized the steam that produces in the causticizing tank to carry out preheating here; Also carry out causticizing reaction, effectively utilized heat energy, reduced production energy consumption with the causticization water after the preheating.Steam in the fore-warmer tank goes out the pipe 14 to spread out of from steam, because the air setting effect forms zero(ppm) water in tank 3, collects zero(ppm) water, and its circulation is used for the big production of the present invention.

The setting of recycle pump is in order round-robin power to be provided for the reactant that gets in the circulation tube, to let reactant run to the other end from an end of circulation tube, can making lime and Li ₂CO ₃React effectively; The capacity of circulation tube is certain, and the inventory that gets in the circulation tube is less relatively, and material circulation time, the power of recycle pump can constantly not increase along with the increase of charging capacity, thereby have saved production energy consumption effectively.Also be provided with heating chamber on the circulation tube, can let the temperature of reactant remain at best causticization temperature.

Replace the whisking appliance in the existing installation with circulation tube and recycle pump in this causticizing reaction equipment, the mode of this circulation causticization, stirring intensity is big, and it is low to consume energy, and can make lime and Li ₂CO ₃React completely rapidly, and, because the capacity of circulation tube is certain; Only need the less circulation pump power just can the material circulation of device interior is even, need not to worry in the reaction kettle that inventory is excessive and causticization that cause is incomplete, therefore; During this equipment of employing, conventional charging capacity can reach 30～60m ³/ inferior, if the production needs are arranged, can reach 100m ³/ inferior more than, each inventory of handling is more suitable for industrialized production much larger than existing installation.Simultaneously, this causticizing reaction equipment does not have whisking appliance, makes to need not its better tightness special seal and handle, and has reduced equipment cost, and the setting of circulation tube and recycle pump, has further reduced the energy consumption of reaction yet.

In sum, utilize causticizing reaction equipment provided by the invention and reaction method, can significantly improve the feeding quantity that the single causticization is produced, realized heavy industrialization continuous production technical grade, battery-stage monohydrate lithium hydroxide and pure Lithium Carbonate; Can effectively reduce the consumption of water resources and energy, and only need use cheap precipitation agent or complexing agent in the reaction, reduce production cost; This operation is easy, and environmental pollution is little, and products obtained therefrom quality and yield are all higher, and stay in grade has favorable industrial application prospect.

Claims

1. method with lithium ore deposit industriallization manufacture level, cell-grade or high-purity monohydrate lithium hydroxide, it is characterized in that: it comprises the steps:

(2) thermal precipitator method removal of impurities:

2. method according to claim 1 is characterized in that: the said method of grinding of step () is:

Thick broken: as to get salt lake type lithium ore deposit, be crushed to particle diameter less than 5mm;

Oven dry: bake out temperature is less than 350 ℃, dry to material moisture less than 3%;

Fine grinding: be finely ground to material particular diameter less than 50 μ m.

3. method according to claim 2 is characterized in that: said salt lake type lithium ore deposit is lithium ore deposit, carbonate type salt lake, wherein contains the lithium amount with Li ₂O counts 5.0～40.3%w/w.

4. method according to claim 1 is characterized in that: step (two) the said first time of sinker with the concrete operations step of the sinker second time is:

Getting the solid-liquid mass volume ratio is 1:2-5, is heated to 80-100 ℃, and constant temperature stirs 20-30min, and stirring velocity is 80-150r/min, after stirring is accomplished, and spinning again.

5. method according to claim 4 is characterized in that: the solid-liquid mass volume ratio is 1:2, and Heating temperature is 90 ℃.

6. method according to claim 1 is characterized in that: said causticizing reaction carries out in causticizing reaction equipment; Causticizing reaction equipment comprises causticizing tank (1), fore-warmer tank (2) and tank (3);

Opening for feed one (4), circulation tube one (5) and steam are set on the causticizing tank (1) pipe one (6); Discharge port one (7), recycle pump one (8) and heating chamber one (9) are set on the circulation tube one (5), steam inlet one (10) and vapour outlet one (11) are set on the heating chamber one (9);

Opening for feed two (12), circulation tube two (13) and steam are set on the fore-warmer tank (2) pipe two (14); Discharge port two (15), recycle pump two (16) and heating chamber two (17) are set on the circulation tube two (13), steam inlet two (18) and vapour outlet two (19) are set on the heating chamber two (17);

Outlet (20) is set on the tank (3);

Steam on the causticizing tank (1) goes out pipe one (6) and links to each other with steam inlet two (18) on the fore-warmer tank (2), and the steam on the fore-warmer tank (2) goes out to manage two (14) ends and is positioned at tank (3) inside.

7. method according to claim 6; It is characterized in that: the said causticizing reaction of step (three) carries out in causticizing tank (1); Pressure is 0～0.5MPa in the causticizing tank (1), and temperature of reaction is 85～135 ℃, and the flow velocity in the causticizing tank (1) in the circulation tube one (5) is 2～8m/s.

8. method according to claim 7 is characterized in that: pressure is 0.05～0.44MPa in the causticizing tank (1), and temperature is 95～135 ℃.

9. method according to claim 1 is characterized in that: the concrete operation method of step (four) is:

10. method according to claim 9 is characterized in that: in the step (four), the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 100～130g/L (solidliquid mixture).

11. method according to claim 1 is characterized in that: the concrete operation method of step (four) is:

12. method according to claim 11 is characterized in that: in the steps A, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 100～130g/L (solidliquid mixture); Among the step B, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 110～130g/L (solidliquid mixture).

13. method according to claim 1 is characterized in that: the concrete operation method of step (four) is:

A, get step (threes') lithium hydroxide solution; A mother liquor that adds pure water or recycle is handled lithium hydroxide solution, evaporation concentration, Crystallization Separation with precipitation agent or complexing agent; Get bullion of Lithium Hydroxide MonoHydrate and a mother liquor, one time mother liquor is used to recycle;

14. method according to claim 13 is characterized in that: among the step a, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 10～130g/L (solidliquid mixture); Among the step b, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 110～130g/L (solidliquid mixture); Among the step c, the final concentration of evaporation concentration is with LiO in total solidliquid mixture ₂Content count 110～120g/L (solidliquid mixture).

15. according to any described method of claim 9-14, it is characterized in that: said precipitation agent is Na ₂S, thioacetic acid amine, oxalic acid, lithium oxalate, sodium oxalate, phosphoric acid, Trilithium phosphate, sodium phosphate, monometallic or SODIUM PHOSPHATE, MONOBASIC, said complexing agent are YD 30, YD 30 lithium salts or disodium edta; The crystalline temperature is below 40 ℃.

16. a Preparation of High Pure Lithium Carbonate method is characterized in that: comprise the steps:

I, weighting profit require three wet elaboration of the described Lithium Hydroxide MonoHydrate of step c in 13, add the pure water dissolving;

17. preparation method according to claim 16 is characterized in that: precipitation agent described in the step II is Na ₂S, thioacetic acid amine, oxalic acid, lithium oxalate, sodium oxalate, phosphoric acid, Trilithium phosphate, sodium phosphate, monometallic or SODIUM PHOSPHATE, MONOBASIC, said complexing agent are YD 30, YD 30 lithium salts or disodium edta;