CN102583453A - Industrial method for producing battery-grade lithium carbonate or high-purity lithium carbonate - Google Patents

Industrial method for producing battery-grade lithium carbonate or high-purity lithium carbonate Download PDF

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CN102583453A
CN102583453A CN2012100159790A CN201210015979A CN102583453A CN 102583453 A CN102583453 A CN 102583453A CN 2012100159790 A CN2012100159790 A CN 2012100159790A CN 201210015979 A CN201210015979 A CN 201210015979A CN 102583453 A CN102583453 A CN 102583453A
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lithium
quilonum retard
carbonate
sodium
lithium carbonate
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CN102583453B (en
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苏康
杜洪文
向东
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SICHUAN CHANGHEHUALI TECHNOLOGY Co Ltd
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SICHUAN CHANGHEHUALI TECHNOLOGY Co Ltd
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Abstract

The invention provides an industrial method for producing battery-grade lithium carbonate or high-purity lithium carbonate. The industrial method comprises the following steps of: carbonizing; placing a carbonate-type lithium source in a hydriding reaction kettle for one time or more than two times of carbonization to obtain a wet lithium carbonate product, wherein the content of Li2O in the lithium source is 5.0-40.3% (w/w); and drying the wet lithium carbonate product obtained by one-time carbonization, thus obtaining battery-grade lithium carbonate; or drying the wet lithium carbonate product obtained by more than two times of carbonization, thus obtaining high-purity lithium carbonate. The method provided by the invention can continuously produce battery-grade lithium carbonate or high-purity lithium carbonate on large scale, is low in energy consumption and environmentally friendly and has strong practical value.

Description

A kind of industrial method of producing battery-level lithium carbonate or pure Lithium Carbonate
Technical field
The present invention relates to a kind of Preparation of High Pure Lithium Carbonate method, be specifically related to the method for suitability for industrialized production pure Lithium Carbonate and battery-level lithium carbonate.
Background technology
Lithium, the lightest known, the minimum silvery white basic metal of nuclear radius, 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 ".
Quilonum Retard is a kind of important lithium salts, and it is of many uses, has very strong application market and is worth.According to relevant GB and rowers such as GB/T 11075-2003, GB 10576-89, YS/T 582-2006, Quilonum Retard can be divided into level Four:
Technical grade Li 2CO 3Li 2CO 3Content＜99.50%,
Cell-grade Li 2CO 399.50%≤Li 2CO 3Content＜99.90%,
High-purity 3N level Li 2CO 399.90%≤Li 2CO 3Content＜99.99%,
High-purity 4N level Li 2CO 3Above Li 2CO 3Content>=99.99%.
Yet; Domestic majority Quilonum Retard manufacturer all can only provide the comparatively technical grade Quilonum Retard of low side at present; The manufacturer that some strength is stronger can provide battery-level lithium carbonate, and their actual application value can not show a candle to pure Lithium Carbonate, causes China's Quilonum Retard industry not have an international competitiveness.
By " Quilonum Retard Study on Crystallization Process " that the Sun Yu post was delivered on April 20th, 2010, East China University of Science's doctorate paper can be known for the 5th～7 page, at present by elementary Li 2CO 3(purity is less than 95%) prepares high-purity Li 2CO 3The kinds of processes route is arranged: 1, recrystallization method, recrystallization method are divided into Quilonum Retard recrystallization method and lithium formate recrystallization method, but because of the coprecipitation phenomena in the recrystallization process, the content of impurity silicon is difficult to drop to 5 * 10 -4Below the %; 2, LiOH solution carborization comprises causticization carborization and electrolysis carborization, and the former needs exquisite milk of lime; And purity requirement is very high, and there is the foreign ion pollution problems in the latter, and electrolyzer needs the high price corrosion material simultaneously; Electrolytic power consumption is big, and is very high to the barrier film requirement, all is inappropriate for industrial application; 3, carborization comprises the carbonization precipitator method and carbonization decomposition method, and the carbonization precipitator method are with elementary Li 2CO 3Be mixed into an aqueous slurry with deionized water,, change the Quilonum Retard of indissoluble into solubleness bigger LiHCO again to wherein feeding high-purity dioxide gas 3, then in another reactor drum with high-purity LiOH react throw out, be high-purity Li after the oven dry 2CO 3Product; The carbonization decomposition method is with Li 2CO 3Be mixed into water-soluble slurry with deionized water, under condition of stirring, to wherein feeding high-purity carbon dioxide gas, change the Quilonum Retard of indissoluble into solubleness bigger LiHCO 3, filtering slurry then to remove insoluble impurity, the impurity that is dissolved in filtrating can be removed through methods such as IX and extractions, the LiHCO after in another reactor drum, adding thermal purification 3Solution, constant temperature stir removes dioxide gas, LiHCO 3Decompose deposition and generate Li 2CO 3, filtering out deposition through cooling again, oven dry obtains highly purified Li 2CO 3Product.Heat of carbonization solution is easy to get because of raw material is relatively inexpensive, and technology is simple, and the process environmental protection has higher operability.
The bibliographical information of existing Carbonization Preparation pure Lithium Carbonate is laboratory method, is not suitable for large-scale industrial production.
A kind of technological process of production is reasonable, production cost is low, energy consumption is low, environmental pollution is little, quality product is high, but the method for stay in grade heavy industrialization continuous production pure Lithium Carbonate has important environmental protection, economy and social effect so explore.
Summary of the invention
In order to address the above problem, the invention provides a kind of new suitability for industrialized production battery-level lithium carbonate or the method and the relevant specific equipment (hydrogenation still) of pure Lithium Carbonate.
The invention provides a kind of industrial method of producing battery-level lithium carbonate or pure Lithium Carbonate, it comprises the steps:
A kind of industrial method of producing battery-level lithium carbonate or pure Lithium Carbonate, it comprises the steps:
(1) carbonization: get carbonate type lithium source, wherein Li 2O content is 5.0～40.3%w/w, places the hydrogenation still to carry out above once or twice carbonizing treatment, gets the wet elaboration of Quilonum Retard;
(2) after the wet elaboration oven dry of Quilonum Retard with a carbonizing treatment gained, promptly get battery-level lithium carbonate; Or, after the wet elaboration oven dry of Quilonum Retard with twice above carbonizing treatment gained, promptly get pure Lithium Carbonate.
Carbonate type lithium source (Li described in the present invention 2O:5.0～40.3%w/w) comprising: carbonate type salt lake lithium concentrate, technical grade Quilonum Retard (or wherein product, substandard products, waste product etc.) and other contain the material of Quilonum Retard.
Wherein, the said carbonizing treatment of step () comprises the steps:
I hydrogenation: with the carbonate type lithium source of particle diameter≤80 μ m, one or more the mixed solution with pure water, mother liquor, wash water adds in the hydrogenation still, feeds CO 2To liquid pH be 7.0～8.5, promptly get hydride;
II removal of impurities: in above-mentioned hydride, add precipitation agent or complexing agent, contamination precipitation is perhaps existed with the stable water soluble complex compound;
The III sinker: hydride heated and stirred or adding LiOH that Step II is handled stir, and solid-liquid separation gets the Quilonum Retard bullion, and mother liquor is used for step I and recycles;
IV washing: the Quilonum Retard bullion is centrifugal after with the pure water heated and stirred, and wash water is used for step I and recycles, and is precipitated as the Quilonum Retard elaboration that wets.
Wherein, said hydrogenation still comprises tank body (1), circulation tube (2) and recycle pump (3), and wherein, circulation tube (2) one ends are connected with tank body (1) bottom, and the other end of circulation tube (2) is connected with the middle part of tank body (1), and recycle pump (3) is arranged in the circulation tube (2).
Further, leakage fluid dram, inlet mouth are set on the circulation tube.
Preferably, inlet mouth, recycle pump are arranged on the bottom of circulation tube.
Further, circulation tube outer setting prolong.
Further, tank body top is provided with relief port and opening for feed.
Wherein, in the hydrogenation process of step I, the temperature in the hydrogenation still is 0～50 ℃, CO 2Pressure be 0.1～0.5MPa; The flow velocity of material is 2～8m/s in the circulation tube of hydrogenation still (2).Wherein, temperature of reaction is preferably 0～25 ℃, CO 2Pressure is preferably 0.2～0.3MPa, and flow velocity is preferably 3～5m/s.
Wherein, during carbonization for the first time, the Ca of Quilonum Retard bullion among the Step II I 2+≤0.0050%, Mg 2+≤0.010% o'clock, mother liquor was used for step I and recycles; The Ca of the wet elaboration of Quilonum Retard among the step IV 2+≤0.0050%, Mg 2+≤0.010% o'clock, wash water was used for step I and recycles;
During carbonization for the second time, the Ca of Quilonum Retard bullion among the Step II I 2+≤0.001%, Mg 2+≤0.001% o'clock, mother liquor was used for step I and recycles; The Ca of the wet elaboration of Quilonum Retard among the step IV 2+≤0.001%, Mg 2+≤0.001% o'clock, wash water was used for step I and recycles.
Wherein, adopt the method sinker of heated and stirred among the Step II I, wherein, temperature is 85～100 ℃, and preferred 90 ℃, constant temperature stirs 10～60min, preferred 20～30min; Or, adopt the method sinker that adds LiOH among the Step II I, wherein, LiHCO 3: LiOH=1: 0.5～1.2w/w, stir 10～60min, preferred 20～30min;
The condition of step IV washing, the Quilonum Retard bullion: the mass volume ratio of pure water is 1: 2～5w/v, stirs 10～60min at 70～100 ℃ of following constant temperature.Be preferably the Quilonum Retard bullion: the mass volume ratio of pure water is 1: 2.5-3.5w/v, 90-95 ℃ of following constant temperature stirs 20～30min.
Wherein, In the impurity removal process of Step II; Said precipitation agent is one or more the compsn in oxalic acid, lithium oxalate, sodium oxalate, phosphoric acid, Trilithium phosphate, sodium phosphate, monometallic, SODIUM PHOSPHATE, MONOBASIC, sodium sulphite, the thioacetamide, and said complexing agent is one or more the compsn in YD 30, YD 30 lithium salts, the disodium edta.
Further, step () adopts twice carbonizing treatment, wherein, removes for the first time and uses mixedly precipitation agent, removes for the second time and uses mixedly complexing agent.
Further, in the said carbonate type lithium of step () source, Li 2O content is 32.0～40.3%w/w, and this carbonate type lithium source need not pre-treatment, directly carries out carbonizing treatment;
Or the carbonate type lithium contains Li in the source 2O≤32.0%w/w after pre-treatment is carried out earlier in this carbonate type lithium source, carries out carbonizing treatment again; Wherein, pretreatment process is following:
(1) lithium sodium separates for the first time: get carbonate type lithium source, add pure water or/and contain in the sodium liquid, and heated and stirred, solid-liquid separation must contain the lithium precipitate A; For the second time lithium sodium separates: will contain the lithium precipitate A and add in the pure water, and heated and stirred, solid-liquid separation promptly gets and contains the lithium precipitate B, and separating obtained solution recycles for containing sodium liquid and being used for lithium sodium separation for the first time; Or,
(2) earlier with after the calcining of carbonate type lithium source, handle through step (1) again.
Majority only contains inorganic impurity in the carbonate type lithium source commonly used at present, for this type lithium source, only adopts the pretreatment process of step (1); Yet, when having a large amount of organic impurity in the carbonate type lithium source, after needing to remove organic impurity according to conventional method for calcinating earlier, adopt the pretreatment process of step (1) again.Adopt the inventive method, also can carry out the carbonization flow process as not carrying out pre-treatment, but its suitability for industrialized production economy not high (hydrogenation length consuming time, water loss is big, energy consumption is big, solid-liquid separation is difficult).
Wherein, in lithium sodium separation for the first time, the lithium sodium sepn process for the second time, the solid-liquid mass volume ratio is 1: 2～5w/v, and Heating temperature is 70～100 ℃, and mixing speed is 50～200r/min, lithium sodium disengaging time 10～60min.Be preferably, the solid-liquid mass volume ratio is 1: 2-3w/v, Heating temperature is 85-95 ℃, lithium sodium disengaging time 20～30min.
Further, Li in the said carbonate type lithium of step () source 2Content 32.0～40.3%w/w of O selects for use technical grade Quilonum Retard or its substandard products as the lithium source;
Or the said carbonate type lithium of step () contains Li in the source 2O≤32.0%w/w selects for use carbonate type salt lake lithium concentrate as the lithium source.
Wherein, when adopting carbonate type salt lake lithium concentrate, grind the lithium source and can adopt following method as the lithium source:
A, thick broken: get carbonate type salt lake lithium concentrate, be crushed to particle diameter≤5mm;
B, oven dry: bake out temperature≤350 ℃, dry to material moisture≤3%;
C, fine grinding: be finely ground to material particular diameter≤80 μ m.
The inventive method has realized heavy industrialization continuous production pure Lithium Carbonate (Li 2CO 3>=99.90%), this method is with carbonate type lithium source (Li 2O:5.0～40.3%w/w) progressively prepare battery-level lithium carbonate and pure Lithium Carbonate for starting substance; Such lithium source comprises: carbonate type salt lake lithium concentrate, technical grade Quilonum Retard or wherein between product, substandard products, waste product etc., and other contains the material of Quilonum Retard.Preparing method of the present invention makes Li 2Minimum is reduced in the loss of O, and total recovery can reach more than 95%, and the various wash waters and the mother liquor that produce in the production process can be recycled, and the water saving rate can reach more than 83.5%, greatly reduces the consumption of water resources; Adopt common precipitation agent or complexing agent in the removal of impurities process, need not to expend the higher resin of price and carry out removal of impurities, greatly reduced production cost, and, environment friendly had.Simultaneously, the inventive method can also make battery-level lithium carbonate (Li 2CO 3>=99.50%), total recovery can reach more than 97%, can be according to the market requirement, and selectivity is produced battery-level lithium carbonate or pure Lithium Carbonate, has better market 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
The process flow sheet of Fig. 1 suitability for industrialized production pure Lithium Carbonate of the present invention
Fig. 2 hydrogenation still of the present invention structural representation
Wherein, 1 is tank body, and 2 is circulation tube, and 3 is recycle pump, and 4 is the relief port, and 5 is leakage fluid dram, and 6 is inlet mouth, and 7 is water-cooled tube, and 8 is opening for feed.
Embodiment
In the carbonate type lithium source described in the present invention, Li 2O content: 5.0～40.3%w/w comprises: carbonate type salt lake lithium concentrate, technical grade Quilonum Retard (or wherein product, substandard products, waste product etc.) and other contain the material of Quilonum Retard.
Embodiment 1 adopts the industrial method of carbonate type salt lake lithium concentrate direct production battery-level lithium carbonate
According to technical process as shown in Figure 1, the preparation battery-level lithium carbonate:
(1), grinds
1. get carbonate type salt lake lithium concentrate (like carbonate type salt lake, Tibet lithium concentrate).Such lithium concentrate can obtain through purchase, also can utilize common process to extract the lithium resource in the salt lake brine and obtains.
This lithium mineralising composition:
Li 2O：10.0～30.0％ Na +：5.0～16.5％ K +：2.6～4.0％
CO 3 2-：8.0～56.0％ Cl -：8.0～11.0％ SO 4 2-：1.5～4.0％
Ca 2+：0.4～1.5％ Mg 2+：0.4～5.0％
2. thick broken with the direct broken particle diameter≤5mm of material;
3. dry bake out temperature≤350 ℃, material moisture content≤3%;
4. ultra-fine micropowder grind materials particle diameter≤80 μ m are adopted in fine grinding.
(2), thermal precipitator method removal of impurities
5. lithium sodium separate with material 4. add pure water or/and contain sodium liquid 10. in, solid-liquid mass volume ratio 1: 2 is heated to 90 ℃ in the hydrogenation still; After constant temperature stirs 20～30min; Separate to dry with whizzer, must contain the lithium solid 6. with contain sodium liquid 7., contain the lithium solid and be used for for the second time that lithium sodium separates; Contain the working cycle that sodium liquid then no longer gets into present method, can be used for preparing Na 2CO 3And NaCl.Wherein, it is specific as follows with the chemical ingredients that contains in the sodium liquid to contain the lithium solid:
Contain the lithium solid 6.: material moisture content≤8%
Chemical Composition:
Li 2O：28.0～31.0％ Na +：1.5～3.5％
K +：0.1～0.4％ Cl -：1.2～2.0％
Contain sodium liquid Chemical Composition 7.:
Li 2O：2.5～5.0g/L Na +：50.0～80.0g/L K +：8.0～11.0g/L
CO 3 2-：90.0～110.0g/L Cl -：35.0～55.0g/L SO 4 2-：6.0～12.0g/L
Ca 2+：0.002～0.05g/L Mg 2+：0.03～0.07g/L
8. secondary lithium sodium separates and to contain the lithium solid 6. after separating through a lithium sodium: pure water=1: 2w/v; Be heated to 90 ℃; Constant temperature stirs 20～30min, and centrifuge dripping separates, must contain the lithium solid 9. with contain sodium liquid 10.; Contain the lithium solid and 9. be used to be further purified, contain sodium liquid 10. then circulation be used for lithium sodium and separate 5..Wherein, contain the lithium solid 9. with to contain sodium liquid chemical ingredients 10. specific as follows:
Contain the lithium solid 9.: material moisture content≤8%
Chemical Composition:
Li 2O：30.0～34.0％ Na +：0.5～1.0％
K +：0.05～0.15％ Cl -：0.15～0.5％
Contain sodium liquid 10.:
Chemical Composition:
Li 2O：2.5～3.5g/L Na +：5.0～7.0g/L K +：0.4～0.7g/L
CO 3 2-：8.0～12.0g/L Cl -：2.0～4.0g/L SO 4 2-：0.2～0.16g/L
Ca 2+：0.002～0.05g/L Mg 2+：0.03～0.07g/L
(3) carbonization
1, a carbonization
Figure BDA0000132131290000061
9. or technical grade Quilonum Retard or its substandard products (Li a hydrogenation contains the lithium solid 2O:32.0～40.3%), adds pure water, Li 2CO 3Wash water
Figure BDA0000132131290000062
Or Li 2CO 3Mother liquor
Figure BDA0000132131290000063
One or more mixed solutions in, once contain the lithium solid 9. charging capacity be 3000kg～6000kg, liquid add-on 50～100m 3, airtight feeding CO in hydrogenation still provided by the invention (reaction kettle is seen embodiment 3) 2, temperature≤25 ℃, the time is 1～2h, keeps CO in the reaction kettle 2Pressure 0.2～0.3MPa, terminal point is as the criterion with hydride pH 7.0～8.5, and the flow velocity of material is 3～5m/s in the circulation tube, and every still can prepare hydride 50～100m 3
Figure BDA0000132131290000064
After hydrogen treatment is treated in removal of impurities, in solution, add precipitation agents such as oxalic acid, lithium oxalate, phosphoric acid, Trilithium phosphate, monometallic, SODIUM PHOSPHATE, MONOBASIC, sodium sulphite or thioacetamide, make Ca 2+, Mg 2+Divalence, trivalent ion are precipitated, after the filtration, and filter residue
Figure BDA0000132131290000065
Carry out special disposal, do not get into the preparation process of present method, filtrating
Figure BDA0000132131290000066
Be used for further processing.
Figure BDA0000132131290000067
sinker
Will be through a hydrogenation
Figure BDA0000132131290000068
Removal of impurities After liquid put into the pyrolysis groove, be heated to 90 ℃, constant temperature 20～30min, Li in mother liquor during terminal point 2O≤5g/L; Spinning promptly obtains Li one time 2CO 3Bullion And mother liquor
Figure BDA00001321312900000611
To filtrate
Figure BDA00001321312900000612
Add in the pyrolysis groove, be heated to 90 ℃, constant temperature 20～30min, the pyrolysis terminal point is with Li in the mother liquor 2O≤5g/L is an index, treat that pyrolysis is accomplished after, centrifugal, dry, deposition is Li one time 2CO 3Bullion
Figure BDA00001321312900000613
Contain moisture 6～10%, remaining carbonization mother liquor
Figure BDA00001321312900000614
In contain following chemical ingredients:
Li 2O：5.0～6.5g/L Na +：0.4～19.0g/L Cl -：0.02～1.2g/L
SO 4 2-：0.1～4.5g/L Ca 2+：0.0015～0.05g/L Mg 2+：0.02～0.05g/L
This mother liquor
Figure BDA00001321312900000615
Be used for step
Figure BDA00001321312900000616
Recycle Ca in the Quilonum Retard bullion in the hydrogenation 2+≤0.0050%, Mg 2+≤0.010% o'clock, mother liquor
Figure BDA0000132131290000071
Can be recycled, when surpassing this scope, mother liquor
Figure BDA0000132131290000072
Do not answer recycling to use.
Step
Figure BDA0000132131290000073
In the sinker, can also adopt the method for direct adding LiOH, deposition Li 2CO 3: Li in mother liquor during terminal point 2O≤5g/L; Spinning promptly obtains Li one time 2CO 3Bullion And mother liquor
Figure BDA0000132131290000075
Figure BDA0000132131290000076
Washing Li 2CO 3Bullion
Figure BDA0000132131290000077
Pure water=1: 3w/v, 95 ℃ of constant temperature stir 20～30min, centrifuge dripping, the gained deposition is Li one time 2CO 3Wet elaboration
Figure BDA0000132131290000078
Wherein, moisture≤8%, Quilonum Retard content oven dry back>=99.50% promptly obtains battery-level lithium carbonate; The Li that obtains after the washing 2CO 3Wash water
Figure BDA0000132131290000079
In, Li 2O≤5g/L, Li 2CO 3Wash water
Figure BDA00001321312900000710
Circulation is used for a hydrogenation, as a Li 2CO 3Wet elaboration
Figure BDA00001321312900000711
Middle Ca 2+≤0.0050%, Mg 2+≤0.010% o'clock, wash water
Figure BDA00001321312900000712
Can be recycled, when surpassing this scope, wash water
Figure BDA00001321312900000713
Do not answer recycling to use.
Embodiment 2 adopts the industrial method of carbonate type salt lake lithium concentrate direct production pure Lithium Carbonate
With reference to the method for embodiment 1, prepare Li earlier one time 2CO 3Wet elaboration
Figure BDA00001321312900000714
Carry out the carbonization second time again, step is following:
1, secondary carbonization
Li is got in secondary hydrogenation one time 2CO 3Wet elaboration
Figure BDA00001321312900000716
Add pure water, Li 2CO 3Mother liquor Or wash water
Figure BDA00001321312900000718
One or more mixed solution in carry out secondary hydrogenation, concrete grammar and condition are with a hydrogenation
Figure BDA00001321312900000719
Figure BDA00001321312900000720
The secondary removal of impurities adds YD 30 lithium salts, oxalic acid, lithium oxalate, phosphoric acid, Trilithium phosphate, monometallic etc. and carries out removal of impurities filtration, deposition
Figure BDA00001321312900000721
Be mainly the not Li of complete reaction 2CO 3Reach a small amount of slag that removal of impurities stays, this deposition
Figure BDA00001321312900000722
Be used for special disposal, do not get into present method and prepare in the process.
Figure BDA00001321312900000723
The secondary sinker obtains secondary Li with a sinker 2CO 3Bullion
Figure BDA00001321312900000724
Moisture≤8%, remaining mother liquor
Figure BDA00001321312900000725
In, Li 2O≤5g/L, this mother liquor
Figure BDA00001321312900000726
Be used for step
Figure BDA00001321312900000727
Recycle Ca in the Quilonum Retard bullion in the hydrogenation 2+≤0.001%, Mg 2+≤0.001% o'clock, mother liquor
Figure BDA00001321312900000728
But recycling is used, if exceed this scope, mother liquor Do not answer recycling to use.
Figure BDA00001321312900000730
Wash same step
Figure BDA00001321312900000731
The gained deposition is secondary Li 2CO 3Wet elaboration
Figure BDA00001321312900000732
Moisture≤8%, the wash water of washing back gained
Figure BDA00001321312900000733
In, Li 2O:3～5g/L is as secondary Li 2CO 3Ca in the wet elaboration 2+≤0.001%, Mg 2+≤0.001% o'clock, wash water
Figure BDA00001321312900000734
Can be used for secondary hydrogenation, if exceed this scope, wash water
Figure BDA00001321312900000735
Do not answer recycling to use.
(4) oven dry
Material moisture content≤0.1% between
Figure BDA00001321312900000736
dried 200～500 ℃
Figure BDA00001321312900000737
Li 2CO 3Main content>=99.90% meets the pure Lithium Carbonate requirement.
In above-mentioned preparation method:
(1) in step (one's) attrition process, the particle diameter of initial material is more carefully good more, and as influencing anaphase effect greater than 80 μ m, therefore, in the actual production process, concrete particle diameter can be drafted according to energy consumption, cost etc., as long as material particular diameter≤80 μ m.
(2) in the thermal precipitator method removal of impurities process of step (two), during sinker, the liquid consumption is many more, and promptly the solid-liquid mass volume ratio is more little, and removal of impurities is good more, but the lithium loss is big, and therefore, the solid-liquid mass volume ratio is not more than 1: 2, but preferred 1: 2.To the selection of temperature, can be chosen in better effects if when constant temperature stirs more than 90 ℃, but consider production cost, preferred 90 ℃.Simultaneously, churning time should be controlled at more than the 20min, stir 30min after, impurity-eliminating effect does not have and significantly improves, therefore, from cost consideration, preferred 20～30min.
(3) in step (threes') carbonization process, CO 2Pressure when 0.1～0.5MPa, hydrogenation time is short, and hydrogenation is effective, in order to shorten the reaction times, selects to feed CO among the present invention 2Pressure at 0.1～0.5MPa, preferred 0.2～0.3MPa.Simultaneously, in the sinker and washing process of carbonization, select 10～50min, after 30min, effect does not significantly improve, therefore, and can preferred 20～30min.
Particular cases such as charging capacity of the present invention and yield are seen table 1:
Table 1
Figure BDA0000132131290000091
Annotate: 1, " Li in the table 1 2O Do", be meant Li in the material (butt) that obtains that converts 2The content of O;
2, stock number please be joined the process flow sheet of accompanying drawing 1 suitability for industrialized production pure Lithium Carbonate in the table.
When adopting the inventive method to prepare pure Lithium Carbonate, the total recovery of pure Lithium Carbonate can reach more than 95%, and the water saving rate can reach 83.5%, about the total 16h consuming time of omnidistance reaction.
Embodiment 3 adopts technical grade Quilonum Retard or its substandard products to prepare the industrial method of battery-level lithium carbonate
According to technical process as shown in Figure 1, the preparation battery-level lithium carbonate:
1 carbonizations
Figure BDA0000132131290000101
Technical grade Quilonum Retard or its substandard products (Li are got in a hydrogenation 2O:38.0～40.3%), adds pure water, Li 2CO 3Wash water
Figure BDA0000132131290000102
Or Li 2CO 3Mother liquor One or more mixed solutions in, once contain the lithium solid 9. charging capacity be 3000kg～6000kg, liquid add-on 50～100m 3, airtight feeding CO in hydrogenation still provided by the invention (the hydrogenation still is seen embodiment 3) 2, temperature≤25 ℃, the time is 1～2h, pressure 0.2～0.3MPa, terminal point is as the criterion with hydride pH 7.0～8.5, and the flow velocity of material is 3～5m/s in the circulation tube, and every still can prepare hydride 50～100m 3
Figure BDA0000132131290000104
After hydrogen treatment is treated in removal of impurities, in solution, add precipitation agents such as oxalic acid, lithium oxalate, phosphoric acid, Trilithium phosphate or monometallic, make Ca 2+, Mg 2+Divalence, trivalent ion are precipitated, after the filtration, and filter residue
Figure BDA0000132131290000105
Carry out special disposal, do not get in the preparation process of present method, filtrating
Figure BDA0000132131290000106
Be used for further processing.
sinker
Will be through a hydrogenation
Figure BDA0000132131290000108
Removal of impurities
Figure BDA0000132131290000109
After liquid put into the pyrolysis groove, be heated to 90 ℃, constant temperature 20～30 minutes, Li in mother liquor during terminal point 2O≤5g/L; Spinning promptly obtains Li one time 2CO 3Bullion And mother liquor
Figure BDA00001321312900001011
To filtrate
Figure BDA00001321312900001012
Add in the pyrolysis groove, be heated to 90 ℃, constant temperature 20～30min, the pyrolysis terminal point is with Li in the mother liquor 2O≤5g/L is an index, treat that pyrolysis is accomplished after, centrifugal, dry, deposition is Li one time 2CO 3Bullion
Figure BDA00001321312900001013
Contain moisture 6～10%, remaining carbonization mother liquor In contain following chemical ingredients:
Li 2O：5.0～6.5g/L Na +：0.4～19.0g/L Cl -：0.02～1.2g/L
SO 4 2-：0.1～4.5g/L Ca 2+：0.0015～0.05g/L Mg 2+：0.02～0.05g/L
This mother liquor
Figure BDA00001321312900001015
Be used for step
Figure BDA00001321312900001016
Recycle Ca in the Quilonum Retard bullion in the hydrogenation 2+≤0.0050%, Mg 2+≤0.010% o'clock, mother liquor
Figure BDA00001321312900001017
Can be recycled, when surpassing this scope, mother liquor
Figure BDA00001321312900001018
Do not answer recycling to use.
Step
Figure BDA00001321312900001019
In the sinker, can also adopt the method for direct adding LiOH, deposition Li 2CO 3: Li in mother liquor during terminal point 2O≤5g/L; Spinning promptly obtains Li one time 2CO 3Bullion
Figure BDA00001321312900001020
And mother liquor
Figure BDA00001321312900001021
Washing Li 2CO 3Bullion
Figure BDA00001321312900001023
Pure water=1: 3w/v, 95 ℃ of constant temperature stir 20～30min, centrifuge dripping, the gained deposition is Li one time 2CO 3Wet elaboration
Figure BDA00001321312900001024
Wherein, moisture≤8%, Quilonum Retard content oven dry back>=99.50% promptly obtains battery-level lithium carbonate; The Li that obtains after the washing 2CO 3Wash water
Figure BDA00001321312900001025
In, Li 2O≤5g/L, Li 2CO 3Wash water Circulation is used for a hydrogenation, as a Li 2CO 3Wet elaboration
Figure BDA00001321312900001027
Middle Ca 2+≤0.0050%, Mg 2+≤0.010% o'clock, wash water Can be recycled, when surpassing this scope, wash water
Figure BDA00001321312900001029
Do not answer recycling to use.
Embodiment 4 adopts technical grade Quilonum Retard or its substandard products to prepare the industrial method of pure Lithium Carbonate
With reference to the method for embodiment 3, prepare Li earlier one time 2CO 3Wet elaboration
Figure BDA00001321312900001030
Carry out the carbonization second time again, step is following:
1, secondary carbonization
Figure BDA0000132131290000111
Li is got in secondary hydrogenation one time 2CO 3Wet elaboration
Figure BDA0000132131290000112
Add pure water, Li 2CO 3Mother liquor
Figure BDA0000132131290000113
Or carrying out secondary hydrogenation in one or more the mixed solution of wash water, concrete grammar and condition are with a hydrogenation
Figure BDA0000132131290000114
Figure BDA0000132131290000115
The secondary removal of impurities adds EDTA lithium salts, oxalic acid, lithium oxalate, phosphoric acid, Trilithium phosphate, monometallic etc. and carries out removal of impurities filtration, deposition Be mainly the not Li of complete reaction 2CO 3Reach a small amount of slag that removal of impurities stays, this deposition
Figure BDA0000132131290000117
Be used for special disposal, do not get into present method and prepare in the process.
Figure BDA0000132131290000118
The secondary sinker obtains secondary Li with a sinker 2CO 3Bullion Moisture≤8%, remaining mother liquor
Figure BDA00001321312900001110
In, Li 2O≤5g/L, this mother liquor
Figure BDA00001321312900001111
Be used for step
Figure BDA00001321312900001112
Recycle Ca in the Quilonum Retard bullion in the hydrogenation 2+≤0.005%, Mg 2+≤0.005% o'clock, mother liquor But recycling is used, if exceed this scope, mother liquor Do not answer recycling to use.
Figure BDA00001321312900001115
Wash same step
Figure BDA00001321312900001116
The gained deposition is secondary Li 2CO 3Wet elaboration
Figure BDA00001321312900001117
Moisture≤8%, the wash water of washing back gained
Figure BDA00001321312900001118
In, Li 2O:3～5g/L is as secondary Li 2CO 3Ca in the wet elaboration 2+≤0.005%, Mg 2+≤0.005% o'clock, wash water
Figure BDA00001321312900001119
Can be used for secondary hydrogenation, if exceed this scope, wash water
Figure BDA00001321312900001120
Do not answer recycling to use.
(4) oven dry
Material moisture content≤0.1% between
Figure BDA00001321312900001121
dried 200～500 ℃
Li 2CO 3Main content>=99.90% meets the pure Lithium Carbonate requirement.
The inventive method has realized heavy industrialization continuous production pure Lithium Carbonate (Li 2CO 3>=99.90%), this method is with carbonate type lithium source (Li 2O:5.0～40.3%w/w) progressively prepare battery-level lithium carbonate and pure Lithium Carbonate for starting substance; Such lithium source comprises: carbonate type salt lake lithium concentrate, technical grade Quilonum Retard or wherein between product, substandard products, waste product etc., and other contains the material of Quilonum Retard.Preparing method of the present invention makes Li 2Minimum is reduced in the loss of O, and total recovery can reach more than 95%, and the various wash waters and the mother liquor that produce in the production process can be recycled, and the water saving rate can reach more than 83.5%, greatly reduces the consumption of water resources; Adopt common precipitation agent or complexing agent in the removal of impurities process, need not to expend the higher resin of price and carry out removal of impurities, greatly reduced production cost, and, environment friendly had.
Simultaneously, the inventive method can also make battery-level lithium carbonate (Li 2CO 3>=99.50%), total recovery can reach more than 97%, can be according to the market requirement, and selectivity is produced battery-level lithium carbonate or pure Lithium Carbonate, has better market prospect.
Embodiment 5 hydrogenation stills of the present invention
Producing the hydrogenation mode of Quilonum Retard at present, all is to adopt the reaction kettle alr mode to carry out hydrogen treatment, 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 Quilonum Retard, needs more duplication of labour time of cost and energy consumption, can satisfy the production in enormous quantities of Quilonum Retard; Simultaneously, because reaction kettle needs sealing, and the sharp pounding that whisking appliance brings has been brought difficulty for Seal of Equipment undoubtedly, further carries out encapsulation process and makes that also production cost increases.
In order further to satisfy the industrialized production of pure Lithium Carbonate; A kind of hydrogenation still also is provided among the present invention, and as shown in Figure 2, hydrogenation still provided by the invention comprises tank body 1, circulation tube 2 and recycle pump 3; Wherein, Circulation tube 2 one ends are connected with tank body 1 bottom, and the other end of circulation tube 2 is connected with the middle part of tank body 1, and recycle pump 3 is arranged in the circulation tube 2.Leakage fluid dram 5, inlet mouth 6 are set on the circulation tube 2.Circulation tube 2 outer setting prolongs 7.Tank body 1 top is provided with relief port 4 and opening for feed 8.
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, carbonic acid gas being reacted with reactant 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.Inlet mouth is mainly used in the input of carbonic acid gas, and inlet mouth is arranged in the circulation tube, helps mixing of carbonic acid gas; Also be provided with prolong on the circulation tube, can let the temperature of reactant remain at best hydrogenation temperature.Among the present invention, recycle pump, leakage fluid dram, inlet mouth all are arranged on the circulation tube, but the position that its particular location is not limited to mark among the figure, as long as can realize above-mentioned functions, also can in other positions.
Replace the whisking appliance in the existing installation with circulation tube and recycle pump in this hydrogenation still, this circulation hydrogenant mode, stirring intensity is big, and it is low to consume energy, and can make carbonic acid gas 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 hydrogenation 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 hydrogenation still 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.
Utilize hydrogenation still provided by the invention once can make 30～100m 3Hydride; Easy and simple to handle, stable equipment operation is reliable, and maintenance capacity is minimum; Shortcomings such as amount of hydrogenation is little, long reaction time, power consumption height have been overcome in the prior art; Realized the large-scale industrial production pure Lithium Carbonate, to the production efficiency that improves battery-level lithium carbonate and pure Lithium Carbonate, reducing production costs is significant, and has better market prospect.

Claims (10)

1. industrial method of producing battery-level lithium carbonate or pure Lithium Carbonate, it is characterized in that: it comprises the steps:
(1) carbonization: get carbonate type lithium source, wherein Li 2O content is 5.0～40.3%w/w, places the hydrogenation still to carry out above once or twice carbonizing treatment, gets the wet elaboration of Quilonum Retard;
(2) after the wet elaboration oven dry of Quilonum Retard with a carbonizing treatment gained, promptly get battery-level lithium carbonate; Or, after the wet elaboration oven dry of Quilonum Retard with twice above carbonizing treatment gained, promptly get pure Lithium Carbonate.
2. method according to claim 1 is characterized in that: the said carbonizing treatment of step () comprises the steps:
I hydrogenation: with the carbonate type lithium source of particle diameter≤80 μ m, one or more the mixed solution with pure water, mother liquor, wash water adds in the hydrogenation still, feeds CO 2To liquid pH be 7.0～8.5, promptly get hydride;
II removal of impurities: in above-mentioned hydride, add precipitation agent or complexing agent, contamination precipitation is perhaps existed with the stable water soluble complex compound;
The III sinker: hydride heated and stirred or adding LiOH that Step II is handled stir, and solid-liquid separation gets the Quilonum Retard bullion, and mother liquor is used for step I and recycles;
IV washing: the Quilonum Retard bullion is centrifugal after with the pure water heated and stirred, and wash water is used for step I and recycles, and is precipitated as the Quilonum Retard elaboration that wets.
3. method according to claim 2; It is characterized in that: said hydrogenation still comprises tank body (1), circulation tube (2) and recycle pump (3); Wherein, Circulation tube (2) one ends are connected with tank body (1) bottom, and the other end of circulation tube (2) is connected with the middle part of tank body (1), and recycle pump (3) is arranged in the circulation tube (2).
4. method according to claim 3 is characterized in that: in the hydrogenation process of step I, the temperature in the hydrogenation still is 0～50 ℃, CO 2Pressure be 0.1～0.5MPa; The flow velocity of material is 2～8m/s in the circulation tube of hydrogenation still (2).
5. according to any described method of claim 2～4, it is characterized in that: during carbonization for the first time, Ca in the Quilonum Retard bullion among the Step II I 2+≤0.0050%, Mg 2+≤0.010% o'clock, mother liquor was used for step I and recycles; Ca in the wet elaboration of Quilonum Retard among the step IV 2+≤0.0050%, Mg 2+≤0.010% o'clock, wash water was used for step I and recycles;
During carbonization for the second time, Ca in the Quilonum Retard bullion among the Step II I 2+≤0.001%, Mg 2+≤0.001% o'clock, mother liquor was used for step I and recycles; Ca in the wet elaboration of Quilonum Retard among the step IV 2+≤0.001%, Mg 2+≤0.001% o'clock, wash water was used for step I and recycles.
6. according to the described method of claim 2～5, it is characterized in that: adopt the method sinker of heated and stirred among the Step II I, wherein, temperature is 85～100 ℃, and constant temperature stirs 10～60min; Or, adopt the method sinker that adds LiOH among the Step II I, wherein, LiHCO 3: LiOH=1: 0.5～1.2w/w, stir 10～60min;
The condition of step IV washing is the Quilonum Retard bullion: the mass volume ratio of pure water is 1: 2～5w/v, stirs 10～60min at 70～100 ℃ of following constant temperature.
7. method according to claim 2; It is characterized in that: in the impurity removal process of Step II; Said precipitation agent is one or more the compsn in oxalic acid, lithium oxalate, sodium oxalate, phosphoric acid, Trilithium phosphate, sodium phosphate, monometallic, SODIUM PHOSPHATE, MONOBASIC, sodium sulphite, the thioacetamide, and said complexing agent is one or more the compsn in YD 30, YD 30 lithium salts, the disodium edta.
8. according to the described method of claim 1～7, it is characterized in that: in the said carbonate type lithium of step () source, Li 2O content is 32.0～40.3%w/w, and this carbonate type lithium source need not pre-treatment, directly carries out carbonizing treatment;
Or the carbonate type lithium contains Li in the source 2O≤32.0%w/w after pre-treatment is carried out earlier in this carbonate type lithium source, carries out carbonizing treatment again; Wherein, pretreatment process is following:
(1) lithium sodium separates for the first time: get carbonate type lithium source, add pure water or/and contain in the sodium liquid, and heated and stirred, solid-liquid separation must contain the lithium precipitate A; For the second time lithium sodium separates: will contain the lithium precipitate A and add in the pure water, and heated and stirred, solid-liquid separation promptly gets and contains the lithium precipitate B, and the solution after the separation recycles for containing sodium liquid and being used for lithium sodium separation for the first time; Or,
(2) earlier with after the calcining pulverizing of carbonate type lithium source, handle through step (1) again.
9. method according to claim 8; It is characterized in that: in lithium sodium separation for the first time, the lithium sodium sepn process for the second time, the solid-liquid mass volume ratio is 1: 2～5w/v, and Heating temperature is 70～100 ℃; Mixing speed is 50～200r/min, lithium sodium disengaging time 10～60min.
10. method according to claim 8 is characterized in that: Li in the said carbonate type lithium of step () source 2When the content of O is 32.0～40.3%w/w, select for use technical grade Quilonum Retard or its substandard products as the lithium source;
Or, Li in the said carbonate type lithium of step () source 2During O≤32.0%w/w, select for use carbonate type salt lake lithium concentrate as the lithium source.
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CN107804861A (en) * 2017-11-14 2018-03-16 大余县旭日矿业科技有限公司 A kind of method that battery-level lithium carbonate is manufactured using industrial level lithium carbonate
CN107857283A (en) * 2017-12-13 2018-03-30 清华大学 It is a kind of that the isolation technics method for preparing battery-level lithium carbonate is consolidated based on selectivity
CN107857283B (en) * 2017-12-13 2019-11-22 清华大学 A method of isolation technics is consolidated based on selectivity and prepares battery-level lithium carbonate
CN108217699A (en) * 2018-02-08 2018-06-29 江苏九九久科技有限公司 A kind of method that pure Lithium Carbonate is prepared using industrial level lithium carbonate
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CN110894078B (en) * 2019-12-26 2023-09-26 合肥天晟锂业科技有限公司 Method and device for purifying battery-grade lithium carbonate
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CN113461035A (en) * 2021-08-03 2021-10-01 四川国理锂材料有限公司 Method for preparing battery-grade lithium carbonate from high-calcium crude lithium carbonate
CN113620320A (en) * 2021-09-10 2021-11-09 宜春银锂新能源有限责任公司 Process for preparing high-purity lithium carbonate by adopting continuous carbonization method
CN114105172A (en) * 2021-12-20 2022-03-01 福州大学 Method for producing high-purity lithium carbonate by causticizing and carbonizing rough lithium carbonate lime
CN114105172B (en) * 2021-12-20 2023-11-14 福州大学 Method for producing high-purity lithium carbonate by causticizing and carbonizing crude lithium carbonate lime
CN116425178A (en) * 2022-08-02 2023-07-14 兰州交通大学 Method for preparing high-purity lithium solution from salt lake lithium ore
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