CN106365182A - Method for preparing battery grade lithium carbonate by using impulse type hydrogenated industrial grade lithium carbonate - Google Patents
Method for preparing battery grade lithium carbonate by using impulse type hydrogenated industrial grade lithium carbonate Download PDFInfo
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- CN106365182A CN106365182A CN201610755874.7A CN201610755874A CN106365182A CN 106365182 A CN106365182 A CN 106365182A CN 201610755874 A CN201610755874 A CN 201610755874A CN 106365182 A CN106365182 A CN 106365182A
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- lithium carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
Abstract
The invention discloses a method for preparing battery grade lithium carbonate by using impulse type hydrogenated industrial grade lithium carbonate. The method comprises the steps of preparing the industrial grade lithium carbonate and common pure water into slurry according to a certain proportion, adding high-purity CO2 in a pulse mode, controlling reaction temperature to be within a range of 20-25 DEG C until the solution is converted into clearer liquid, and filtering the liquid; injecting filtrate into a decomposition reaction kettle, decomposing the filtrate, then transferring the decomposed filtrate into a causticizing reaction kettle, adding a right amount of a Ca(OH)2 solution into the causticizing reaction kettle, controlling reaction temperature to be within a range of 90-100 DEG C, and filtering and washing the solution while the solution is hot; injecting filtrate into a concentration kettle, and removing impurities such as Ca and Mg of concentrated liquor by using ion exchange resin; then, injecting the concentrated liquor without the impurities into a synthesis kettle, and replenishing the synthesis kettle with the high-purity CO2 gas so as to further prepare the high-purity battery grade lithium carbonate. The method utilizes the advantage of hydrogenation of lithium carbonate so as to effectively utilize the high-purity CO2 gas and avoid the loss of CO2 as much as possible in a reaction process, and enables the hydrogenation to be carried out smoothly.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity battery-level lithium carbonate, more particularly, to a kind of pulsed hydrogenation industry
The method that level lithium carbonate prepares battery-level lithium carbonate.
Background technology
Lithium carbonate, as the important compound of lithium salts, has more industrial use, according to gb/t 11075-2013, ys/t
The correlation GB such as 582-2013 and rower, technical grade li2co3Content is less than 99.5%, LITHIUM BATTERY li2co3Content 99.5%～
99.9% .
Lithium carbonate is widely used in glass ceramics, new-energy automobile, alloy and medicine and other fields.In recent years, with me
State advocates the policy of low-carbon environment-friendly, new forms of energy Industry Quick Development, is exactly the most significantly that lithium battery industry rapidly increases, cobalt acid
The positive electrodes such as lithium, lithium nickelate, lithium nickel cobalt dioxide, LiFePO4 and nickle cobalt lithium manganate are used mostly lithium carbonate for raw material prepares
Become.Make the demand of lithium carbonate growing, the field of application also constantly expands, but to its purity also more and more higher,
The lithium carbonate low cost, the yield that produce technical grade are big, therefore directly prepare battery-level lithium carbonate with industrial level lithium carbonate for raw material
It is the most effective.
At present with industrial level lithium carbonate for raw material production battery-level lithium carbonate, mainly there are causticizing process, electrolysis, hydrogenative decomposition
Method etc..Wherein conventional causticizing process refers to lithium carbonate and lime reaction, after filtering and impurity removing Lithium hydrate, then with high-purity
The co of degree2Gas synthesis prepare the lithium carbonate of LITHIUM BATTERY；Electrolysis is mainly the lithium chloride solution being electrolysed saturation, prepares high-purity
Lithium hydrate, by highly purified co2Gas prepares battery-level lithium carbonate；Hydrogenative decomposition method refers to will be molten for the lithium carbonate of indissoluble
Liquid changes into the big lithium bicarbonate of dissolubility, so removes the impurity (mainly including ca, mg etc.) being difficult to be hydrogenated, and heats carbonic acid
Hydrogen lithium solution prepares battery-level lithium carbonate.
Such as saline lake lithium resource high purity " a kind of is utilized using the Chinese patent 200710019052.3 of having of hydrogenation process
The process of lithium carbonate ", industrial level lithium carbonate is prepared for raw material with salt lake bittern, is passed through co2Gas hydrogenates, through related
After dedoping step, decompose lithium bicarbonate under condition of negative pressure, the lithium carbonate of LITHIUM BATTERY is repeatedly prepared in washing；Also there is related journals literary composition
Offer the lithium carbonate and two that " impact that hydrogenation conditions purify " (material Leader b, 2011.7,25, Wu Jian) points out 10 g to lithium carbonate
Oxidation carbon flow is 1l/min, reacts 40min at 25 DEG C, and the utilization rate of carbon dioxide obtaining only only has 7.6%；" thick level carbon
Sour lithium purifying technique process study " select in (inorganic chemicals industry, 2013.8,8, Li Yanru) lithium carbonate of 10 g at 20 DEG C and
1l/min carbon dioxide reaction 150 min, utilization rate of carbon dioxide 2.02%, affect above utilization rate of carbon dioxide low the reason
It is because the amount of dissolved carbon dioxide in solution in the unit interval seldom, affects mass transport process, and then affect co2The utilization of gas
Rate, leads to gas raw material to waste.
Content of the invention
It is an object of the invention to provide the method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate, this invention
In hydrogenation process high-purity co can be greatly improved2The utilization rate of gas.
The present invention is achieved by the following technical programs: first industrial lithium carbonate and water is hybridly prepared into slurry, leads to
Cross electromagnetic pulse feeding device and add high-purity co in slurry2Gas, solution becomes the stronger lithia water of solubility,
And then lithium bicarbonate is decomposed by decomposing pot, remove the impurity being difficult to be hydrogenated, then pass through causticizing reaction, concentrate, ion exchange
The resin removal of impurity ca, mg etc., are passed through highly purified co2Gas, is prepared for the lithium carbonate of LITHIUM BATTERY.Its reaction principle is as follows:
(1) hydrogenation: by industrial level lithium carbonate and water mixed preparing slurry by a certain percentage, according to certain pressure in hydriding reactor
Co is added with pulsed2Gas, reacts between temperature is 20～25 DEG C, lithium carbonate is converted into lithium bicarbonate, reaction equation is such as
Under:
li2co3+co2+nh2o=2lihco3+(n-1)h2o
(2) decomposition reaction: the lithia water obtaining is passed through in decomposing pot, temperature is promoted to 90 DEG C～100 DEG C, bicarbonate
Lithium is decomposed into lithium carbonate, and reaction equation is as follows:
2lihco3= li2co3+h2o+co2
(3) causticizing reaction: industrial level lithium carbonate and ca (oh) 2 press certain mass than hybrid reaction, and temperature in the kettle is maintained 90
DEG C～100 DEG C, with the carrying out of reaction, solution gradually becomes cloudy, and has insoluble matter caco3Produce, reaction equation is as follows:
li2co3+ ca(oh)2=caco3+lioh+h2o
(4) synthetic reaction: filter above-mentioned causticization liquid, filtrate is proceeded to synthesis reactor, and high-purity thereto
Co2Gas, with the carrying out of reaction, solution turned cloudy, filtration drying, you can obtain battery-level lithium carbonate, reaction equation is such as
Under:
2lioh+co2+h2o=li2co3+2h2o
Electromagnetic pulse formula feeding device therein is mainly made up of micro-pressure sensor, carbon dioxide solenoid valve, plc control chamber, micro-
Pressure sensor is used for detecting hydriding reactor internal gas pressure, and air pressure signal is transferred to plc control chamber；Plc control chamber is used for receiving, locates
The air pressure signal of reason micro-pressure sensor transmission, when the atmospheric pressure value of micro-pressure sensor detection is less than default atmospheric pressure value, to electromagnetism
Valve transmission valve opening instruction；Electromagnetic valve is located at connection high-purity co2On the pipeline of storage tank and hydriding reactor, receive the valve opening of plc transmission
Valve opening after instruction；The structural representation of this device is shown in accompanying drawing 2.
The present invention provides a kind of pulsed hydrogenation method that industrial level lithium carbonate prepares battery-level lithium carbonate, including following work
Sequence:
Operation one, hydrogenation, filtration:
Weigh industrial level lithium carbonate and common pure water (commonly pure electrical conductivity of water≤0.5 μ s/cm, the na of certain mass+≤
0.01%, resistivity≤10 m ω；) it is mixedly configured into slurry, squeeze in hydriding reactor, hydrogenation temperature in the kettle controls at 20～25 DEG C,
Open the stirring paddle stirring in hydriding reactor；By high-purity co2Gas (high-purity co2Gas meets gb/t 23938-2009 regulation
Purity be more than 99.99%) with impulse form add hydriding reactor, according in hydriding reactor pressure feedback adjust co2Air inlet frequency
Rate, remains that in hydriding reactor, pressure is 0.11～0.12 mpa；When solution ph is 7～8, obtain the carbonic acid of more clarification
Hydrogen lithium solution, now hydrogenation is complete；
Lithia water described in filtration washing, removes sio2, the insoluble impurity such as silicate, obtain filtrate；
Operation two, decomposition reaction, filtration:
Filtrate is squeezed into decomposing pot, decomposition temperature controls at 90 DEG C～100 DEG C, open stirring paddle stirring in decomposing pot, point
Charge door opens wide solution kettle during the course of the reaction, it is to avoid decomposes and produces co2Gas pressure suppresses equipment in bad kettle, when in decomposing pot more no
A large amount of bubbles are the terminal of decomposition reaction when producing；
Filtered while hot, obtains filtering residue；
Operation three, causticizing reaction, filtration washing, concentration, remove impurity:
By filtering residue and food stage ca (oh)2(described food stage ca (oh)2The purity of GB gb25572-2010 95.0% with
On) with mass ratio 1:1-1.5 mixing, gained mixture and common pure water are configured to causticization liquid with mass ratio 1:3-4, squeeze into causticization
In kettle, causticization temperature in the kettle is promoted to 90 DEG C～100 DEG C, opens stirring paddle stirring in causticization kettle, fully react, obtain causticization
Liquid；
Causticization liquid described in filtration washing repeatedly, each filtration washing gained filtrate is concentrated in together, obtains filtrate；
Filtrate is transferred in concentration kettle, the concentration of Lithium hydrate is concentrated into 20～25 g/l, now ca, mg impurity enriched,
Obtain concentrated solution；
Concentrated solution is passed through ion exchange resin, removes ca, mg impurity, obtain concentrated solution ＇；
Operation four, synthetic reaction, filtration, drying:
Concentrated solution ＇ is squeezed in synthesis reactor, in synthesis reactor, is passed through high-purity co2Gas, synthesis temperature in the kettle controls 90
DEG C～100 DEG C, stirring, synthesising reacting time controlled at 1～1.5 hour；
Filtered while hot, obtains filtering residue；
Filtering residue is dried 5～6 hours in 90～100 DEG C of baking oven, finally gives fair and clear lithium carbonate.
In above-mentioned operation one, by high-purity co2Gas adds hydriding reactor with impulse form, by electromagnetic pulse feeding device
It is achieved；Described electromagnetic pulse feeding device mainly by micro-pressure sensor, electromagnetic valve, plc control chamber, electric power generating composition, wherein:
Micro-pressure sensor is used for detecting hydriding reactor internal gas pressure, and air pressure signal is transferred to plc control chamber；
Plc control chamber is used for receiving, process the air pressure signal of micro-pressure sensor transmission, when the atmospheric pressure value of micro-pressure sensor detection is low
When default atmospheric pressure value, to electromagnetic valve transmission valve opening instruction；
Electromagnetic valve is located at connection high-purity co2On the pipeline of storage tank and hydriding reactor, receive valve opening after the valve opening instruction of plc transmission；
Power supply is used for plc control chamber, micro-pressure sensor, solenoid valve.
In above-mentioned electromagnetic pulse feeding device, micro-pressure sensor is py210 type micro-pressure sensor；Electromagnetic valve is lik type two
Carbonoxide electromagnetic valve.
In above-mentioned operation one, the addition quality of common pure water is 3～4 times of industrial lithium carbonate quality；
In above-mentioned operation one, by steam heat up or cooling water temperature by way of by hydriding reactor temperature control 20～25 DEG C it
Between；In hydriding reactor, stirring paddle at the uniform velocity stirs, and stir speed (S.S.) controls in 170～180 r/min, and the rotating speed of fixing stirring slurry can have
Effect controls reaction rate, and the hydrogenation reaction rate under this stir speed (S.S.) is maximum；Hydrogenation time control is in 2～5 h, now hydrogen
Change reaction completely.
In above-mentioned operation one, high-purity co2Gas inlet flow controls in 2～2.5 m3/ min, by being arranged on co2Storage
Full-range gas usage in gas usage analyzer (model: wxlugb) detection hydrogenation on tank, now co2Utilization rate
Highest.
In above-mentioned operation two, by filtering residue and food stage ca (oh)2Deng mass mixing, gained mixture and common pure water are pressed
Mass ratio 1:3 is configured to causticization liquid, and now lithium carbonate loss amount is minimum；Stirring paddle turning with 170～180 r/min in causticization kettle
Speed stirring 4～5 hours, filtering residue and food stage ca (oh)2Fully react.
In above-mentioned operation three, ion exchange resin can be ch-90 type, 8-hydroxyquinoline or edta-2na, concentrated solution
By described ion exchange resin, ca, mg impurity can be completely removed, obtain concentrated solution ＇.
In above-mentioned operation three, by high-purity co2Gas is with 1-1.5m3The flow of/min is continuously passed through in synthesis reactor, and control is stirred
Mix speed in 150～170 r/min, generated time now and high-purity co2Utilization rate is optimal, high-purity co2Utilization rate reach
To more than 90%；
Filtration washing causticization liquid 3～4 times, each slurry amount is 15～20 times of material；
Thickening temperature all controls more than 90 DEG C.
Hydriding reactor and its stirring paddle, decomposing pot endosexine and its blade, all using titanium matter, have very strong alkali corrosion resistance
Performance.
The inventive method compared with prior art has the advantages that
(1) hydrogenation adopts pulsed to add high-purity co2Add high-purity co with using continuous way2Compare, not only product
The requirement of battery-level lithium carbonate can be reached and product quality is excellent, and hydrogenation high-purity co2Gas effciency is high, rises
Arrive saving co2The purpose of gas, improves the hydrogenation efficiency of lithium carbonate, ensures the homogeneity of pressure in kettle so that hydrogenating simultaneously
Reacting balance is carried out
(2) in hydriding process, by high-purity co2Gas (high-purity co2Gas meets gb/t 23938-2009 regulation
Purity is more than 99.99%) hydriding reactor is added with impulse form, co is adjusted according to pressure feedback in hydriding reactor2Air inlet frequency,
Remain that in hydriding reactor, pressure is 0.11～0.12 mpa, the li of preparation2co3Li in product2co3High purity 99.85%,
Wherein k, ca, na, mg content be respectively 0.0001%, 0.004%, 0.02%, 0.0076%, reached gb/t 11075-2013,
The correlation GB such as ys/t 582-2013 and LITHIUM BATTERY li that specifies of rower2co3The standard of content 99.5%～99.9%；And, with
In hydriding process, high-purity co is passed through with given pace2The preparation method of gas compares, and product purity is higher.
(3) present invention process is simple, easy to operate.
Brief description
Fig. 1 is the process chart of the inventive method；
Fig. 2 is the electromagnetic pulse feeding device of the present invention.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
With reference to embodiment, the present invention is further detailed.
Embodiment 1
The embodiment of the present invention provides the pulsed hydrogenation method that industrial level lithium carbonate prepares battery-level lithium carbonate, comprises the following steps that
Shown:
Hydrogenation: weigh the industrial level lithium carbonate of certain mass and common pure water is mixedly configured into slurry, common pure water consumption
It is 3～4 times of material, open in the stirring paddle that hydriding reactor carries, this hydriding reactor and stirring paddle is all using titanium matter, prevent strong
Corrosion reaction equipment under the conditions of alkali, by the rate adaptation of stirring paddle to 170～180 r/min, the rotating speed of fixing stirring slurry is permissible
Effective control reaction rate, the hydrogenation reaction rate under this stir speed (S.S.) is maximum, is added high-purity using electromagnetic pulse feeding device
co2Gas (purity is more than 99.99%), gas velocity controls in 2～2.5 m3/ min, temperature control, at 20～25 DEG C, is passed through
It is arranged on co2Gas usage analyzer on storage tank detects full-range gas usage, when solution ph is 7～8, solution
Become more clarifies lithia water soluble in water, and now hydrogenation is completely and co2Utilization rate highest.
Decomposition reaction: this solution of filtration washing, remove the impurity being difficult to be hydrogenated, gained filtrate is passed through in decomposing pot, should
Decomposing pot endosexine and blade, also all using titanium matter, decomposition temperature are controlled at 90 DEG C～100 DEG C, the rotating speed of stirring paddle is
170～180 r/min, charge door opens wide decomposing pot during the course of the reaction, it is to avoid decomposes and produces co2Gas pressure is suppressed in bad kettle and is set
Standby, this reaction end is that do not have a large amount of bubbles to produce, filtered while hot.
Causticizing reaction: by the filtering residue obtaining and food stage ca (oh)2Deng mass mixing, mixed quality and common pure water
1:3 in mass ratio is configured to causticization liquid, and causticization liquid is squeezed into causticization kettle, and temperature is promoted to 90 DEG C～100 DEG C, stirring paddle turn
Speed is 170～180 r/min, and through the causticizing reaction of 4～5 hours, now lithium carbonate loss amount was minimum, this causticization of filtration washing
Liquid 3～4 times, each slurry amount is 15～20 times of material, and filtrate is transferred in concentration kettle, and the concentration of Lithium hydrate is dense
Be reduced to 20～25 g/l, now ca, mg impurity be also enriched with more, by this concentrated solution slow transit through equipped with ch-90 type ion hand over
Change the pillar of resin, ca, mg impurity can be completely removed.
Synthetic reaction: the concentrated solution after remove impurity is squeezed into synthesis reactor, is passed through high-purity co in synthesis reactor2Gas
(purity is more than 99.99%), at 90 DEG C～100 DEG C, stir speed (S.S.) is 150～170 r/min to temperature control, and gas velocity is
1m3/ min, generated time now and efficiency are optimal, high-purity co2Efficiency can reach more than 90%, and the time controls 1 as far as possible～
1.5 hours, this solution of filtered while hot, filtering residue is dried 5～6 hours in 100 DEG C of baking oven, finally gives fair and clear carbonic acid
Lithium.
The index of correlation of the common pure water more than used: electrical conductivity≤0.5 μ s/cm, na+≤ 0.01%, resistivity≤10 m
ω, and the material of hydriding reactor, decomposing pot, causticization kettle, synthesis reactor all applies titanium using titanium alloy or surface, prevents caustic corrosion from setting
Standby.
Embodiment 2
The method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate: weigh 200 kg industry level lithium carbonates, add
To 1 m3Reactor in, take 600 l water for industrial uses to be added thereto, temperature maintains 25 DEG C, and the rate controlled of stirring paddle is existed
180 r/min, add high-purity co with electromagnetic pulse feeding device2Gas, gas velocity controls in 2.4 m3/ min, reaction 2.5 is little
Shi Hou, high-purity co2The consumption of gas is 250 m3(standard atmosphere pressure), the ph value in ph meter detection reactor is 7.6, filters
This solution, gained filtrate is passed through in decomposing pot, and temperature control is 90 DEG C, and the rotating speed of stirring paddle is 180 r/min, little through 2
When decomposition reaction, filtered while hot obtains filtering residue, by filtering residue and food stage ca (oh)2Deng mass mixing, mixed quality and general
Logical pure water 1:3 in mass ratio is configured to causticization liquid, and temperature is promoted to 90 DEG C, and the rotating speed of stirring paddle is 180 r/min, passes through
The causticizing reaction of 4.5 hours, is filtered to remove Calcium Carbonate, with pure water 3 times, the concentration of filtrate Lithium hydrate is concentrated into 25
G/l, concentrated solution is passed through ion exchange resin with the speed of 2l/min, then the concentrated solution after remove impurity is passed through in synthesis reactor, to
It is passed through high-purity co in synthesis reactor2Gas (purity is more than 99.99%), at 90 DEG C, stir speed (S.S.) is 170 r/ to temperature control
Min, gas velocity is 1m3/ min, generated time is 1.2 h, filtered while hot, filtering residue is placed in 100 DEG C of baking oven dry 6 little
When, obtain lithium carbonate product l2.
Embodiment 3
The method that the industrial level lithium carbonate of hydrogenation prepares battery-level lithium carbonate: weigh 200 kg industry level lithium carbonates, add to 1 m3
Reactor in, take 600 l water for industrial uses to be added thereto, temperature maintains 25 DEG C, by the rate controlled of stirring paddle in 180 r/
Min, gas velocity controls in 2.4 m3/ min, after reacting 5 hours, high-purity co2The consumption of gas is 700 m3(normal atmosphere
Under) ph meter detection reactor in ph value be 7.5, filter this solution, gained filtrate is passed through in decomposing pot, by temperature control be 90
DEG C, the rotating speed of stirring paddle is 180 r/min, and through the decomposition reaction of 2.5 hours, filtered while hot obtained filtering residue, by filtering residue and food
Level ca (oh)2Deng mass mixing, mixed quality and common pure water 1:3 in mass ratio are configured to causticization liquid, and temperature is lifted
To 90 DEG C, the rotating speed of stirring paddle is 180 r/min, through the causticizing reaction of 5 hours, is filtered to remove Calcium Carbonate, with pure water 3
Secondary, the concentration of filtrate Lithium hydrate is concentrated into 25 g/l, concentrated solution is passed through ion exchange resin with the speed of 2l/min, then
Concentrated solution after remove impurity is passed through in synthesis reactor, in synthesis reactor, is passed through high-purity co2Gas (purity is more than 99.99%), temperature
Degree controls at 90 DEG C, and stir speed (S.S.) is 170 r/min, and gas velocity is 1m3/ min, generated time is 2 h, filtered while hot, will
Filtering residue is placed in 100 DEG C of baking oven and is dried 6 hours, obtains lithium carbonate product l3.
Embodiment 3 ＇
The method that the industrial level lithium carbonate of hydrogenation prepares battery-level lithium carbonate: weigh 200 kg industry level lithium carbonates, add to 1 m3
Reactor in, take 600 l water for industrial uses to be added thereto, temperature maintains 25 DEG C, by the rate controlled of stirring paddle in 180 r/
Min, adds high-purity co with electromagnetic pulse feeding device2Gas, gas velocity controls in 2.4 m3/ min, after reacting 2.5 hours,
High-purity co2The consumption of gas is 330 m3(standard atmosphere pressure), the ph value in ph meter detection reactor is 7.6, filters this molten
Liquid, gained filtrate is passed through in decomposing pot, and temperature control is 90 DEG C, and the rotating speed of stirring paddle was 180 r/min, through 2 hours
Decomposition reaction, filtered while hot obtains filtering residue, by filtering residue and food stage ca (oh)2Deng mass mixing, mixed quality and commonly pure
Water 1:3 in mass ratio is configured to causticization liquid, and temperature is promoted to 90 DEG C, and the rotating speed of stirring paddle is 180 r/min, little through 4.5
When causticizing reaction, be filtered to remove Calcium Carbonate, with pure water 3 times, the concentration of filtrate Lithium hydrate be concentrated into 25 g/l, will
Concentrated solution passes through ion exchange resin with the speed of 2l/min, then the concentrated solution after remove impurity is passed through in synthesis reactor, to synthesis reactor
In be passed through high-purity co2Gas (purity is more than 99.99%), at 90 DEG C, stir speed (S.S.) is 170 r/min to temperature control, gas
Body speed is 1m3/ min, generated time is 1.2 h, and filtering residue is placed in 100 DEG C of baking oven and is dried 6 hours, obtains by filtered while hot
Lithium carbonate product l3 ＇.
Embodiment 4
Treating excess syndrome industrial level lithium carbonate sample l1, product l3, Yi Jishi that the product l2 that embodiment 2 is obtained, embodiment 3 obtain before testing
Apply the product l3 ＇ that example 3 ＇ obtains and adopt acid-base titrations detection in gb/t 11064.1-2013, obtaining l1 lithium carbonate purity is
99.02%th, l2 lithium carbonate purity be 99.85%, l3 lithium carbonate purity be 99.51%, l3 ＇ lithium carbonate purity be 99.45%；By l1,
L2, l3, l3 ＇ product according to Flame Atomic Absorption Spectrometry Determination k, na content in gb/t 11064.4-2013, wherein k
Content is respectively 0.02%, 0.0001%, 0.0008%, the content of 0.001%, na be respectively 0.18%, 0.02%, 0.03%,
0.031%；L1, l2, l3, l3 ＇ product is contained according to the Flame Atomic Absorption Spectrometry Determination ca in gb/t 11064.5-2013
Amount, respectively 0.01%, 0.004%, 0.0052%, 0.006%；By l1, l2, l3, l3 ＇ product according to gb/t 11064.6-2013
In Flame Atomic Absorption Spectrometry Determination mg content, respectively 0.012%, 0.0076%, 0.0088%, 0.0086%.
The result of comprehensive various embodiments above compares with the national standard of battery-level lithium carbonate, and result is as shown in table 1 below.
The constituent content of table 1 tetra- kinds of products of l1, l2, l3, l3 ＇ compares
| Detection project | l1 | l2 | l3 | L3 ＇ | National standard |
| li2co3(wt%) | 99.02% | 99.85% | 99.51% | 99.45% | 99.5% |
| k(wt%) | 0.02% | 0.0001% | 0.0008% | 0.001% | 0.001% |
| ca(wt%) | 0.01% | 0.004% | 0.0052% | 0.006% | 0.005% |
| na(wt%) | 0.18% | 0.02% | 0.03% | 0.031% | 0.025% |
| mg(wt%) | 0.012% | 0.0076% | 0.0088% | 0.0086% | 0.008% |
Meanwhile, it is clearer comparative product l2, l3 and hydrogenation high-purity co of l3 ＇2Gas effciency, lists table 2.
Hydrogenation high-purity co of table 2 tri- kinds of products of l2, l3 and l3 ＇2Gas effciency compares
| Sample | Hydrogenation theory should consume high-purity co2Amount/m3 | Hydrogenation high-purity consumes actual co2Amount/m3 | Hydrogenation high-purity co2Gas effciency/% |
| l2 | 60.54 | 250 | 24.20% |
| l3 | 60.54 | 700 | 8.60% |
| L3 ＇ | 60.54 | 330 | 18.35% |
Remarks: v (actual consumption high-purity co2Amount)=[m (amount of lithium carbonate) ÷ m (molal weight of lithium carbonate)] × 22.4l/
mol；η (high-purity co2Gas effciency)=[v (theoretical consumption high-purity co2Amount) ÷ v (actual consumption high-purity co2Amount) ×
100%, wherein high-purity consumes actual co2Measure and read for gas usage instrument.
From the results shown in Table 1, the lithium carbonate product l2, li of the method preparation being provided using the present invention2co3And k, ca,
The content of na, mg, all in the range of national standard, reaches the requirement of battery-level lithium carbonate；Product l3 also reaches battery-level lithium carbonate
Requirement；Product l3 ＇ is not reaching to the requirement of battery-level lithium carbonate.
From the result of table 1 it can also be seen that l2 is compared with l3, li2co3Purity is significantly improved, and k content substantially reduces,
Its excess-three kind element ca, na, mg content also has different degrees of reduction.
From table 2 it can be seen that hydrogenation high-purity co of product l22The utilization rate of gas is 24.2%, and product l3
Hydrogenation high-purity co2Gas effciency is only 8.6%, hydrogenation high-purity co of product l32Gas effciency and other
High-purity co mentioned on document2The utilization rate of gas is similar to, and " hydrogenation conditions are to lithium carbonate for the document that such as background technology is quoted
In the impact of purification ", utilization rate of carbon dioxide is 7.6%；Hydrogenation high-purity co of product l2 simultaneously2Gas effciency is l3
Nearly 3 times, have larger lifting, greatly reduce hydrogenation high-purity co2Gas usage amount.
As can also be seen from Table 2, hydrogenation high-purity co of product l22Gas effciency is above l3 ＇'s.
The embodiment 2 preparing l2 is differed only in the preparation technology's of embodiment 3 ＇ preparing l3 ＇, hydriding process
Middle high-purity co2Feed postition different, that is, the former adopts pulsed to add, the latter adopts continuous way to add.And, prepare l2
Hydrogenation high-purity co of actual consumption2Amount is less than l3 ＇, is shown in Table 2.Therefore, hydrogenation adopts pulsed to add height
Purity co2Add high-purity co with using continuous way2Compare, not only product can reach requirement and the product of battery-level lithium carbonate
Good quality, and hydrogenation high-purity co2Gas effciency is high.
Claims (10)
1. the industrial level lithium carbonate of pulsed hydrogenation prepares the method for battery-level lithium carbonate it is characterised in that including following operation:
Operation one, hydrogenation, filtration:
Weigh the industrial level lithium carbonate of certain mass and common pure water is mixedly configured into slurry, squeeze in hydriding reactor, in hydriding reactor
Temperature control, at 20～25 DEG C, opens the stirring paddle stirring in hydriding reactor；By high-purity co2Gas adds hydrogenation with impulse form
Kettle, adjusts co according to pressure feedback in hydriding reactor2Air inlet frequency, remain in hydriding reactor that pressure is 0.11～0.12
mpa；When solution ph is 7～8, obtain the lithia water of more clarification, now hydrogenation is complete；
Lithia water described in filtration washing, obtains filtrate；
Operation two, decomposition reaction, filtration:
Filtrate is squeezed into decomposing pot, decomposition temperature controls at 90 DEG C～100 DEG C, open stirring paddle stirring in decomposing pot, point
Charge door opens wide solution kettle during the course of the reaction, the terminal of as decomposition reaction when no a large amount of bubbles produce again in decomposing pot；
Filtered while hot, obtains filtering residue；
Operation three, causticizing reaction, filtration washing, concentration, remove impurity:
By filtering residue and food stage ca (oh)2With mass ratio 1:1-1.5 mixing, gained mixture and common pure water are with mass ratio 1:
3-4 is configured to causticization liquid, squeezes in causticization kettle, and causticization temperature in the kettle is promoted to 90 DEG C～100 DEG C, opens stirring in causticization kettle
Oar stirs, and fully reacts, obtains causticization liquid；
Causticization liquid described in filtration washing repeatedly, each filtration washing gained filtrate is concentrated in together, obtains filtrate；
Filtrate is transferred in concentration kettle, the concentration of Lithium hydrate is concentrated into 20～25 g/l, obtains concentrated solution；
Concentrated solution is passed through ion exchange resin, obtains concentrated solution ＇；
Operation four, synthetic reaction, filtration, drying:
Concentrated solution ＇ is squeezed in synthesis reactor, in synthesis reactor, is passed through high-purity co2Gas, synthesis temperature in the kettle controls at 90 DEG C
～100 DEG C, stirring, synthesising reacting time controlled at 1～1.5 hour；
Filtered while hot, obtains filtering residue；
Filtering residue is dried 5～6 hours in 90～100 DEG C of baking oven, finally gives fair and clear lithium carbonate.
2. the method that pulsed hydrogenation industry level lithium carbonate as claimed in claim 1 prepares battery-level lithium carbonate, its feature exists
In:
In operation one,
By high-purity co2Gas adds hydriding reactor with impulse form, is achieved by electromagnetic pulse feeding device；Described electromagnetism
Pulse feeding device mainly by micro-pressure sensor, electromagnetic valve, plc control chamber, electric power generating composition, wherein:
Micro-pressure sensor is used for detecting hydriding reactor internal gas pressure, and air pressure signal is transferred to plc control chamber；
Plc control chamber is used for receiving, process the air pressure signal of micro-pressure sensor transmission, when the atmospheric pressure value of micro-pressure sensor detection is low
When default atmospheric pressure value, to electromagnetic valve transmission valve opening instruction；
Electromagnetic valve is located at connection high-purity co2On the pipeline of storage tank and hydriding reactor, receive valve opening after the valve opening instruction of plc transmission；
Power supply is used for plc control chamber, micro-pressure sensor, solenoid valve.
3. the method that pulsed hydrogenation industry level lithium carbonate as claimed in claim 2 prepares battery-level lithium carbonate, its feature exists
In:
Micro-pressure sensor is py210 type micro-pressure sensor；Electromagnetic valve is lik type carbon dioxide solenoid valve.
4. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, it is special
Levy and be:
In operation one,
The addition quality of common pure water is 3～4 times of industrial lithium carbonate quality.
5. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, it is special
Levy and be:
In operation one,
By steam heat up or cooling water temperature by way of by hydriding reactor temperature control between 20～25 DEG C；Stir in hydriding reactor
Oar at the uniform velocity stirs, and stir speed (S.S.) controls in 170～180 r/min；Hydrogenation time control is in 2～5 h.
6. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, it is special
Levy and be:
In operation one,
High-purity co2Gas inlet flow controls in 2～2.5 m3/min.
7. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, it is special
Levy and be:
In operation two,
By filtering residue and food stage ca (oh)2Deng mass mixing, gained mixture and common pure water 1:3 in mass ratio are configured to severe
Change liquid；In causticization kettle, stirring paddle is stirred 4～5 hours with the rotating speed of 170～180 r/min.
8. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, it is special
Levy and be:
In operation three,
Ion exchange resin can be ch-90 type, 8-hydroxyquinoline or edta-2na, and concentrated solution passes through described amberlite
Fat, obtains concentrated solution ＇.
9. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, it is special
Levy and be:
In operation three,
By high-purity co2Gas is with 1-1.5m3The flow of/min is continuously passed through in synthesis reactor, controls stir speed (S.S.) 150～170
r/min；
Filtration washing causticization liquid 3～4 times, each slurry amount is 15～20 times of material；
Thickening temperature all controls more than 90 DEG C.
10. the method that the industrial level lithium carbonate of pulsed hydrogenation as described in claim 1,2 or 3 prepares battery-level lithium carbonate, its
It is characterised by:
Hydriding reactor and its stirring paddle, decomposing pot endosexine and its blade are all using titanium matter.
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| CN107265483A (en) * | 2017-07-17 | 2017-10-20 | 中国恩菲工程技术有限公司 | The method for preparing monohydrate lithium hydroxide |
| CN107902680A (en) * | 2017-11-15 | 2018-04-13 | 天元锂电材料河北有限公司 | A kind of method of industry level lithium carbonate refined raw production battery-level lithium carbonate |
| CN108217700A (en) * | 2018-03-12 | 2018-06-29 | 安徽科达洁能股份有限公司 | A kind of system and method for preparing battery-level lithium carbonate |
| CN108295791A (en) * | 2018-04-11 | 2018-07-20 | 宜春市鼎鑫高能科技有限公司 | A kind of lithium carbonate carbonic acid hydrogenation apparatus |
| CN110817908A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | System and method for preparing high-purity lithium carbonate by using lithium-containing waste material |
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| CN110937613A (en) * | 2019-12-18 | 2020-03-31 | 甘肃睿思科新材料有限公司 | Hydrogenation purification process method |
| CN112357937A (en) * | 2020-11-12 | 2021-02-12 | 萍乡市拓源实业有限公司 | Method for preparing battery-grade lithium carbonate from lithium iron phosphate |
| CN115849414A (en) * | 2022-12-22 | 2023-03-28 | 甘肃睿思科新材料有限公司 | Method for preparing ultrapure lithium carbonate with uniform and stable particle size |
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| CN107265483A (en) * | 2017-07-17 | 2017-10-20 | 中国恩菲工程技术有限公司 | The method for preparing monohydrate lithium hydroxide |
| CN107902680A (en) * | 2017-11-15 | 2018-04-13 | 天元锂电材料河北有限公司 | A kind of method of industry level lithium carbonate refined raw production battery-level lithium carbonate |
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| CN108217700B (en) * | 2018-03-12 | 2024-01-26 | 安徽科达新能源装备有限公司 | System and method for preparing battery-grade lithium carbonate |
| CN108295791A (en) * | 2018-04-11 | 2018-07-20 | 宜春市鼎鑫高能科技有限公司 | A kind of lithium carbonate carbonic acid hydrogenation apparatus |
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| CN110937613A (en) * | 2019-12-18 | 2020-03-31 | 甘肃睿思科新材料有限公司 | Hydrogenation purification process method |
| CN110894077A (en) * | 2019-12-26 | 2020-03-20 | 合肥天晟锂业科技有限公司 | Preparation method and preparation device of battery-grade lithium carbonate |
| CN112357937A (en) * | 2020-11-12 | 2021-02-12 | 萍乡市拓源实业有限公司 | Method for preparing battery-grade lithium carbonate from lithium iron phosphate |
| WO2024040907A1 (en) * | 2022-08-25 | 2024-02-29 | 广东邦普循环科技有限公司 | Preparation method for battery-grade lithium carbonate |
| CN115849414A (en) * | 2022-12-22 | 2023-03-28 | 甘肃睿思科新材料有限公司 | Method for preparing ultrapure lithium carbonate with uniform and stable particle size |
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