CN106365182B - The method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate - Google Patents
The method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate Download PDFInfo
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- CN106365182B CN106365182B CN201610755874.7A CN201610755874A CN106365182B CN 106365182 B CN106365182 B CN 106365182B CN 201610755874 A CN201610755874 A CN 201610755874A CN 106365182 B CN106365182 B CN 106365182B
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 105
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000012141 concentrate Substances 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000009993 causticizing Methods 0.000 claims abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 55
- 238000004845 hydriding Methods 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229920001429 chelating resin Polymers 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 17
- 229910052791 calcium Inorganic materials 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 57
- 239000000047 product Substances 0.000 description 26
- 239000011575 calcium Substances 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- 229960004424 carbon dioxide Drugs 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the method that a kind of industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate, industrial level lithium carbonate and common pure water are configured to slurry according to a certain percentage, the CO of high-purity is added using pulse mode2, controlling reaction temperature is between 20~25 DEG C, until solution changes into the liquid more clarified, filters the liquid, filtrate is squeezed into decomposition reaction kettle, by decomposing, transfers them in causticizing reaction kettle, appropriate Ca (OH) is added thereto2Solution, controlling reaction temperature is between 90~100 DEG C, filtration washing solution while hot, the filtrate is squeezed into concentration kettle, gained concentrate removes the impurity such as Ca, Mg by ion exchange resin, then the concentrate after removal of impurities is squeezed into synthesis reactor, and the CO of high-purity is passed through thereto2Gas, and then prepare the battery-level lithium carbonate of high-purity.This method is the advantage using lithium carbonate energy hydrogenation, effectively utilizes the CO of high-purity2Gas, avoids CO as far as possible during the course of the reaction2Loss, and ensure that hydrogenation is steadily carried out.
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 hydrogenation industry of pulsed
The method that level lithium carbonate prepares battery-level lithium carbonate.
Background technology
Lithium carbonate has more industrial use as the important compound of lithium salts, according to GB/T 11075-2013, YS/T
The correlation national standard 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, and new 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 mostly using lithium carbonate for raw material preparation
Into.So that the demand of lithium carbonate is growing, the field of application also constantly expands, but to its purity also more and more higher,
Produce technical grade lithium carbonate cost is low, yield big, therefore directly prepare battery-level lithium carbonate using industrial level lithium carbonate as raw material
It is most effective.
Battery-level lithium carbonate is produced by raw material of industrial level lithium carbonate at present, mainly there is causticizing process, electrolysis, hydrogenative decomposition
Method etc..Wherein conventional causticizing process refers to lithium carbonate and lime reaction, after filtering and impurity removing lithium hydroxide, then with high-purity
The CO of degree2Gas synthesis prepares the lithium carbonate of LITHIUM BATTERY；Electrolysis is mainly the lithium chloride solution of electrolysis saturation, prepares high-purity
Lithium hydroxide, pass through the CO of high-purity2Gas prepares battery-level lithium carbonate；Hydrogenative decomposition method refers to the lithium carbonate of indissoluble is molten
Liquid changes into the big lithium bicarbonate of solubility, so removes the impurity (mainly including Ca, Mg etc.) for being difficult to be hydrogenated, heats carbonic acid
Hydrogen lithium solution prepares battery-level lithium carbonate.
Such as there is Chinese patent 200710019052.3 using hydrogenation process《One kind utilizes saline lake lithium resource high purity
The process of lithium carbonate》, industrial level lithium carbonate is prepared by raw material of salt lake bittern, CO is passed through2Gas is hydrogenated, by correlation
After dedoping step, lithium bicarbonate is decomposed under condition of negative pressure, washing repeatedly prepares the lithium carbonate of LITHIUM BATTERY；Also there is related journals text
Offer《The influence that hydrogenation conditions are purified to lithium carbonate》(material Leader B, 2011.7,25, Wu Jian) points out 10g lithium carbonate and dioxy
Change carbon flow is 1L/min, and 40min is reacted at 25 DEG C, and obtained utilization rate of carbon dioxide only only has 7.6%；《Thick level carbon
Sour lithium purifying technique process study》In (inorganic chemicals industry, 2013.8,8, Li Yanru) selection 10g lithium carbonate at 20 DEG C and
1L/min carbon dioxide reaction 150min, utilization rate of carbon dioxide 2.02%, the reason for influence above utilization rate of carbon dioxide is low
It is because the amount of dissolved carbon dioxide seldom, influences mass transport process, and then influence CO in solution in the unit interval2The utilization of gas
Rate, causes gas raw material to waste.
The 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, the invention
High-purity CO in hydrogenation process can be greatly improved2The utilization rate of gas.
The present invention is achieved by the following technical programs：Industrial lithium carbonate and water are hybridly prepared into slurry first, led to
Cross electromagnetic pulse feeding device and high-purity CO is added into slurry2Gas, solution becomes soluble stronger lithia water,
And then lithium bicarbonate is decomposed by decomposing pot, the impurity for being difficult to be hydrogenated is removed, then pass through causticizing reaction, concentration, ion exchange
The resin removal of impurity Ca, Mg etc., are passed through the CO of high-purity2Gas, 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 in hydriding reactor
Pressure adds CO with pulsed2Gas, reacts between temperature is 20~25 DEG C, lithium carbonate is converted into lithium bicarbonate, react
Formula is as follows：
Li2CO3+CO2+nH2O=2LiHCO3+(n-1)H2O
(2) decomposition reaction：Obtained lithia water is passed through in decomposing pot, temperature be promoted to 90 DEG C~100 DEG C, carbon
Sour hydrogen 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, than hybrid reaction, temperature in the kettle are maintained by certain mass
At 90 DEG C~100 DEG C, with the progress 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：Above-mentioned causticization liquid is filtered, filtrate is transferred into synthesis reactor, and high-purity thereto
CO2Gas, with the progress of reaction, solution turned cloudy, filtration drying, you can obtain battery-level lithium carbonate, reaction
Formula is as follows：
2LiOH+CO2+H2O=Li2CO3+2H2O
Electromagnetic pulse formula feeding device therein is main by micro-pressure sensor, carbon dioxide solenoid valve, PLC control cabinet structure
Into micro-pressure sensor is used to detect air pressure in hydriding reactor, and air pressure signal is transferred into PLC control cabinet；PLC control cabinet is used to connect
The air pressure signal of micro-pressure sensor transmission is received, handles, when the atmospheric pressure value that micro-pressure sensor is detected is less than default atmospheric pressure value, to
Magnetic valve transmission valve opening instruction；Magnetic valve is located at connection high-purity CO2On the pipeline of storage tank and hydriding reactor, PLC transmission is received
Valve opening after valve opening instruction；The structural representation of the device is shown in accompanying drawing 2.
The present invention provides a kind of method that industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate, including following work
Sequence：
Process one, hydrogenation, filtering：
Weigh the industrial level lithium carbonate and common pure water (electrical conductivity of common pure water≤0.5 μ S/cm, Na of certain mass+≤
0.01%, resistivity≤10M Ω；) be hybridly prepared into slurry, squeeze into hydriding reactor, in hydriding reactor temperature control at 20~25 DEG C,
Open the agitating paddle stirring in hydriding reactor；By high-purity CO2Gas (high-purity CO2Gas meets GB/T 23938-2009 regulations
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 pressure is 0.11~0.12MPa in hydriding reactor；When solution ph is 7~8, the carbonic acid more clarified
Hydrogen lithium solution, now hydrogenation is complete；
Lithia water described in filtration washing, removes SiO2, the insoluble impurity such as silicate, obtain filtrate I；
Process two, decomposition reaction, filtering：
Filtrate I is squeezed into decomposing pot, decomposition temperature is controlled at 90 DEG C~100 DEG C, open agitating paddle in decomposing pot and stir
Mix, charge door is opened wide decomposing pot during the course of the reaction, it is to avoid is decomposed and is produced CO2Gas pressure suppresses equipment in bad kettle, works as decomposing pot
It is the terminal of decomposition reaction when inside being produced again without a large amount of bubbles；
Filter while hot, obtain filter residue II；
Process three, causticizing reaction, filtration washing, concentration and removal：
By filter residue II and food-grade Ca (OH)2(the food-grade Ca (OH)2National standard GB25572-2010 purity exists
More than 95.0%) with mass ratio 1:1-1.5 is mixed, and gained mixture and common pure water are with mass ratio 1:3-4 is configured to causticization liquid,
Squeeze into causticization kettle, causticization temperature in the kettle be promoted to 90 DEG C~100 DEG C, open agitating paddle stirring in causticization kettle, fully reaction,
Obtain causticization liquid；
Causticization liquid described in filtration washing repeatedly, filtrate obtained by each filtration washing is concentrated in together, filtrate III is obtained；
Filtrate III is transferred in concentration kettle, the concentration of lithium hydroxide is concentrated into 20~25g/L, now Ca, Mg impurity are rich
Collection, obtains concentrate III；
By concentrate III by ion exchange resin, Ca, Mg impurity are removed, the ＇ of concentrate III is obtained；
Process four, synthetic reaction, filtering, drying：
The ＇ of concentrate III is squeezed into synthesis reactor, high-purity CO is passed through into synthesis reactor2Temperature control in gas, synthesis reactor
At 90 DEG C~100 DEG C, stirring, synthesising reacting time was controlled at 1~1.5 hour；
Filter while hot, obtain filter residue IV；
Filter residue IV is dried 5~6 hours in 90~100 DEG C of baking oven, fair and clear lithium carbonate is finally given.
In above-mentioned operation one, by high-purity CO2Gas adds hydriding reactor with impulse form, passes through electromagnetic pulse feeding device
It is achieved；The electromagnetic pulse feeding device is main by micro-pressure sensor, magnetic valve, PLC control cabinet, electric power generating composition, wherein：
Micro-pressure sensor is used to detect air pressure in hydriding reactor, and air pressure signal is transferred into PLC control cabinet；
PLC control cabinet is used for the air pressure signal for receiving, handling micro-pressure sensor transmission, the air pressure detected when micro-pressure sensor
When value is less than default atmospheric pressure value, to magnetic valve transmission valve opening instruction；
Magnetic valve is located at connection high-purity CO2On the pipeline of storage tank and hydriding reactor, opened after the valve opening instruction for receiving PLC transmission
Valve；
Power supply is used for PLC control cabinet, micro-pressure sensor, solenoid valve.
In above-mentioned electromagnetic pulse feeding device, micro-pressure sensor is PY210 type micro-pressure sensors；Magnetic valve is LIK types two
Carbonoxide magnetic 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 hydriding reactor temperature control at 20~25 DEG C by way of steam heating or cooling water temperature
Between；Agitating paddle is at the uniform velocity stirred in hydriding reactor, and stir speed (S.S.) control is in 170~180r/min, and the rotating speed of fixed stirring slurry can be with
Effectively control the hydrogenation reaction rate under reaction rate, this stir speed (S.S.) maximum；Hydrogenation time control is in 2~5h, now
Hydrogenation is complete.
In above-mentioned operation one, high-purity CO2Gas inlet flow is controlled in 2~2.5m3/ min, by installed in CO2Storage tank
On gas usage analyzer (model：WXLUGB full-range gas usage in hydrogenation) is detected, now CO2Utilization rate is most
It is high.
In above-mentioned operation three, by filter residue II and food-grade Ca (OH)2Deng mass mixing, gained mixture and common pure water are pressed
Mass ratio 1:3 are configured to causticization liquid, and now lithium carbonate loss amount is minimum；Agitating paddle turning with 170~180r/min in causticization kettle
Speed stirring 4~5 hours, filter residue II and food-grade Ca (OH)2Fully reaction.
In above-mentioned operation three, ion exchange resin can be CH-90 types, 8-hydroxyquinoline or EDTA-2Na, concentrate III
By the ion exchange resin, Ca, Mg impurity can be removed completely, obtain the ＇ of concentrate III.
In above-mentioned operation four, by high-purity CO2Gas is with 1-1.5m3/ min flow is continuously passed through in synthesis reactor, and control is stirred
Speed is mixed in 150~170r/min, generated time and high-purity CO now2Utilization rate is optimal, high-purity CO2Utilization rate reach
To more than 90%；
In above-mentioned operation three, filtration washing causticization liquid 3~4 times, each slurry amount is 15~20 times of material；
Thickening temperature is controlled more than 90 DEG C.
Hydriding reactor and its agitating paddle, decomposing pot endosexine and its blade use titanium matter, with very strong alkali corrosion resistance
Performance.
The inventive method has the advantages that compared with prior art：
(1) hydrogenation adds high-purity CO using pulsed2With adding high-purity CO using continous way2Compare, not only produce
Product can reach the requirement of battery-level lithium carbonate and product quality is excellent, and hydrogenation high-purity CO2Gas effciency is high,
Serve saving CO2The purpose of gas, improves the hydrogenation efficiency of lithium carbonate, while ensureing the homogeneity of pressure in kettle so that hydrogen
Change reacting balance to carry out
(2) in hydriding process, by high-purity CO2Gas (high-purity CO2Gas meets GB/T 23938-2009 regulations
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 pressure is 0.11~0.12MPa, the Li of preparation in hydriding reactor2CO3Li in product2CO3High purity
99.85%, wherein K, Ca, Na, Mg content are respectively 0.0001%, 0.004%, 0.02%, 0.0076%, have reached GB/T
LITHIUM BATTERY Li as defined in the correlation national standard such as 11075-2013, YS/T 582-2013 and rower2CO3Content 99.5%~99.9%
Standard；Also, with being passed through high-purity CO in hydriding process with given pace2The preparation method of gas compares, and product is pure
Du Genggao.
(3) present invention process is simple and easy to apply, easy to operate.
Brief description of the drawings
Fig. 1 is the process chart of the inventive method；
Fig. 2 is electromagnetic pulse feeding device of the invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The present invention is further detailed with reference to embodiment.
Embodiment 1
The embodiment of the present invention provides the pulsed hydrogenation method that industrial level lithium carbonate prepares battery-level lithium carbonate, specific steps
It is as follows：
Hydrogenation：The industrial level lithium carbonate and common pure water for weighing certain mass are hybridly prepared into slurry, common pure water
Consumption is 3~4 times of material, opens in the agitating paddle that hydriding reactor is carried, the hydriding reactor and agitating paddle uses titanium matter, prevent
The corrosion reaction equipment under basic conditions, by the rate adaptation of agitating paddle to 170~180r/min, the rotating speed of fixed stirring slurry can
Effectively to control reaction rate, the hydrogenation reaction rate under this stir speed (S.S.) is maximum, is added using electromagnetic pulse feeding device high
Pure CO2Gas (purity is more than 99.99%), gas velocity is controlled in 2~2.5m3/ min, temperature control is led at 20~25 DEG C
Cross installed in CO2Gas usage analyzer on storage tank detects full-range gas usage, when solution ph is 7~8, solution
Also what is become more clarifies lithia water soluble in water, now hydrogenation completely and CO2Utilization rate highest.
Decomposition reaction：The filtration washing solution, removes the impurity for being difficult to be hydrogenated, and gained filtrate is passed through in decomposing pot, should
Decomposing pot endosexine and blade also use titanium matter, and by decomposition temperature control at 90 DEG C~100 DEG C, the rotating speed of agitating paddle is
170~180r/min, charge door is opened wide decomposing pot during the course of the reaction, it is to avoid is decomposed and is produced CO2Gas pressure is suppressed in bad kettle and set
Standby, the reaction end is produced without a large amount of bubbles, is filtered while hot.
Causticizing reaction：By obtained filter residue and food-grade Ca (OH)2Deng mass mixing, mixed quality and common pure water
In mass ratio 1:3 are configured to causticization liquid, and causticization liquid is squeezed into causticization kettle, and temperature is promoted into 90 DEG C~100 DEG C, turn of agitating paddle
Speed is 170~180r/min, and by the causticizing reaction of 4~5 hours, now lithium carbonate loss amount was minimum, the filtration washing causticization
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 hydroxide is dense
20~25g/L is reduced to, now Ca, Mg impurity are also enriched with more, and the concentrate is slow transitted through equipped with CH-90 type ion exchanges
The pillar of resin, Ca, Mg impurity can be removed completely.
Synthetic reaction：Concentrate after removal of impurities is squeezed into synthesis reactor, high-purity CO is passed through into synthesis reactor2Gas
(purity is more than 99.99%), temperature control is at 90 DEG C~100 DEG C, and stir speed (S.S.) is 150~170r/min, and gas velocity is
1m3/ min, generated time and efficiency now is optimal, high-purity CO2Efficiency can reach more than 90%, the time try one's best control 1~
1.5 hours, the solution is filtered while hot, and filter residue is dried 5~6 hours in 100 DEG C of baking oven, fair and clear carbonic acid is finally given
Lithium.
The index of correlation for the common pure water used above：Electrical conductivity≤0.5 μ S/cm, Na+≤ 0.01%, resistivity≤10M
Ω, and the material of hydriding reactor, decomposing pot, causticization kettle, synthesis reactor apply titanium using titanium alloy or surface, prevent caustic corrosion from setting
It is standby.
Embodiment 2
The method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate：The industrial level lithium carbonates of 200kg are weighed, plus
Enter to 1m3Reactor in, take 600L industrial waters to be added thereto, temperature maintains 25 DEG C, the speed control of agitating paddle existed
180r/min, high-purity CO is added with electromagnetic pulse feeding device2Gas, gas velocity is controlled in 2.4m3/ min, reacts 2.5 hours
Afterwards, high-purity CO2The consumption of gas is 250m3PH value in (normal atmosphere pressure), pH meter detection reactor is 7.6, filters this molten
Liquid, gained filtrate is passed through in decomposing pot, is 90 DEG C by temperature control, and the rotating speed of agitating paddle was 180r/min, by point of 2 hours
Solution reaction, filters to obtain filter residue, by filter residue and food-grade Ca (OH) while hot2Deng mass mixing, mixed quality and common pure water
In mass ratio 1:3 are configured to causticization liquid, temperature are promoted into 90 DEG C, the rotating speed of agitating paddle was 180r/min, by 4.5 hours
Causticizing reaction, is filtered to remove calcium carbonate, with pure water 3 times, the concentration of filtrate lithium hydroxide is concentrated into 25g/L, will be concentrated
Liquid is passed through in synthesis reactor with 2L/min speed by ion exchange resin, then by the concentrate after removal of impurities, is led into synthesis reactor
Enter high-purity CO2Gas (purity is more than 99.99%), temperature control is at 90 DEG C, and stir speed (S.S.) is 170r/min, gas velocity
For 1m3/ min, generated time is 1.2h, is filtered while hot, and filter residue is placed in 100 DEG C of baking oven and dried 6 hours, obtains lithium carbonate production
Product L2.
Embodiment 3
The method that the industrial level lithium carbonate of hydrogenation prepares battery-level lithium carbonate：The industrial level lithium carbonates of 200kg are weighed, are added extremely
1m3Reactor in, take 600L industrial waters to be added thereto, temperature maintains 25 DEG C, by the speed control of agitating paddle in 180r/
Min, gas velocity is controlled in 2.4m3/ min, after reacting 5 hours, high-purity CO2The consumption of gas is 700m3(normal atmosphere pressure)
PH value in pH meter detection reactor is 7.5, filters the solution, gained filtrate is passed through in decomposing pot, is 90 DEG C by temperature control,
The rotating speed of agitating paddle is 180r/min, by the decomposition reaction of 2.5 hours, filter residue is filtered to obtain while hot, by filter residue and food-grade Ca
(OH)2Deng mass mixing, mixed quality and common pure water in mass ratio 1:3 are configured to causticization liquid, and temperature is promoted into 90
DEG C, the rotating speed of agitating paddle is 180r/min, by the causticizing reaction of 5 hours, is filtered to remove calcium carbonate, with pure water 3 times, will
The concentration of filtrate lithium hydroxide is concentrated into 25g/L, by concentrate with 2L/min speed by ion exchange resin, then by removal of impurities
Concentrate afterwards is passed through in synthesis reactor, and high-purity CO is passed through into synthesis reactor2Gas (purity is more than 99.99%), temperature control
System is at 90 DEG C, and stir speed (S.S.) is 170r/min, and gas velocity is 1m3/ min, generated time is 2h, is filtered while hot, and filter residue is put
Dried 6 hours in 100 DEG C of baking oven, obtain lithium carbonate product L3.
The ＇ of embodiment 3
The method that the industrial level lithium carbonate of hydrogenation prepares battery-level lithium carbonate：The industrial level lithium carbonates of 200kg are weighed, are added extremely
1m3Reactor in, take 600L industrial waters to be added thereto, temperature maintains 25 DEG C, by the speed control of agitating paddle in 180r/
Min, high-purity CO is added with electromagnetic pulse feeding device2Gas, gas velocity is controlled in 2.4m3/ min is high after reacting 2.5 hours
Pure CO2The consumption of gas is 330m3PH value in (normal atmosphere pressure), pH meter detection reactor is 7.6, filters the solution, institute
Obtain filtrate to be passed through in decomposing pot, be 90 DEG C by temperature control, the rotating speed of agitating paddle is 180r/min, and the decomposition by 2 hours is anti-
Should, filter residue is filtered to obtain while hot, by filter residue and food-grade Ca (OH)2Deng mass mixing, mixed quality and common pure water press matter
Amount compares 1:3 are configured to causticization liquid, temperature are promoted into 90 DEG C, the rotating speed of agitating paddle was 180r/min, by the causticization of 4.5 hours
Reaction, is filtered to remove calcium carbonate, and with pure water 3 times, the concentration of filtrate lithium hydroxide is concentrated into 25g/L, by concentrate with
2L/min speed is passed through in synthesis reactor by ion exchange resin, then by the concentrate after removal of impurities, and height is passed through into synthesis reactor
Purity CO2Gas (purity is more than 99.99%), temperature control is at 90 DEG C, and stir speed (S.S.) is 170r/min, and gas velocity is
1m3/ min, generated time is 1.2h, is filtered while hot, and filter residue is placed in 100 DEG C of baking oven and dried 6 hours, lithium carbonate product is obtained
L3 ＇.
Embodiment 4
Take industrial level lithium carbonate sample L1 before experiment, product L3 that the product L2 that embodiment 2 is obtained, embodiment 3 are obtained, with
And the product L3 ＇ that the ＇ of embodiment 3 is obtained use the acid-base titration in GB/T 11064.1-2013 to detect, obtain L1 lithium carbonates pure
Degree is that 99.02%, L2 lithium carbonate purity is that 99.85%, L3 lithium carbonate purity is that 99.51%, L3 ＇ lithium carbonate purity is
99.45%；By L1, L2, L3, L3 ＇ products according to Flame Atomic Absorption Spectrometry Determination K, Na in GB/T 11064.4-2013
The content of content, wherein K is respectively 0.02%, 0.0001%, 0.0008%, 0.001%, Na content be respectively 0.18%,
0.02%th, 0.03%, 0.031%；By L1, L2, L3, L3 ＇ products according to the Flame Atomic Absorption Spectrometry in GB/T 11064.5-2013
Spectrographic determination Ca contents, respectively 0.01%, 0.004%, 0.0052%, 0.006%；By L1, L2, L3, L3 ＇ products according to
Flame Atomic Absorption Spectrometry Determination Mg contents in GB/T 11064.6-2013, respectively 0.012%, 0.0076%,
0.0088%th, 0.0086%.
In summary the result of each embodiment compares with the national standard of battery-level lithium carbonate, as a result as shown in table 1 below.
The constituent content of the tetra- kinds of products of L1, L2, L3, L3 ＇ of table 1 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 L3 ＇ hydrogenation high-purity CO2Gas effciency, is listed
Table 2.
The hydrogenation high-purity CO of table 2 L2, L3 and L3 ＇, tri- kinds of products2Gas effciency compares
Remarks：V (actual consumption high-purity COs2Amount)=[m (amount of lithium carbonate) ÷ M (molal weight of lithium carbonate)] ×
22.4L/mol；η (high-purity COs2Gas effciency)=[V (theory consumption high-purity COs2Amount) ÷ V (actual consumption high-purity COs2
Amount) × 100%, wherein high-purity consumes actual CO2Measure and read for gas usage instrument.
From the results shown in Table 1, lithium carbonate product L2, Li prepared by the method provided using the present invention2CO3And K,
Ca, Na, Mg content reach the requirement of battery-level lithium carbonate in the range of national standard；Product L3 also reaches LITHIUM BATTERY carbon
The requirement of sour lithium；Product L3 ＇ are not reaching to the requirement of battery-level lithium carbonate.
L2 is can also be seen that compared with L3 from the result of table 1, Li2CO3Purity is significantly improved, and K contents are substantially reduced,
Its excess-three kind Elements C a, Na, Mg content also has different degrees of reduction.
From table 2 it can be seen that product L2 hydrogenation high-purity CO2The utilization rate of gas is 24.2%, and product L3
Hydrogenation high-purity CO2Gas effciency is only 8.6%, product L3 hydrogenation high-purity CO2Gas effciency and its
The high-purity CO mentioned on its document2The utilization rate of gas is similar, such as " hydrogenation conditions are to carbonic acid for the document that background technology is quoted
Utilization rate of carbon dioxide is 7.6% in the influence of lithium purification "；While product L2 hydrogenation high-purity CO2Gas effciency
It is nearly 3 times of L3, has larger lifting, greatly reduce hydrogenation high-purity CO2Gas usage amount.
As can also be seen from Table 2, product L2 hydrogenation high-purity CO2Gas effciency is above L3 ＇'s.
The embodiment 2 for preparing L2 is differed only in the ＇ of embodiment 3 for preparing L3 ＇ preparation technology's, hydriding process
Middle high-purity CO2Feed postition it is different, i.e., the former is added using pulsed, the latter is using continous way addition.Also, prepare L2
The hydrogenation high-purity CO of actual consumption2Amount is less than L3 ＇, is shown in Table 2.Therefore, hydrogenation is added high using pulsed
Purity CO2With adding high-purity CO using continous 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 method that the industrial level lithium carbonate of pulsed hydrogenation prepares battery-level lithium carbonate, it is characterised in that including following process：
Process one, hydrogenation, filtering：
The industrial level lithium carbonate and common pure water for weighing certain mass are hybridly prepared into slurry, squeeze into hydriding reactor, in hydriding reactor
Temperature control opens the agitating paddle stirring in hydriding reactor at 20~25 DEG C；By high-purity CO2Gas is added with impulse form and hydrogenated
Kettle, CO is adjusted according to pressure feedback in hydriding reactor2Air inlet frequency, it is 0.11~0.12 to remain in hydriding reactor pressure
MPa；When solution ph is 7~8, the lithia water more clarified, now hydrogenation is complete；
Lithia water described in filtration washing, obtains filtrate I；
Process two, decomposition reaction, filtering：
Filtrate I is squeezed into decomposing pot, decomposition temperature is controlled at 90 DEG C~100 DEG C, open agitating paddle stirring in decomposing pot, point
Solving kettle, charge door is opened wide during the course of the reaction, is the terminal of decomposition reaction when being produced again without a large amount of bubbles in decomposing pot；
Filter while hot, obtain filter residue II；
Process three, causticizing reaction, filtration washing, concentration and removal：
By filter residue II and food-grade Ca (OH)2With mass ratio 1:1-1.5 is mixed, and gained mixture and common pure water are with mass ratio 1:
3-4 is configured to causticization liquid, squeezes into causticization kettle, and causticization temperature in the kettle is promoted into 90 DEG C~100 DEG C, opens in causticization kettle and stirs
Oar is stirred, fully reaction, obtains causticization liquid；
Causticization liquid described in filtration washing repeatedly, filtrate obtained by each filtration washing is concentrated in together, filtrate III is obtained；
Filtrate III is transferred in concentration kettle, the concentration of lithium hydroxide is concentrated into 20~25 g/L, obtains concentrate III；
By concentrate III by ion exchange resin, the ＇ of concentrate III is obtained；
Process four, synthetic reaction, filtering, drying：
The ＇ of concentrate III is squeezed into synthesis reactor, high-purity CO is passed through into synthesis reactor2Temperature control is at 90 DEG C in gas, synthesis reactor
~100 DEG C, stirring, synthesising reacting time was controlled at 1~1.5 hour；
Filter while hot, obtain filter residue IV；
Filter residue IV is dried 5~6 hours in 90~100 DEG C of baking oven, fair and clear lithium carbonate is finally given.
2. the method that the industrial level lithium carbonate of pulsed hydrogenation as claimed in claim 1 prepares battery-level lithium carbonate, its feature exists
In：
In process one,
By high-purity CO2Gas adds hydriding reactor with impulse form, is achieved by electromagnetic pulse feeding device；The electromagnetism
Pulse feeding device is main by micro-pressure sensor, magnetic valve, PLC control cabinet, electric power generating composition, wherein：
Micro-pressure sensor is used to detect air pressure in hydriding reactor, and air pressure signal is transferred into PLC control cabinet；
PLC control cabinet is used for the air pressure signal for receiving, handling micro-pressure sensor transmission, when the atmospheric pressure value that micro-pressure sensor is detected is low
When default atmospheric pressure value, to magnetic valve transmission valve opening instruction；
Magnetic valve is located at connection high-purity CO2On the pipeline of storage tank and hydriding reactor, valve opening after the valve opening instruction of PLC transmission is received；
Power supply is used for PLC control cabinet, micro-pressure sensor, solenoid valve.
3. the method that the industrial level lithium carbonate of pulsed hydrogenation as claimed in claim 2 prepares battery-level lithium carbonate, its feature exists
In：
Micro-pressure sensor is PY210 type micro-pressure sensors；Magnetic valve is LIK type carbon dioxide solenoid valves.
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 process 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 process one,
By way of steam heating or cooling water temperature by hydriding reactor temperature control between 20~25 DEG C；Stirred in hydriding reactor
Oar is at the uniform velocity stirred, and stir speed (S.S.) is controlled 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 process one,
High-purity CO2Gas inlet flow is controlled 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 process three,
By filter residue II and food-grade Ca (OH)2Deng mass mixing, gained mixture and common pure water in mass ratio 1:3 be configured to it is severe
Change liquid；Agitating paddle is stirred 4~5 hours with 170~180 r/min rotating speed in causticization kettle.
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 process three,
Ion exchange resin can be CH-90 types, 8-hydroxyquinoline or EDTA-2Na, and concentrate III passes through the amberlite
Fat, obtains the ＇ of concentrate III.
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 process four,
By high-purity CO2Gas is with 1-1.5m3/ min flow is continuously passed through in synthesis reactor, and control stir speed (S.S.) is 150~170
r/min；
In process three,
Filtration washing causticization liquid 3~4 times, each slurry amount is 15~20 times of material；
Thickening temperature is controlled 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 agitating paddle, decomposing pot endosexine and its blade use 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 |
| 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 |
| 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 |
| 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 |
| CN115286017B (en) * | 2022-08-25 | 2024-03-12 | 广东邦普循环科技有限公司 | Preparation method of battery-grade lithium carbonate |
| CN115849414B (en) * | 2022-12-22 | 2023-05-09 | 甘肃睿思科新材料有限公司 | Method for preparing ultrapure lithium carbonate with uniform and stable granularity |
| CN116789153A (en) * | 2023-06-30 | 2023-09-22 | 江西金辉锂业有限公司 | A method for preparing high-purity lithium carbonate from crude lithium carbonate |
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