CN106745098A - Multistage hydrogenation apparatus and method - Google Patents

Multistage hydrogenation apparatus and method Download PDF

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Publication number
CN106745098A
CN106745098A CN201611038246.3A CN201611038246A CN106745098A CN 106745098 A CN106745098 A CN 106745098A CN 201611038246 A CN201611038246 A CN 201611038246A CN 106745098 A CN106745098 A CN 106745098A
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level
grades
hydriding reactor
hydriding
gas
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CN106745098B (en
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张云河
许开华
郭苗苗
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Abstract

The present invention provides a kind of multistage hydrogenation apparatus, including multistage hydriding reactor and feeding device, wherein multistage hydriding reactor is main being in series by one-level, two grades ..., N grades of multiple hydriding reactors；Feeding device is used to add CO to hydriding reactors at different levels2Gas, including：For providing high-purity CO to N grades of hydriding reactor2High-purity CO2Storage tank, for reclaiming one-level, two grades ..., the CO in N grades of hydriding reactor2And the CO that will be reclaimed2One-level, two grades ..., the collection CO of 1 grade of hydriding reactor of N are input into again2Storage tank, located at the pressure sensor of hydriding reactors at different levels, for receiving pressure signal and carrying out the signal control cabinet of signal transacting and transmission, located at CO2Electrically operated valve and gas compressor on gas delivery conduit, for the power supply powered to pressure sensor, signal control cabinet, electrically operated valve, gas compressor.The present invention not only saves CO compared to traditional single-stage hydrogenation apparatus2Gas usage amount, while allowing the reacting balance to carry out, improves the hydrogenation efficiency of lithium carbonate.

Description

Multistage hydrogenation apparatus and method
Technical field
The invention belongs to prepare battery-level lithium carbonate technical field, specifically a kind of multistage hydrogenation apparatus and side Method.
Background technology
Lithium carbonate is more important compound in current lithium salts, be mainly used in new energy car battery, glass ceramics, Alloy and medicine and other fields, especially country advocates Green Travel in recent years, and the principles and policies of low-carbon environment-friendly, New Energy Industry is high Speed development, just includes lithium ion battery among these, and the positive electrode cost in the lithium battery accounts for the 70~80% of whole battery, and The main positive electrode such as including nickle cobalt lithium manganate, cobalt acid lithium, LiFePO4 of the main product of market today, can all use carbonic acid Lithium is prepared from, and as new-energy automobile needs to be continuously increased, produced problem is consequently increased, and especially electrokinetic cell is asked Topic is especially prominent, and this is just related to material purity and material property, therefore to the purity requirement more and more higher of lithium carbonate.
Battery-level lithium carbonate mainly is prepared by raw material of industrial level lithium carbonate at present, mainly including causticizing process, electrolysis, hydrogen Change method etc., wherein causticizing process are primarily referred to as lithium carbonate and the soluble lithium hydroxide of calcium hydroxide reaction generation, then will be obtained Lithium hydroxide by resin removal of impurities, then the synthetically prepared LITHIUM BATTERY of carbon dioxide by high-purity lithium carbonate, the method step Rapid relatively complicated, wherein calcium hydroxide just introduces substantial amounts of impurity, extremely disadvantageous removal step later；Electrolysis due to Power consumption is unfavorable for greatly industrialized production, and hydrogenization method is the most reliable, but many dioxies in hydrogenation and synthetic reaction Change carbon not utilize completely, it is too low even with rate, wherein there is periodical literature《The influence that hydrogenation conditions are purified to lithium carbonate》（Material Material Leader B, 2011.7,25, Wu Jian）Point out that the lithium carbonate and carbon dioxide flow of 10 g, for 1L/min, react at 25 DEG C 40min, the utilization rate of carbon dioxide for obtaining only only has 7.6%；《Thick level lithium carbonate purifying technique process study》（Inorganic salt worker Industry, 2013.8,8, Li Yanru）The lithium carbonate of 10 g of middle selection is at 20 DEG C and the min of 1L/min carbon dioxide reactions 150, dioxy Change carbon utilisation rate 2.02%, above hydrogenation step belongs to single-stage hydrogenation, serious waste high-pureness carbon dioxide gas Body, causes gas raw material waste and industrial level lithium carbonate reaction incomplete.
The content of the invention
The present invention is in order to solve the above technical problems, provide a kind of multistage hydrogenation apparatus and method：
A kind of multistage hydrogenation apparatus：
Including multistage hydriding reactor and feeding device, wherein multistage hydriding reactor is main by one-level, two grades ..., N grades of multiple hydriding reactor string Connection is formed；Feeding device is used to add CO to hydriding reactors at different levels2Gas, including high-purity CO2Storage tank, collection CO2Storage tank, pressure sensing Device, signal control cabinet, electrically operated valve, gas compressor, power supply；
High-purity CO2Storage tank, for being passed through high-purity CO to N grades of hydriding reactor2Gas；
Collect CO2Storage tank, for by the CO in one-level, two grades ..., N grades of hydriding reactor2Gas is reclaimed, and by the CO of the recovery2Gas It is passed through one-level, two grades ..., N-1 grades of hydriding reactor；
Pressure sensor includes the hydriding reactor pressure sensor located at one-level, two grades ..., N grades hydriding reactors, for detecting hydrogen at different levels Change air pressure in kettle, and air pressure signal is transferred to signal control cabinet；With located at collect CO2The pressure of storage tank sensor of storage tank, uses CO is collected in detection2Air pressure in storage tank, and air pressure signal is transferred to signal control cabinet；
Signal control cabinet is used to receive, process the air pressure signal of each pressure sensor transmission：When the detection of hydriding reactor pressure sensor Atmospheric pressure value be less than or equal to standard atmospheric pressure when, to electrically operated valve transmission valve opening instruct；When the detection of hydriding reactor pressure sensor Atmospheric pressure value be more than standard atmospheric pressure when, to electrically operated valve transmission close valve instruct；When the atmospheric pressure value of pressure of storage tank sensor detection During less than or equal to standard atmospheric pressure, shutdown command is transmitted to gas compressor；When the atmospheric pressure value of pressure of storage tank sensor detection During more than standard atmospheric pressure, start-up command is transmitted to gas compressor；
Electrically operated valve is located at by high-purity CO2Storage tank conveys high-purity CO to N grades of hydriding reactor2On the pipeline of gas, also located at by collecting CO2The CO that storage tank is reclaimed to one-level, two grades ..., N-1 grades of hydriding reactor conveying from one-level, two grades ..., N grades of hydriding reactor2The pipeline of gas On, closed for valve opening after the valve opening instruction for receiving the transmission of signal control cabinet or after receiving the pass valve instruction that signal control cabinet is transmitted Valve；
Gas compressor is located to be used for CO in one-level, two grades ..., N-1 grades of hydriding reactor2It is recycled to collection CO2The main pipe rail of storage tank On, for stopping after the shutdown command that the transmission of signal control cabinet is worked or received after the start-up command for receiving the transmission of signal control cabinet Work；
Power supply is used to be powered to pressure sensor, signal control cabinet, gas compressor, electrically operated valve.
As improvement, the one-level, two grades ..., N grades of hydriding reactor be according to the discharging opening and latter hydrogen of previous hydriding reactor The dog-house for changing kettle is connected by way of the pipeline with pump is connected.
As improvement, the one-level, two grades ..., N grades of hydriding reactor side wall be provided with filler, for adding water.
Used as improvement, the one-level, the volume of two grades ..., N grades hydriding reactors are sequentially reduced, and one-level hydriding reactor volume is maximum, N Level hydriding reactor volume is minimum.
Used as improvement, pressure sensor is PY210 type sensors；Electrically operated valve is the ZJHP essence miniature thin-film pneumatic tune of single seat Section valve.
Used as improvement, the N grades of hydriding reactor is three-level hydriding reactor or level Four hydriding reactor.
Based on the multistage hydrogenation processes of foregoing multistage hydrogenation apparatus, comprise the following steps：
(1) one-level hydrogenation：The industrial level lithium carbonate and common pure water for weighing certain mass are mixedly configured into slurry, squeeze into one In level hydriding reactor, temperature control opens the agitating paddle stirring in one-level hydriding reactor at 20~25 DEG C in one-level hydriding reactor；
The CO that will be collected2Gas adds one-level hydriding reactor, the CO of the collection by gas feeding apparatus2Gas is from collection CO2 Storage tank；
According to normal pressure feedback regulation CO in one-level hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph At 8~8.5, more muddy lithia water I is obtained, now hydrogenation reaction rate is slower；
(2) second-stage hydrogenation reaction：
Lithia water I in filtration washing one-level hydriding reactor, obtains filtrate I and filter residue I, while filter residue I is pure with common Water is hybridly prepared into slurry and squeezes into second-stage hydrogenation kettle, and second-stage hydrogenation temperature in the kettle is controlled at 20~25 DEG C, opens two grades of hydrogen Change the agitating paddle stirring in kettle；
The CO that will be collected2Gas adds second-stage hydrogenation kettle, the CO of the collection by gas feeding apparatus2Gas is from collection CO2 Storage tank；
According to normal pressure feedback regulation CO in hydriding reactor2Feed rate, while monitor solution in pH value；Treat that solution ph exists When 7.5~8, the lithia water II more clarified, now hydrogenation reaction rate is very fast；
(3) three-level hydrogenation：
Lithia water II in filtration washing second-stage hydrogenation reactor, obtains filtrate II and filter residue II, while by filter residue II Slurry is hybridly prepared into common pure water to squeeze into three-level hydriding reactor, temperature control is opened at 20~25 DEG C in three-level hydriding reactor Open the agitating paddle stirring in three-level hydriding reactor；
By high-purity CO2Gas adds three-level hydriding reactor, high-purity CO by gas feeding apparatus2From high-purity CO2Storage tank；
According to normal pressure feedback regulation CO in three-level hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph At 7~7.5, the lithia water III more clarified, now hydrogenation reaction rate is quickly；
Lithia water III in filtration washing three-level hydriding reactor, obtains filtrate III；
The filtrate I, II, III is used as the raw material for preparing battery-level lithium carbonate.
The present invention compared with prior art, has the advantages that：
(1) saving high-purity CO is served2The purpose of gas, compared to traditional single-stage hydrogenation apparatus, not only saves CO2Gas Usage amount, while allowing the reacting balance to carry out, improves the hydrogenation efficiency of lithium carbonate.
(2) in hydriding process, by high-purity CO2Gas（High-purity CO2Gas meets GB/T 23938-2009 regulations Purity be more than 99.99%）Hydriding reactor is added in common aerating mode, according to pressure feedback regulation CO in hydriding reactor2Air inlet Speed, under remaining in hydriding reactor that pressure is normal atmosphere pressure condition, the Li of preparation2CO3Li in product2CO3High purity 99.88%, the content of wherein K, Ca, Na, Mg is respectively 0.00015%, 0.0035%, 0.015%, 0.0066%, has reached GB/T The LITHIUM BATTERY Li that the correlation GB such as 11075-2013, YS/T 582-2013 and rower specify2CO3The mark of content 99.5%~99.9% It is accurate.
(3) present invention process is simple and easy to apply, easy to operate.
Brief description of the drawings
Fig. 1 is the multistage hydrogenation apparatus schematic diagram of embodiment 1.
In figure：1st, one-level hydriding reactor；2nd, second-stage hydrogenation kettle；3rd, three-level hydriding reactor；4th, motor；5th, dog-house；6th, hydrogenate Kettle pressure sensor；7th, CO is collected2Storage tank；8th, high-purity CO2Storage tank；9th, pressure gauge；10th, a CO2It is passed through pipeline；11st, second CO2It is passed through pipeline；12nd, the 3rd CO2It is passed through pipeline；13rd, electrically operated valve；14th, a CO2Collection conduit；15th, the 2nd CO2Collecting pipe Road；16th, the 3rd CO2Collection conduit；17th, gas compressor；18th, signal control cabinet；19th, power supply；20th, filler；21st, discharge Mouthful；22nd, pressure of storage tank sensor.
Specific embodiment
The ＞ of ＜ embodiments 1
A kind of multistage hydrogenation apparatus, including multistage hydriding reactor and feeding device, wherein multistage hydriding reactor is main by one-level hydrogen Change kettle 1, second-stage hydrogenation kettle 2, three-level hydriding reactor 3 to be in series, hydriding reactors at different levels according to the discharging opening 21 of previous hydriding reactor with The latter dog-house of hydriding reactor 5 is connected by way of the pipeline with pump is connected；
Feeding device is used to add CO to hydriding reactors at different levels2Gas, including high-purity CO2Storage tank 8, collection CO2Storage tank 7, pressure sensing Device, signal control cabinet 18, electrically operated valve 13, gas compressor 17, power supply 19；
High-purity CO2Storage tank 8, for being passed through high-purity CO to three-level hydriding reactor 32Gas；
Collect CO2Storage tank 7, for by the CO in one-level hydriding reactor 1, second-stage hydrogenation kettle 2, three-level hydriding reactor 32Gas is reclaimed, and By the CO of the recovery2Gas is passed through one-level hydriding reactor 1, second-stage hydrogenation kettle 2, three-level hydriding reactor 3；
Pressure sensor includes being located at one-level hydriding reactor 1, second-stage hydrogenation kettle 2, the hydriding reactor pressure sensor 6 of three-level hydriding reactor 3, For detecting air pressure in hydriding reactors at different levels, and air pressure signal is transferred to signal control cabinet 18；With located at collect CO2Storage tank 7 Pressure of storage tank sensor 22, CO is collected for detecting2Air pressure in storage tank 7, and air pressure signal is transferred to signal control cabinet 18；
Signal control cabinet 18 is used to receive, process the air pressure signal of each pressure sensor transmission：When hydriding reactor pressure sensor 6 is examined When the atmospheric pressure value of survey is less than or equal to standard atmospheric pressure, instructed to the transmission valve opening of electrically operated valve 13；When hydriding reactor pressure sensor 6 When the atmospheric pressure value of detection is more than standard atmospheric pressure, closes valve to the transmission of electrically operated valve 13 and instruct；When pressure of storage tank sensor 22 is detected Atmospheric pressure value be less than or equal to standard atmospheric pressure when, to gas compressor 17 transmit shutdown command；When pressure of storage tank sensor 22 When the atmospheric pressure value of detection is more than standard atmospheric pressure, start-up command is transmitted to gas compressor 17；
Electrically operated valve 13 is located at by high-purity CO2Storage tank 8 conveys high-purity CO to three-level hydriding reactor 32On the pipeline of gas, also located at by Collect CO2The CO that storage tank 7 is reclaimed to one-level, two grades, the conveying of three-level hydriding reactor from one-level, two grades, three-level hydriding reactor2The pipe of gas Lu Shang, closes for valve opening after the valve opening instruction for receiving the transmission of signal control cabinet or after receiving the pass valve instruction that signal control cabinet is transmitted Valve；
Gas compressor 17 is located to be used for CO in one-level, two grades, three-level hydriding reactor2It is recycled to collection CO2The main pipe rail of storage tank 7 On, for after the shutdown command that the transmission of signal control cabinet 18 is worked or received after the start-up command for receiving the transmission of signal control cabinet 18 Stop work；
Power supply 19 is used to be powered to pressure sensor, signal control cabinet 18, gas compressor 17, electrically operated valve 13.
In above-mentioned multistage hydrogenation apparatus：One-level, two grades, three-level hydriding reactor side wall be additionally provided with filler 20, for plus Water；One-level, two grades, the volume of three-level hydriding reactor be sequentially reduced, one-level hydriding reactor volume is maximum, and three-level hydriding reactor volume is minimum； The series of hydriding reactor is not limited only to three-level, can also be the multistages such as level Four, Pyatyi；Pressure sensor uses PY210 type sensors, There can also be the sensor of identical function using other；Electrically operated valve is ZJHP essence miniature thin-film single seat pneumatic control valves, There can be the electrically operated valve of identical function using other.
Based on the multistage hydrogenation processes of above-mentioned multistage hydrogenation apparatus, comprise the following steps：
(1) one-level hydrogenation：The industrial level lithium carbonate and common pure water for weighing certain mass are mixedly configured into slurry, squeeze into one In level hydriding reactor, temperature control opens the agitating paddle stirring in one-level hydriding reactor at 20~25 DEG C in one-level hydriding reactor；
The CO that will be collected2Gas adds one-level hydriding reactor, the CO of the collection by gas feeding apparatus2Gas is from collection CO2 Storage tank；
According to normal pressure feedback regulation CO in one-level hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph At 8~8.5, more muddy lithia water I is obtained, now hydrogenation reaction rate is slower；
(2) second-stage hydrogenation reaction：
Lithia water I in filtration washing one-level hydriding reactor, obtains filtrate I and filter residue I, while filter residue I is pure with common Water is hybridly prepared into slurry and squeezes into second-stage hydrogenation kettle, and second-stage hydrogenation temperature in the kettle is controlled at 20~25 DEG C, opens two grades of hydrogen Change the agitating paddle stirring in kettle；
The CO that will be collected2Gas adds second-stage hydrogenation kettle, the CO of the collection by gas feeding apparatus2Gas is from collection CO2 Storage tank；
According to normal pressure feedback regulation CO in hydriding reactor2Feed rate, while monitor solution in pH value；Treat that solution ph exists When 7.5~8, the lithia water II more clarified, now hydrogenation reaction rate is very fast；
(3) three-level hydrogenation：
Lithia water II in filtration washing second-stage hydrogenation reactor, obtains filtrate II and filter residue II, while by filter residue II Slurry is hybridly prepared into common pure water to squeeze into three-level hydriding reactor, temperature control is opened at 20~25 DEG C in three-level hydriding reactor Open the agitating paddle stirring in three-level hydriding reactor；
By high-purity CO2Gas adds three-level hydriding reactor, high-purity CO by gas feeding apparatus2From high-purity CO2Storage tank；
According to normal pressure feedback regulation CO in three-level hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph At 7~7.5, the lithia water III more clarified, now hydrogenation reaction rate is quickly；
Lithia water III in filtration washing three-level hydriding reactor, obtains filtrate III；
The filtrate I, II, III is lithia water, used as the raw material for preparing battery-level lithium carbonate.
Prepare battery-level lithium carbonate：
Operation one, by industrial level lithium carbonate and water mixed preparing slurry by a certain percentage, by above-mentioned multistage hydrogenation apparatus And according to above-mentioned multistage hydrogenation processes, obtain lithia water；
Reaction principle：Li2CO3+CO2+nH2O=2LiHCO3+(n-1)H2O。
Operation two, and then lithium bicarbonate is decomposed, removing is difficult the impurity being hydrogenated；
Reaction principle：2LiHCO3= Li2CO3+H2O+CO2。
Operation three, then by causticizing reaction, concentrate, the ion exchange resin removal of impurity Ca, Mg etc.；
Reaction principle：Li2CO3+ Ca(OH)2=CaCO3+LiOH+H2O。
Operation four, is passed through the CO of high-purity2Gas, is prepared for the lithium carbonate of LITHIUM BATTERY.
Reaction principle：2LiOH+CO2+H2O=Li2CO3+2H2O。
Battery-level lithium carbonate is prepared using above-mentioned multistage hydrogenation apparatus and multistage hydrogenation processes：
Hydrogenation：200 kg industry level lithium carbonates are weighed, is added to 1 m3One-level hydriding reactor in, take 600 L industrial waters It is added thereto, temperature maintains 25 DEG C, by the speed control of agitating paddle in 180 r/min, is added with gas feeding apparatus and collected The CO for coming2Gas, gas velocity is controlled in 2.4 m3/ min, after reacting 1.8 hours, collects the CO of coming2Gas usage is 300 m3 (normal atmosphere pressure), the pH value in pH meter detection reactor is 8.2, filters the solution, by the kg lithium carbonates of gained filter residue 50, Add into the second-stage hydrogenation kettle of 200 L, take 100 L industrial waters and be added thereto, temperature maintains 25 DEG C, by the speed of agitating paddle Rate control in 175 r/min, added with gas feeding apparatus collect come CO2Gas, gas velocity is controlled in 1.2 m3/ min, After reaction 1 hour, the CO of collection2Gas usage is 100 m3(normal atmosphere pressure), pH meter detects that the pH value in reactor is 7.6, the solution is filtered, the kg lithium carbonates of gained filter residue 10 are added into the three-level level hydriding reactor of 50 L, take 20 L industrial Water is added thereto, and temperature maintains 25 DEG C, by the speed control of agitating paddle in 170 r/min, is added with gas feeding apparatus high The CO of purity2Gas, gas velocity is controlled in 1.2 m3/ min, after reacting 1 hour, high-purity CO2Gas usage is 75 m3(standard Under atmospheric pressure), the pH value in pH meter detection reactor is 7.2, filters the solution；
Decomposition reaction：One-level, two grades, three-level gained filtrate are all passed through in decomposing pot, are 90 DEG C, agitating paddle by temperature control Rotating speed be 180 r/min, by the decomposition reaction of 2 hours, filter residue is filtered to obtain while hot；
Causticizing reaction：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, and the rotating speed of agitating paddle is 180 r/min, by the causticizing reaction of 4.5 hours, Calcium carbonate is filtered to remove, with pure water 3 times, the concentration of filtrate lithium hydroxide 25 g/L is concentrated into, by concentrate with 2 L/ The speed of min passes through ion exchange resin；
Synthetic reaction：The concentrate after removal of impurities is passed through in synthesis reactor again, to being passed through high-purity CO in synthesis reactor2Gas (purity It is more than 99.99%), at 90 DEG C, stir speed (S.S.) is 170 r/min to temperature control, and gas velocity is 1m3/ min, generated time is 1.2 h, filter while hot, filter residue is placed in 100 DEG C of baking oven and is dried 6 hours, obtain lithium carbonate product L1.
The ＞ of ＜ embodiments 2
Prepare battery-level lithium carbonate：
Hydrogenation：200 kg industry level lithium carbonates are weighed, is added to 1 m3Reactor in, take 600 L industrial waters addition Wherein, temperature maintains 25 DEG C, and by the speed control of agitating paddle in 180 r/min, gas velocity is controlled in 2.4 m3/ min, instead After answering 5 hours, high-purity CO2The consumption of gas is 700 m3PH value in (normal atmosphere pressure) pH meter detection reactor is 7.5, Filter the solution；
Decomposition reaction：Method is with embodiment 1；
Causticizing reaction：Method is with embodiment 1；
Synthetic reaction：Method is with embodiment 1；
Obtain lithium carbonate product L2.
Industry level lithium carbonate sample L0 before experiment is taken, the product L2 uses that the product L1 and embodiment 2 that embodiment 1 is obtained are obtained Acid-base titration detection in GB/T 11064.1-2013, obtains L0 lithium carbonates purity for 99.02%, L1 lithium carbonate purity is 99.88%th, L2 lithium carbonates purity is 99.51%；L0, L1, L2 product are inhaled according to the NITRATE BY FLAME ATOMIC in GB/T 11064.4-2013 Receive spectrographic determination K, Na content, wherein the content of K be respectively 0.02%, 0.00015%, the content of 0.00082%, Na is respectively 0.18%、0.015%、0.025%；By L0, L1, L2 product according to the flame atomic absorption spectrometry in GB/T 11064.5-2013 Determine Ca contents, respectively 0.01%, 0.0035%, 0.0055%；By L0, L1, L2 product according in GB/T 11064.6-2013 Flame Atomic Absorption Spectrometry Determination Mg contents, respectively 0.012%, 0.0066%, 0.009%.
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 tri- kinds of products of L0, L1 and L2 of table 1 compares
Detection project L0 L1 L2 National standard
Li2CO3 99.02% 99.88% 99.51% 99.5%
K 0.02% 0.00015% 0.00082% 0.001%
Ca 0.01% 0.0035% 0.0055% 0.005%
Na 0.18% 0.015% 0.025% 0.025%
Mg 0.012% 0.0066% 0.009% 0.008%
From the results shown in Table 1, lithium carbonate product prepared by the method for being provided using the present invention, Li2CO3And K, Ca, Na, The content of Mg reaches the requirement of battery-level lithium carbonate in the range of national standard.
Also, the Li of product L12CO3Purity is significantly improved compared with L2：K contents are substantially reduced, its excess-three kind unit Plain Ca, Na, Mg content also has different degrees of reduction.
The hydrogenation high-purity CO of two kinds of products of the L1 of table 2 and L22Gas effciency compares
Sample Hydrogenation theory should consume high-purity CO2Amount/m3 Hydrogenation high-purity consumes actual CO2Amount/m3 Hydrogenation high-purity CO2Gas effciency/%
L1 60.54 75 80.7%
L2 60.54 700 8.60%
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 COs2Amount) × 100%, wherein high-purity consumes actual CO2Measure as gas usage instrument reads.
Product L1 hydrogenation high-purity COs after using three-level hydrogenation apparatus2The utilization rate of gas is 80.7%, and product L2 Hydrogenation high-purity CO2Gas effciency is only 8.6%, the hydrogenation high-purity CO of product L22Gas effciency and other The high-purity CO mentioned on document2The utilization rate of gas is similar to, such as " hydrogenation conditions are to lithium carbonate for the document that background technology is quoted Utilization rate of carbon dioxide is 7.6% in the influence of purification "；While the hydrogenation high-purity CO of product L12Gas effciency is L2 Nearly 10 times, have larger lifting, greatly reduce hydrogenation high-purity CO2Gas usage amount.

Claims (8)

1. a kind of multistage hydrogenation apparatus, it is characterised in that：
Including multistage hydriding reactor and feeding device, wherein multistage hydriding reactor is main by one-level, two grades ..., N grades of multiple hydriding reactor string Connection is formed；Feeding device is used to add CO to hydriding reactors at different levels2Gas, including high-purity CO2Storage tank, collection CO2Storage tank, pressure sensing Device, signal control cabinet, electrically operated valve, gas compressor, power supply；
High-purity CO2Storage tank, for being passed through high-purity CO to N grades of hydriding reactor2Gas；
Collect CO2Storage tank, for by the CO in one-level, two grades ..., N grades of hydriding reactor2Gas is reclaimed, and by the CO of the recovery2Gas It is passed through one-level, two grades ..., N-1 grades of hydriding reactor；
Pressure sensor includes the hydriding reactor pressure sensor located at one-level, two grades ..., N grades hydriding reactors, for detecting hydrogen at different levels Change air pressure in kettle, and air pressure signal is transferred to signal control cabinet；With located at collect CO2The pressure of storage tank sensor of storage tank, uses CO is collected in detection2Air pressure in storage tank, and air pressure signal is transferred to signal control cabinet；
Signal control cabinet is used to receive, process the air pressure signal of each pressure sensor transmission：When the detection of hydriding reactor pressure sensor Atmospheric pressure value be less than or equal to standard atmospheric pressure when, to electrically operated valve transmission valve opening instruct；When the detection of hydriding reactor pressure sensor Atmospheric pressure value be more than standard atmospheric pressure when, to electrically operated valve transmission close valve instruct；When the atmospheric pressure value of pressure of storage tank sensor detection During less than or equal to standard atmospheric pressure, shutdown command is transmitted to gas compressor；When the atmospheric pressure value of pressure of storage tank sensor detection During more than standard atmospheric pressure, start-up command is transmitted to gas compressor；
Electrically operated valve is located at by high-purity CO2Storage tank conveys high-purity CO to N grades of hydriding reactor2On the pipeline of gas, also located at by collecting CO2The CO that storage tank is reclaimed to one-level, two grades ..., N-1 grades of hydriding reactor conveying from one-level, two grades ..., N grades of hydriding reactor2The pipeline of gas On, closed for valve opening after the valve opening instruction for receiving the transmission of signal control cabinet or after receiving the pass valve instruction that signal control cabinet is transmitted Valve；
Gas compressor is located to be used for CO in one-level, two grades ..., N-1 grades of hydriding reactor2It is recycled to collection CO2The main pipe rail of storage tank On, for stopping after the shutdown command that the transmission of signal control cabinet is worked or received after the start-up command for receiving the transmission of signal control cabinet Work；
Power supply is used to be powered to pressure sensor, signal control cabinet, gas compressor, electrically operated valve.
2. multistage hydrogenation apparatus according to claim 1, it is characterised in that：
The one-level, two grades ..., N grades of hydriding reactor it is logical with the latter dog-house of hydriding reactor according to the discharging opening of previous hydriding reactor The mode for crossing the connection of the pipeline with pump is connected.
3. multistage hydrogenation apparatus according to claim 1, it is characterised in that：
The one-level, two grades ..., N grades of hydriding reactor side wall be provided with filler, for adding water.
4. multistage hydrogenation apparatus according to claim 1, it is characterised in that：
The one-level, the volume of two grades ..., N grades hydriding reactors are sequentially reduced, and one-level hydriding reactor volume is maximum, N grades of hydriding reactor volume It is minimum.
5. multistage hydrogenation apparatus according to claim 1, it is characterised in that：
Pressure sensor is PY210 type sensors；Electrically operated valve is ZJHP essence miniature thin-film single seat pneumatic control valves.
6. multistage hydrogenation apparatus according to any one of claim 1 to 5, it is characterised in that：
The N grades of hydriding reactor is three-level hydriding reactor or level Four hydriding reactor.
7. multistage hydrogenation processes based on the multistage hydrogenation apparatus described in claim 6, it is characterised in that including with Lower step：
(1) one-level hydrogenation：The industrial level lithium carbonate and common pure water for weighing certain mass are mixedly configured into slurry, squeeze into one In level hydriding reactor, temperature control opens the agitating paddle stirring in one-level hydriding reactor at 20~25 DEG C in one-level hydriding reactor；
The CO that will be collected2Gas adds one-level hydriding reactor, the CO of the collection by gas feeding apparatus2Gas is from collection CO2 Storage tank；
According to normal pressure feedback regulation CO in one-level hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph At 8~8.5, more muddy lithia water I is obtained, now hydrogenation reaction rate is slower；
(2) second-stage hydrogenation reaction：
Lithia water I in filtration washing one-level hydriding reactor, obtains filtrate I and filter residue I, while filter residue I is pure with common Water is hybridly prepared into slurry and squeezes into second-stage hydrogenation kettle, and second-stage hydrogenation temperature in the kettle is controlled at 20~25 DEG C, opens two grades of hydrogen Change the agitating paddle stirring in kettle；
The CO that will be collected2Gas adds second-stage hydrogenation kettle, the CO of the collection by gas feeding apparatus2Gas is from collection CO2 Storage tank；
According to normal pressure feedback regulation CO in hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph 7.5 When~8, the lithia water II more clarified, now hydrogenation reaction rate is very fast；
(3) three-level hydrogenation：
Lithia water II in filtration washing second-stage hydrogenation reactor, obtains filtrate II and filter residue II, while by filter residue II Slurry is hybridly prepared into common pure water to squeeze into three-level hydriding reactor, temperature control is opened at 20~25 DEG C in three-level hydriding reactor Open the agitating paddle stirring in three-level hydriding reactor；
By high-purity CO2Gas adds three-level hydriding reactor, high-purity CO by gas feeding apparatus2From high-purity CO2Storage tank；
According to normal pressure feedback regulation CO in three-level hydriding reactor2Feed rate, while monitor solution in pH value；Treat solution ph At 7~7.5, the lithia water III more clarified, now hydrogenation reaction rate is quickly；
Lithia water III in filtration washing three-level hydriding reactor, obtains filtrate III.
8. the product that prepared by multistage hydrogenation processes according to claim 7, it is characterised in that：
The filtrate I, II, III is used as the raw material for preparing battery-level lithium carbonate.
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