CN107244681A - A kind of continuous method and apparatus for preparing lithium hexafluoro phosphate - Google Patents
A kind of continuous method and apparatus for preparing lithium hexafluoro phosphate Download PDFInfo
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- CN107244681A CN107244681A CN201710198852.XA CN201710198852A CN107244681A CN 107244681 A CN107244681 A CN 107244681A CN 201710198852 A CN201710198852 A CN 201710198852A CN 107244681 A CN107244681 A CN 107244681A
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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
- C01D15/005—Lithium hexafluorophosphate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
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- 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
- C01P2006/82—Compositional purity water content
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of continuous device and method for preparing lithium hexafluoro phosphate.The device includes continuous crystallizing evaporator, and condensation recovering device, heater, device outer circulation pump, product crystal sends pump, separator outside；Agitating device is wherein provided with continuous evaporating crystallizer, continuous evaporating crystallizer bottom has elutriation leg；Device outer circulation pump, heater, continuous evaporating crystallizer are sequentially connected；Elutriation leg is sent pump outside with product crystal and is connected；Product crystal is sent pump outside and is connected with separator；Condensation recovering device is connected to the top of continuous evaporating crystallizer.The present invention uses high-efficiency evaporating and crystallizing method and advanced DBT types continuous high-efficient crystallizing evaporator, make the crystalline particle of lithium hexafluoro phosphate more uniform, the cost of investment and ton energy consumption of product are effectively reduced, it is achieved thereby that continuous, efficient, the large-scale production of lithium hexafluoro phosphate.
Description
Technical field
The invention belongs to power lithium-ion battery manufacturing technology field, be specifically that one kind rapidly and efficiently prepares, purifies electricity
The method and apparatus for solving matter salt lithium hexafluoro phosphate.
Background technology
Lithium ion battery has operating voltage high, energy density big (lightweight), self-discharge rate bottom, memory-less effect, followed
Ring long lifespan and the outstanding advantages such as pollution-free, have captured rapidly many fields, extensively with the incomparable advantage of other batteries
Applied in the products such as well known mobile phone, notebook computer, miniature camera, electric automobile, with electronic vapour
The industrialization of car, consumption certainly will be increasing.Using showing, lithium ion battery is a kind of preferably small-sized green power supply.
Electrolyte is one of big critical material of lithium ion battery four, is referred to as " blood " of lithium ion battery, in both positive and negative polarity
Between play a part of conducting electronics, be that lithium ion battery obtains high voltage, the guarantee of the performance such as high specific energy.Electrolyte it is general by
The raw materials such as organic solvent, electrolyte lithium salt, the necessary additive of high-purity, under certain condition, be adjusted to by a certain percentage and
Into.
Lithium hexafluoro phosphate is the critical materials of lithium-ion battery electrolytes, its production technology be related to low temperature, high temperature, vacuum,
Requirement in terms of corrosion resistant, safety and environmental protection, as disclosed in CN 106430255A, CN 105845931A etc., its equipment
It is required that high, technology difficulty is big.With the raising year by year of China's lithium ion battery manufacturing technology and output, to lithium hexafluoro phosphate
Demand is also increasing.Therefore, realize that lithium hexafluoro phosphate is continuously produced, improve the yield and quality of lithium hexafluoro phosphate, be to improve
Market competitiveness of enterprises and the key factor of resource utilization.
The content of the invention
Therefore, an object of the present invention is to provide a kind of device for preparing lithium hexafluoro phosphate.The system that the present invention is provided
The device of standby lithium hexafluoro phosphate makes crystalline particle more uniform, reduces the influence to impurity in product and acidity, realizes six
Continuous, efficient, the large-scale production of lithium fluophosphate.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：
A kind of device for preparing lithium hexafluoro phosphate, including continuous evaporating crystallizer, condensation recovering device, vavuum pump, heater,
Device outer circulation pump, product crystal sends pump, separator outside；Agitating device, continuous steaming are wherein provided with continuous evaporating crystallizer
Hair crystallizer bottom has elutriation leg；Device outer circulation pump, heater, continuous evaporating crystallizer are sequentially connected；Elutriation leg and product
Crystal is sent pump outside and is connected；Product crystal is sent pump outside and is connected with separator；Condensation recovering device is connected to continuous evaporating crystallizer
Top, the outlet connection vavuum pump of condensation recovering device.
Traditional static cooling crystallization technology, is also easy to produce brilliant scar on the inside of wall, and particle is uneven.The present invention is using stirring dress
Put achievable crystal more uniform.Compared with traditional crystallizer, crystalliser volume of the invention is smaller, and disposal ability is high.
Preferably, described agitating device is magnetic agitation motor.Using magnetic agitation, stirred in equipment without tradition
Machine is due to the leakage phenomenon produced by the gap between axle and sealing.
Preferably, the continuous evaporating crystallizer can realize adiabatic heat-insulation.
Preferably, the main material of the continuous evaporating crystallizer is SUS316L.
Preferably, the tube side of the condensation recovering device uses tetrafluoro material, shell side uses S316L materials.
Preferably, the separator is centrifugal separator.
Preferably, the centrifugal separator is centrifugal filter, preferably micro-filtration type centrifugal type filter.
Preferably, condensation recovering device outlet is provided with temperature teletransmission, is realized by the control of this temperature to AHF gases
Condense (temperature can control 0~5 DEG C).
Preferably, the bottom of continuous evaporating crystallizer is provided with temperature teletransmission, in real time display crystallizer internal temperature (temperature
45~50 DEG C can be controlled).
Preferably, heater outlet is provided with temperature teletransmission, is realized by the control of this temperature and device outer circulation is returned
The control of temperature (temperature can control 45~50 DEG C).
Preferably, the top of continuous evaporating crystallizer is provided with pressure teletransmission, is realized by the switch of vacuum breaker
Control to continuous evaporating crystallizer negative pressure (pressure can control -15~-25kPa).
Preferably, the top of separator is provided with pressure teletransmission, is realized by the switch of vacuum breaker to separation
The control of device negative pressure (pressure can control -5~0kPa).
Preferably, the entrance of device outer circulation pump is provided with regulating valve, and Synthesis liquid carrys out regulating valve, for controlling the stream of Synthesis liquid
Amount.
Preferably, the outlet of device outer circulation pump is provided with regulating valve, all the way to elutriation leg regulating valve, for controlling to elutriation
Leg flushing flow rate；Another road is to continuous evaporating crystallizer regulating valve, for controlling the mixed liquor into crystallizer.
Preferably, elutriation leg is provided with discharging regulating valve.
Preferably, product crystal sends the outlet of pump outside and is provided with regulating valve, for controlling magma to the amount of separator.
Preferably, the outlet of condensation recovering device is provided with regulating valve, for controlling the vacuum of continuous evaporating crystallizer.
Preferably, the outlet of separator is provided with regulating valve, for controlling the vacuum of separator.
An object of the present invention, which is also resided in, provides a kind of method for preparing lithium hexafluoro phosphate using device of the present invention,
Comprise the following steps：
(1) Synthesis liquid is sent to device outer circulation entrance, with from crystallizer come circulating tank be entrained with small crystals mother liquor mix
After conjunction, heater heating is delivered to；
(2) Synthesis liquid after heating enters in continuous evaporating crystallizer, and the feed liquid in crystallizer is stirred under vacuum,
In the presence of magnetic stirrer propeller, the feed liquid in crystallizer rises to liquid surface along on the outside of guide shell, from top to bottom
Circulation canal flowing is constituted along guide shell, circulation is formed；Because general mixer can produce sealing leak phenomenon, it is contemplated that nothing
The particularity and medium of water hydrogen fluoride material can not be with air contact factor, therefore, herein from magnetic stirrer；
(3) crystal of more than 350 μm of particle diameter is dropped into the elutriation leg of crystalliser feet, in the elutriation stream flowed up
Under effect, it is graded again, small crystal returns to continued growth in crystallizer with elutriation stream；
(4) crystal of more than 350 μm of particle diameter stays in elutriation leg and sends pump discharge outside to separator from product crystal, enters
Row separation of solid and liquid and drying, obtain purity height, evengranular hexafluorophosphoric acid crystalline lithium；
Mother liquor optionally after (5) separation, which is returned to crystallizer interior circulation, to be used.
Preferably, Synthesis liquid is the lithium hexafluoro phosphate Synthesis liquid that lithium fluoride and phosphorus pentafluoride synthetic reaction are generated.
Preferably, the temperature of Synthesis liquid is 5~15 DEG C in step (1), it is for example, 7 DEG C, 9 DEG C, 12 DEG C, 14 DEG C etc., excellent
Elect 10 DEG C as.
Preferably, the temperature of the heating be 40~50 DEG C, for example, 43 DEG C, 46 DEG C, 49 DEG C, 51 DEG C, 54 DEG C etc., preferably
For 45~50 DEG C.Lithium hexafluoro phosphate will produce decomposed at 55 DEG C, and farthest anhydrous hydrogen fluoride is volatilized, both
It is higher than 19.54 DEG C of the boiling point of anhydrous hydrogen fluoride, so considering, the temperature selection of heating is 40~50 DEG C, 45~50 DEG C
Actual effect is more notable.
Research finds that negative pressure value has direct influence to the size of crystalline particle, when vacuum is high, crystalline product purity
Relatively low, granularity is also smaller.Because during condition of high vacuum degree, solvent evaporation is fast, crystalline rate is big, nucleus that is producing is more, crystal it
Between be easily mingled with too many free acid and can not separate.So, it can obtain under rough vacuum evaporation conditionses larger and purer
Product.Preferably, the vacuum of vacuum described in step (2) be -5~-50kPa, be, for example, -30kPa, -35kPa, -
40kPa, -46kPa, -52kPa, -58kPa, -62kPa, -66kPa, -69kPa etc., are preferably -15~-25kPa.Can from Fig. 2
Go out vacuum it is high when, crystalline product purity is relatively low, and granularity is also smaller；It can obtain under rough vacuum evaporation conditionses larger and purer
Product；Whole crystallization process needs to carry out under the operation of negative pressure in addition, preferably anhydrous hydrogen fluoride could be made evaporated, institute
To consider, -5~-50kPa vacuum is selected, -15kp~-25kp actual effects are more notable.
Preferably, the vacuum in crystallizer tip exterior by setting Fluorine-lined vavuum pump to realize.
Preferably, it is evaporated to knot rapidly into part anhydrous hydrogen fluoride (AHF) in the Synthesis liquid in continuous evaporating crystallizer
Brilliant device top exit, is condensed into anhydrous liquid hydrogen fluoride, is recycled.A large amount of anhydrous hydrogen fluorides of traditional crystallizer discharge
Gas is reclaimed by way of washing, and while causing substantial amounts of anhydrous hydrogen fluoride waste, produced waste acid water is difficult to reclaim.
The anhydrous hydrogen fluoride gas that the present invention comes out to evaporated on top is reclaimed by the way of condensation, substantially increases the utilization of resources
Rate, has saved cost.
Preferably, the condensation with refrigerant by carrying out heat exchange progress.
Preferably, the temperature of the refrigerant is -20~-5 DEG C, is preferably -10 DEG C.
Preferably, the refrigerant is glycol water, and preferably 15-60wt% glycol water is further excellent
Elect 30wt% glycol water as.
Preferably, condensation time control cooler outlet temperature is 0 DEG C.
Preferably, vacuum during condensation is -5kPa~-50kPa, is preferably -15kPa~-25kPa.
Preferably, pressure when being separated in step (4) is -10kPa~0kPa, it is preferably -5kPa~0kPa.
The present invention uses high-efficiency evaporating and crystallizing method and advanced DBT types continuous high-efficient crystallizing evaporator, makes lithium hexafluoro phosphate
Crystalline particle it is more uniform；Product drying is carried out using efficient centrifugal machine, the moisture in product is effectively reduced, dissociates
Acid, metal, insoluble matter；This technology does not use deep cooling, the cost of investment and ton energy consumption of product is effectively reduced, it is achieved thereby that six
Continuous, efficient, the large-scale production of lithium fluophosphate.
The present invention is on the basis of using anhydrous hydrogen fluoride, lithium fluoride, phosphorus pentachloride as raw material, to pass through 2 step synthetic reactions
Synthesis liquid is formed, the method for the static crystallisation by cooling discarded tradition prepares six using the method for advanced, efficient evaporative crystallization
Mother liquor after lithium fluophosphate crystal, then the lithium hexafluoro phosphate finished product made by centrifugal separation of solid and liquid, packaging, Crystallization Separation is pure
Change, recycling is applied mechanically.
In the technical process of the present invention, overall process is preferred to use nitrogen as protection gas, it is to avoid whole process Central Plains
The possibility of material and finished product and air contact.The nucleus equipment that the present apparatus is used is DTB type continuous high-efficient crystallizing evaporator, ton
Energy consumption is lower, equipment cost is lower, security is higher.This crystallizer is different from general static mold, is a kind of collection evaporation
The crystallizer that crystallization, separation of solid and liquid, disposing mother liquor are integrated.
The main material of crystallizing evaporator used of the invention is SUS316L, and relatively lining PFA, special alloy equipment have very big
Cost advantage, also prevented under nitrogen atmosphere because a large amount of metals of the corrosion of equipment enter product.
The present invention has the advantage that compared with the prior art：
1. traditional handicraft uses the method for static crystallisation by cooling, it is necessary to which Synthesis liquid, which is passed through certain thermograde, to be reduced
To -50 DEG C, it is necessary to which using special deep freeze refrigeration plant, consuming electric power is big, deep cooling loss is big.Present invention process uses the work of evaporative crystallization
Skill, it is not necessary to deep freeze refrigeration plant, has fundamentally prevented the drawbacks of power consumption is big, greatly reduces energy consumption, the ton energy consumption of product compared with
80% is reduced before.
2. traditional handicraft is using intermittent static cooling crystallizer, and particle is big, and uniformity coefficient is low, and particle parcel impurity is more.
Present invention process uses continuous evaporating crystallizer, and magma can reach the purpose of optimization product quality by centrifugal filter,
Make crystalline particle more uniform, reduce the influence to impurity in product and acidity, while intermittent production is changed to continuity life
Production, realizes continuous, efficient, the large-scale production of lithium hexafluoro phosphate, can greatly improve production capacity.
3. compared with traditional crystallizer, crystalliser volume of the invention is small, and the equipment capacity of equal volume is added
50%, production efficiency is greatly improved.
4. traditional static cooling crystallization technology, is also easy to produce brilliant scar on the inside of wall, and particle is uneven.The present invention uses magnetic force
Mixer technology avoids the material from leakage of helical screw agitator generation and the phenomenon of contaminated material, also makes wall be difficult to scab, can be real
Existing crystal is more uniform, and uses magnetic agitation so that do not have traditional mixer in equipment due to the gap between axle and sealing
Produced leakage phenomenon.
5. traditional handicraft only crystallization procedure is indoor observation, and computer program control, very flexible is handled when occurring abnormal
Comparison of getting up is passive.This technique is truly realized the behaviour of " people decides " by indoor distribution type control system (DCS) remote control
Target is controlled, manipulation is got up more actively, is truly realized continuous remote operation.
6. turn to make crystal constantly collide, it is necessary to which crystallizer is followed after the completion of the static crystallisation by cooling of traditional handicraft, become small
Particle, needs to disconnect substantial amounts of metal hose in the process, easily causes the material from leakage accident caused by disconnecting flexible pipe.This hair
Bright technique uses continuous evaporating crystallizer, fundamentally prevented because disconnect metal hose and caused by leakage accident.
7. moisture≤4ppm in lithium hexafluoro phosphate produced by the present invention, acid≤70ppm, insoluble matter≤150ppm, iron≤
3ppm。
Brief description of the drawings
Fig. 1 is DBT type continuous evaporating crystallizers of the invention, wherein：1- continuous evaporating crystallizers, 2- magnetic agitations electricity
Machine, 3- condensation recovering devices, 4- heaters, 5- elutriation legs, 6- device outer circulation pumps, 7- product crystals send pump, the centrifugal separation of 8- outside
Machine, 9- vavuum pumps, 10- refrigerants are returned, and 11-AHF is reclaimed, 12- to centrifugal separator, 13- Synthesis liquids, and 14- refrigerants come, and 15- is extremely
Exhaust system, 16- mother liquors to crystallizer, 17- product barrellings, 18- steam；
Fig. 2 is influence of the vacuum to product granularity.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
The device used in the present invention is shown in Fig. 1, including continuous evaporating crystallizer, condensation recovering device, vavuum pump, heater,
Device outer circulation pump, product crystal sends pump, separator outside；Agitating device, continuous steaming are wherein provided with continuous evaporating crystallizer
Hair crystallizer bottom has elutriation leg；Device outer circulation pump, heater, continuous evaporating crystallizer are sequentially connected；Elutriation leg and product
Crystal is sent pump outside and is connected；Product crystal is sent pump outside and is connected with separator；Condensation recovering device is connected to continuous evaporating crystallizer
Top, the outlet connection vavuum pump of condensation recovering device.
Embodiment 1
A, Synthesis liquid heating
The lithium hexafluoro phosphate Synthesis liquid (6000L/h, 10 DEG C of temperature, concentration 20%) and knot of liquid pump are beaten from synthesis liquid storage tank
The mother liquor (2000L/h, 30 DEG C of temperature, concentration 5%) of brilliant device circulation enters crystallizer outer circulation pump intake together, passes through outer circulation
Pump, which is forced into after 0.15MPa, enters steam heater, and mixed liquor is warming up to 45 DEG C~50 DEG C, and into crystallizer, (concentration is about
16%).
Agitation cycle inside B, crystallizer
Into the mixed liquor in crystallizer, in the presence of magnetic stirrer, circulated along the circulation canal that guide shell is constituted
Negative pressure is between -15kPa~-25kPa in flowing, control crystallizer, and boiling liquid level is the region for producing degree of supersaturation, by steaming
Hair, as crystal contact in oversaturated solution and crystallizer, crystal is constantly grown up.Experiment proves negative pressure value to crystalline particle
Size has direct influence, when vacuum is high, and crystalline product purity is relatively low, and granularity is also smaller.Because during condition of high vacuum degree,
Solvent evaporation is fast, crystalline rate is big, nucleus that is producing is more, is easily mingled with too many free acid between crystal and can not isolate
Come.So, larger and purer product is can obtain under rough vacuum evaporation conditionses, Fig. 2 is seen.In Fig. 2 it can be seen that -15kpa~-
Particle diameter is more than 350 μm during 25kpa.
C, the condensation of crystallizer outlet anhydrous hydrogen fluoride are reclaimed
A large amount of anhydrous hydrogen fluoride gas of traditional crystallizer discharge are reclaimed by way of washing, cause substantial amounts of anhydrous fluorine
While changing hydrogen waste, produced waste acid water is difficult to reclaim.The present invention is adopted to the anhydrous hydrogen fluoride gas that evaporated on top comes out
Reclaimed with the mode of condensation, cooler material uses tetrafluoro material, refrigerant mass concentration is 30% glycol water,
- 10 DEG C of refrigerant temperature, cooler outlet temperature control is at 0 DEG C, in vacuum -15kPa~-25kPa, because anhydrous hydrogen fluoride
Boiling point is 19.45 DEG C, so the organic efficiency of anhydrous hydrogen fluoride can reach more than 90%.Recovery anhydrous hydrogen fluoride is 4500L/H,
The anhydrous hydrogen fluoride reclaimed is used as mother liquor tank dissolving lithium fluoride and used.
D, elutriation leg go out magma
Only crystal of the granularity more than 350 μm can be just dropped into elutriation leg, and magma is formed together with anhydrous hydrogen fluoride,
In the presence of the elutriation stream up walked, be graded again, small crystal returns to continued growth in crystallizer with elutriation stream, it is big into
Product crystallization harvesting is with building up to certain content outside finished product magma outlet ejector in elutriation leg, magma amount is 1000L/h.
E, magma separation
The magma come out from elutriation leg is beaten to micro-filtration type centrifugal type filter by force (forcing) pump, controlling filter pressure-
5kPa~0kPa, hexafluorophosphoric acid crystalline lithium is separated with anhydrous hydrogen fluoride, the anhydrous hydrogen fluoride being separated about 340L/
H, 100L/h self-loopa washing filter screen, prevent from blocking filter opening, 240L/h beats to crystallizer after pressurizeing by pump, is separated
Lithium hexafluoro phosphate fine work 990kg/h, moisture≤2ppm, acid≤50ppm, insoluble matter≤100ppm, iron≤1ppm.
Embodiment 2
In detailed process be the same as Example 1, except following difference：
The temperature that Synthesis liquid is fed in A is 5 DEG C；The temperature of Synthesis liquid heating is 55 DEG C；
Negative pressure is -25kPa in B；
The temperature of refrigerant is -5 DEG C in C；The refrigerant is 60wt% glycol water；
Vacuum during condensation is -50kp；
Pressure when being separated in E is -10kPa.
Gained lithium hexafluoro phosphate fine work, moisture≤2.8ppm, acid≤59ppm, insoluble matter≤130ppm, iron≤2.4ppm.
Embodiment 3
In detailed process be the same as Example 1, except following difference：
The temperature that Synthesis liquid is fed in A is 15 DEG C；The temperature of Synthesis liquid heating is 40 DEG C；
Negative pressure is -50kPa in B；
The temperature of refrigerant is -20 DEG C in C；The refrigerant is 15wt% glycol water；
Vacuum during condensation is -40kPa；
Pressure when being separated in E is 0kPa.
Gained lithium hexafluoro phosphate fine work, moisture≤3.4ppm, acid≤65ppm, insoluble matter≤146ppm, iron≤2ppm.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of continuous device for preparing lithium hexafluoro phosphate, including continuous evaporating crystallizer, condensation recovering device, vavuum pump, heating
Device, device outer circulation pump, product crystal sends pump, separator outside；Agitating device is wherein provided with continuous evaporating crystallizer, continuously
Crystallizing evaporator bottom has elutriation leg；Device outer circulation pump, heater, continuous evaporating crystallizer are sequentially connected；Elutriation leg and production
Product crystal is sent pump outside and is connected；Product crystal is sent pump outside and is connected with separator；Condensation recovering device is connected to continuous evaporating crystallizer
Top, condensation recovering device outlet connection vavuum pump.
2. device according to claim 1, it is characterised in that described agitating device is magnetic agitation motor；
Preferably, the continuous evaporating crystallizer can realize adiabatic heat-insulation；
Preferably, the main material of the continuous evaporating crystallizer is SUS316L；
Preferably, the tube side of the condensation recovering device uses tetrafluoro material, and shell side uses S316L materials；
Preferably, the separator is centrifugal separator；
Preferably, the centrifugal separator is centrifugal filter, preferably micro-filtration type centrifugal type filter.
3. device according to claim 1 or 2, it is characterised in that condensation recovering device outlet is provided with temperature teletransmission, passes through
The condensation to gas is realized in the control of this temperature；
Preferably, the bottom of continuous evaporating crystallizer is provided with temperature teletransmission, in real time display crystallizer internal temperature；
Preferably, heater outlet is provided with temperature teletransmission, is realized by the control of this temperature and returns to temperature to device outer circulation
Control；
Preferably, the top of continuous evaporating crystallizer is provided with pressure teletransmission, is realized by the switch of vacuum breaker to even
The control of continuous crystallizing evaporator negative pressure；
Preferably, the top of separator is provided with pressure teletransmission, is realized by the switch of vacuum breaker to separator
The control of negative pressure；
Preferably, the entrance of device outer circulation pump is provided with regulating valve, for controlling the flow of Synthesis liquid；
Preferably, the outlet of device outer circulation pump is provided with regulating valve, all the way to elutriation leg regulating valve, for controlling to elutriation leg to rush
Wash flow；Another road is to continuous evaporating crystallizer regulating valve, for controlling the mixed liquor into crystallizer；
Preferably, elutriation leg is provided with discharging regulating valve；
Preferably, product crystal sends the outlet of pump outside and is provided with regulating valve, for controlling magma to the amount of separator；
Preferably, the outlet of condensation recovering device is provided with regulating valve, for controlling the vacuum of continuous evaporating crystallizer；
Preferably, the outlet of separator is provided with regulating valve, for controlling the vacuum of separator.
4. a kind of usage right requires the method that any one of 1-3 described device prepares lithium hexafluoro phosphate, comprise the following steps：
(1) Synthesis liquid is sent to device outer circulation pump intake, with being entrained with from crystallizer after the mother liquor of small crystals mixes, delivered to
Heater is heated；
(2) Synthesis liquid after heating enters in continuous evaporating crystallizer, and the feed liquid in crystallizer is stirred under vacuum；
(3) crystal of more than 350 μm of particle diameter is dropped into the elutriation leg of crystalliser feet, in the elutriation stream effect flowed up
Under, it is graded again, small crystal returns to continued growth in crystallizer with elutriation stream；
(4) crystal of more than 350 μm of particle diameter stays in elutriation leg and sends pump discharge outside to separator from product crystal, consolidate
Liquid is separated and dried, and obtains hexafluorophosphoric acid crystalline lithium；
Mother liquor optionally after (5) separation, which is returned to crystallizer interior circulation, to be used.
5. method according to claim 4, it is characterised in that Synthesis liquid is that lithium fluoride and phosphorus pentafluoride are closed in step (1)
Into the lithium hexafluoro phosphate Synthesis liquid of reaction generation；
Preferably, the temperature of Synthesis liquid is 5~15 DEG C, preferably 10 DEG C；
Preferably, the temperature of the heating is 40~50 DEG C, preferably 45~50 DEG C.
6. the method according to claim any one of 3-5, it is characterised in that the vacuum of vacuum described in step (2) for-
5~-50kPa, is preferably -15~-25kPa.
7. the method according to claim any one of 3-6, it is characterised in that vacuum described in step (2) passes through in crystallization
Device tip exterior sets Fluorine-lined vavuum pump to realize.
8. the method according to claim any one of 3-7, it is characterised in that step enters continuous evaporating crystallizer in (2)
Part anhydrous hydrogen fluoride is evaporated to rapidly crystallizer top exit in interior Synthesis liquid, is condensed into anhydrous liquid hydrogen fluoride, carries out
Recycle.
9. method according to claim 8, it is characterised in that the condensation with refrigerant by carrying out heat exchange progress；
Preferably, the temperature of the refrigerant is -20~-5 DEG C, is preferably -10 DEG C；
Preferably, the refrigerant is glycol water, preferably 15-60wt% glycol water, is more preferably
30wt% glycol water；
Preferably, condensation time control cooler outlet temperature is 0 DEG C；
Preferably, vacuum during condensation is -5kPa~-50kPa, is preferably -15kPa~-25kPa.
10. the method according to claim any one of 3-9, it is characterised in that pressure when being separated in step (4) for-
10kPa~0kPa, is preferably -5kPa~0kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710198852.XA CN107244681B (en) | 2017-03-29 | 2017-03-29 | A kind of method and apparatus continuously preparing lithium hexafluoro phosphate |
Applications Claiming Priority (1)
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| CN109481952A (en) * | 2018-11-28 | 2019-03-19 | 江苏瑞升华能源科技有限公司 | A kind of MVR crystallizes out salt crystal grain control system and control method |
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| CN110683564A (en) * | 2019-12-10 | 2020-01-14 | 中化蓝天集团有限公司 | Lithium hexafluorophosphate-containing mixture crystal and application thereof |
| CN112723392A (en) * | 2020-12-02 | 2021-04-30 | 江苏昌吉利新能源科技有限公司 | Anhydrous lithium chloride continuous crystallization method |
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