CN105036100A - Preparation method of crystal lithium hexafluorophosphate - Google Patents
Preparation method of crystal lithium hexafluorophosphate Download PDFInfo
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Abstract
The invention discloses a preparation method of crystal lithium hexafluorophosphate. The method comprises: 1) preparing industrial lithium carbonate and water into a slurry with concentration of 2%-5%; reacting with CO2, conducting resin exchange and gradient crystallization to obtain a high purity lithium hydrogencarbonate solution; reacting the high purity lithium hydrogencarbonate with high purity hydrogen fluoride, filtering, washing and drying to obtain high purity lithium fluoride; 2) reacting high purity hydrogen fluoride with high purity lithium fluoride to prepare a hydrogen fluoride lithium solution; 3) reacting high purity hydrogen fluoride with phosphorus pentachloride to obtain a mixture of phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride; introducing the mixture as stream stirred bubble stream into a hydrogen fluoride lithium solution to obtain a lithium hexafluorophosphate solution; and 4) crystallizing, filtering and drying lithium hexafluorophosphate solution to obtain the crystal lithium hexafluorophosphate. The method uses conventional raw materials for industrial production, ensures product quality and stability, and has the advantages of high utilization of raw materials, low production cost, and good environmental performance.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of preparation method of crystal lithium hexafluorophosphate.
Background technology
Along with increasingly sharpening of energy dilemma and environmental pollution, new-energy automobile is more and more subject to chasing after rod, and the development of new-energy automobile is now all risen to national strategy aspect by countries in the world.China is as resource big country and consumption big country, and production and consumption all ranks the first in the world.But due to the manufacture bottleneck of new-energy automobile---lithium ion battery manufacturing technology, be limited by U.S., monopoly enterprise of Japan and Korea S., cause the New Energy Industry of China to be substantially in stagnation.
Lithium hexafluoro phosphate manufactures core starting materials as lithium ion battery that is irreplaceable, compound only, and its product form, purity, trace impurity, consistence and homogeneity all determine lithium ion battery charge-discharge performance, energy density and work-ing life etc.Lithium hexafluoro phosphate product physicochemical property indicates its poor heat stability, and decomposition temperature is low, meets water and easily decomposes, and preparation need be carried out under the operating mode that anhydrous dustless, low temperature, corrosion resistant apparatus etc. are harsh.Many scientific workers are studied the industrialized process for preparing of cell-grade lithium hexafluoro phosphate.
Patent CN101570327A discloses a kind of method of producing lithium hexafluoro phosphate, comprises the following steps: anhydrous hydrogen fluoride for industrial use is carried out rectification and purification by (1), removes moisture wherein and beavy metal impurity; (2) anhydrous hydrogen fluoride after refining is reacted with phosphorus pentachloride obtain phosphorus pentafluoride and chlorine hydride mixed gas body; (3) high purity lithium fluoride is dissolved in anhydrous hydrogen fluoride solution, forms the anhydrous hydrogen fluoride solution of lithium fluoride; (4) filling in the anhydrous hydrogen fluoride solution of lithium fluoride by importing to after the cooling of the mixed gas of phosphorus pentafluoride and hydrogenchloride, obtaining pure lithium hexafluoro phosphate product through reaction, crystallization, separation, drying; (5) unreacted phosphorus pentafluoride and hydrogen chloride gas after reaction being continued to be passed into another fills in the anhydrous hydrogen fluoride solution of lithium fluoride, continues to be obtained by reacting lithium hexafluoro phosphate finished product.The reactivity that the method has is high, the advantage that continuous production is good; Because starting material directly use high purity lithium fluoride, cause production cost higher, and the quality stability of domestic high purity lithium fluoride is poor, is difficult to ensure product quality.
Summary of the invention
The object of this invention is to provide a kind of preparation method of crystal lithium hexafluorophosphate, the starting material prepared by lithium hexafluoro phosphate of purifying further, ensure that product quality; Construct the method being suitable for crystal lithium hexafluorophosphate large-scale industrial production, there is the advantage that raw material availability is high, production cost is low, the feature of environmental protection is good.
In order to realize above object, the technical solution adopted in the present invention is:
A preparation method for crystal lithium hexafluorophosphate, comprises the following steps:
1) industrial lithium carbonate and water are prepared the slip that weight percent concentration is 2% ~ 5%; CO is passed in described slip
2react, obtain thick lithia water; Described thick lithia water, through resins exchange, gradient crystallization, obtains high-purity lithia water;
In described high-purity lithia water, pass into high-purity hydrogen fluoride react, reaction product more after filtration, washing, obtain high purity lithium fluoride after drying;
2) at-40 DEG C ~-20 DEG C, under protection of inert gas, in high-purity hydrogen fluoride, high purity lithium fluoride is added, obtained hydrogen fluoride lithium solution;
3), at-5 ~ 50 DEG C, under protection of inert gas, in high-purity hydrogen fluoride, pass into phosphorus pentachloride react, obtain the mixture of phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride;
At-10 DEG C ~ 25 DEG C, under protection of inert gas, the mixture of gained phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride is passed into step 2 as the bubble flow of airflow stirring) carry out being obtained by reacting lithium hexafluorophosphate solution in gained hydrogen fluoride lithium solution;
4) by step 3) gained lithium hexafluorophosphate solution, obtain crystal lithium hexafluorophosphate through crystallization, filtration, drying.
Step 1) the foreign matter content sum≤0.0005wt% of described high-purity lithia water.
Step 1) purity >=99.95wt% of described high purity lithium fluoride.
Step 1) CO
2the speed that passes into be 5 ~ 15m
3/ h, the reaction times is 4 ~ 5h.
The present invention is by step 1) purifying process of raw material, ensure that preparation crystal lithium hexafluorophosphate basic raw material---the stay in grade of high purity lithium fluoride, and then decrease the removal of impurities difficulty of subsequent technique, be conducive to the crystal lithium hexafluorophosphate finished product obtaining stay in grade; The purity of the method to basic raw material controls, avoid raw-material batch of quality discrepancy to the impurities affect of lithium hexafluoro phosphate, mother liquor in preparation process can realize recycled, tail gas can the fluorine-containing hydrochloric acid of preparation quality concentration 20% through degassed, washing, thus jointly produce for sodium aluminum fluoride with the fluorine-containing waste residue of electrolytic aluminum or photovoltaic industry by-product, whole production technique three wastes discharge capacity is few, really can meet the demand of lithium hexafluoro phosphate suitability for industrialized production, there is the advantage that product with stable quality is good, utilization rate of raw materials is high, production cost is low, the feature of environmental protection is good.
Described high-purity hydrogen fluoride can directly adopt existing purification techniques, and high-purity hydrofluoric purity is at more than 99.999wt%.Described high-purity hydrogen fluoride is preferably obtained by fluorine gas oxidation, rectifying and membrane filtration by commercial fluorided hydrogen.
Described rectifying is preferably multistage rectification; More preferably two-stage rectification; Rectifying pressure-controlling is at below 0.1Mpa, and the bottom temperature of one-level rectifying is 20 DEG C ~ 35 DEG C, and temperature out is 19 ~ 25 DEG C; The bottom temperature of two-stage rectification is 15 DEG C ~ 25 DEG C, and temperature out is 12 ~ 18 DEG C.
Described membrane filtration is preferably the accurate membrane filtration of two-stage; More preferably the hydrogen fluoride after rectifying is passed through one-level 0.2 μm of microporous membrane and secondary 0.05 μm of micro-pore-film filtration.Thus the molecule impurity removed in commercial fluorided hydrogen raw material.
In high-purity hydrofluoric preparation, the metal ions such as the calcium in commercial fluorided hydrogen, magnesium, chromium are easily removed by rectifying means, but due to the boiling point of arsenic compound and hydrogen fluoride close, be difficult to effectively be removed by rectifying; Adopt fluorine gas method for oxidation effectively can remove arsonium ion, greatly reduce the content of arsenic in commercial fluorided hydrogen; Meanwhile, fluorine gas can react with water, reduces being mixed into of moisture in rectifying, is conducive to the content reducing water in commercial fluorided hydrogen; Commercial fluorided hydrogen is oxidized arsenic removal by fluorine gas, is dewatered, and converting substances fusing point, reduces follow-up rectifying energy consumption on the one hand; Avoid the lithium hexafluoro phosphate caused because moisture is too high on the other hand to decompose, in product, insolubles can effectively be reduced.Employing fluorine gas oxidation cooperation multistage rectification effectively can remove cation impurity, anionic impurity and moisture in commercial fluorided hydrogen raw material, ensures that hydrofluoric quality stability is good.
Step 1) industrial lithium carbonate is prepared the slip that weight percent concentration is 2% ~ 5%, be conducive to and CO
2carry out abundant highly effective reaction, obtain filter cake and filtrate, filtrate is lithia water; For removing other soluble impurities in lithia water further, the method for resins exchange, gradient crystallization can be adopted, foreign ion is removed further, obtaining high-purity lithia water.
Described resins exchange, refers to and adopts macropore polystyrene chelating ion exchange resin to carry out resins exchange.Resins exchange can effectively remove the foreign ion such as calcium, magnesium.Described macropore polystyrene chelating ion exchange resin belongs to commercially available convenient source, it can form many co-ordination complexs with metal ion, in single order and divalent metal solion, selectivity and divalent metal ion form stable comple, can effectively remove the foreign ion such as calcium, magnesium, have structural integrity and chemical stability is good, mesh degree is high, the feature that chelating capacity is large.
Described gradient crystallization carries out crystallization at-40 DEG C ~ 25 DEG C.
Can be obtained by resins exchange and gradient crystallization that purity is high, high-purity lithia water of stay in grade, thus ensure that the quality stability of lithium fluoride is good.
When high-purity hydrogen fluoride and high-purity lithium bicarbonate react, high-purity fluorine hydrogen can be selected little over amount, to ensure the transformation efficiency of high-purity lithium bicarbonate, the mass ratio of preferred fluorinated hydrogen and lithium bicarbonate is 1:(3 ~ 3.5).Take industrial lithium carbonate as the lithium fluoride that raw material is prepared by aforesaid method, can increase substantially the purity of product, in reaction process, by-product can be used for the Anhydrous Aluminium Chloride product of production containing 1wt% lithium containing lithium waste residue, the mother liquor that reaction generates and excessive CO
2can recycled be realized, thus while raising productivity effect, alleviate environmental protection pressure.
Step 2), lithium fluoride very easily dissolves and obtains hydrogen fluoride lithium solution in hydrogen fluoride, and its reaction is as follows:
LiF+HF→LiHF
2；
The dissolution process of lithium fluoride in hydrogen fluoride is exothermic process, and high purity lithium fluoride and high-purity hydrofluoric mass ratio are preferably 1:(5 ~ 15); More preferably 1:(10 ~ 15).React in above scope, the security of experiment, reaction efficiency reach best.
Step 3) be phosphorus pentachloride and high-purity hydrofluoric reactions steps, described phosphorus pentachloride can be industrial goods, and reaction product completes dedoping step by the mode of gas-liquid separation, obtains the mixture of phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride; For making phosphorus pentachloride fully transform, phosphorus pentachloride and high-purity hydrofluoric mass ratio are preferably (1.4 ~ 2.1): 1.
Phosphorus pentafluoride is very easily dissolved in hydrogen fluoride, and reaction process is as follows:
PF
5(g)+HF(l)→HPF
6(l)
Step 3) in, the mixture of phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride and the mass ratio of hydrogen fluoride lithium solution are 1:1.8 ~ 2.5.
For improving the transformation efficiency of phosphoric further, improve the productive rate of phosphorus pentachloride, preferably by step 3) mixture of unreacted phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride continues to pass into step 2) carry out being obtained by reacting lithium hexafluorophosphate solution in gained hydrogen fluoride lithium solution, obtain crystal lithium hexafluorophosphate through crystallization, filtration, drying; The mode that two still switches can be adopted in actual production; By 1
#, 2
#be communicated with in reactor and get hydrogen fluoride lithium solution ready, first to 1
#the mixture passing into phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride in reactor reacts, and unreacted completely phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture enters 2
#reactor continues reaction; Now, by 1
#the lithium hexafluorophosphate solution of reactor obtains crystal lithium hexafluorophosphate through crystallization, filtration, drying, continues to add hydrogen fluoride lithium solution for standby, 2 after being disposed
#phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture reenter 1 completely to have reacted rear unreacted in reactor
#reactor reacts, and 1
#, 2
#carry out cyclic switching reaction, supplement the mixture of phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride as required, this kind of technique is adopted not only to be conducive to the continuity of producing, and the transformation efficiency of phosphoric is further enhanced, while raising product income, also reduce further the discharge of tail gas, alleviate environmental protection pressure.
For reducing caking phenomenon during lithium hexafluoro phosphate partial crystallization, reducing the phenomenon of lithium hexafluoro phosphate parcel hydrofluoric acid, step 4 simultaneously further) described crystallization is for carrying out temperature gradient or ultrasonic crystallization.
The Tc of described temperature gradient crystallization is-40 DEG C ~ 25 DEG C.
Described ultrasonic crystallization is by power 200 ~ 400W, and the ul-trasonic irradiation of frequency 15 ~ 40KHz, in lithium hexafluorophosphate solution, carries out crystallization at-20 DEG C ~-15 DEG C.
Step 4) crystallization filter after mother liquor return step 2) prepare hydrogen fluoride lithium solution.Its mother liquor composition is mainly HF, includes the phosphorus pentafluoride and lithium hexafluoro phosphate that are dissolved in wherein, and the recycled of mother liquor, under the prerequisite not reducing product quality, achieves making full use of of raw material.
Step 4) described drying is less than 60 DEG C vacuum-dryings.Lithium hexafluoro phosphate is heated and easily decomposes, and below 60 DEG C, vacuum-drying better can remove hydrogen fluoride, and drying effect is better.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the crystal lithium hexafluorophosphate preparation method of embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
The preparation method of the present embodiment crystal lithium hexafluorophosphate, technical process as shown in Figure 1, comprises the following steps:
1) in 3kg anhydrous hydrogen fluoride for industrial use, pass into fluorine gas fully oxidized, obtain mixed gas; Mixed gas is carried out two-stage rectification at below 0.1Mpa; The bottom temperature of one-level rectifying is 20 DEG C, and temperature out is 19 DEG C; The bottom temperature of two-stage rectification is 15 DEG C, and temperature out is 12 DEG C; By the hydrogen fluoride after rectifying by one-level 0.2 μm of microporous membrane and secondary 0.05 μm of micro-pore-film filtration, remove the molecule impurity in commercial fluorided hydrogen raw material, the obtained high-pure anhydrous hydrogen fluoride of 2.88kg (purity >=99.999wt%);
0.4kg industrial lithium carbonate and water are made into the slip of 3wt%, then (pass into CO through carbonic acid gas carbonization
2react, passing into speed is 15m
3/ h, reaction times is 4h) obtain thick lithia water, after by thick lithia water through the macropore polystyrene chelating ion exchange resin process removing foreign ion such as calcium, magnesium, then obtain the high-purity lithia water (foreign matter content sum≤0.0005wt%) containing 0.566kg lithium bicarbonate through-40 DEG C ~ 25 DEG C gradient crystallizations; In reaction process, the 0.09kg of by-product contains lithium waste residue for the production of the Anhydrous Aluminium Chloride product containing 1wt% lithium;
Get the high-pure anhydrous hydrogen fluoride of 0.2kg and in the synthesis reactor of the airtight liner PFA of normal temperature, react the obtained slip containing 0.2kg high purity lithium fluoride containing high-purity lithia water of 0.6kg lithium bicarbonate, then obtain 0.18kg high purity lithium fluoride (purity >=99.98wt%) product through filtration, washing, vacuum-drying;
2) by high purity lithium fluoride-40 DEG C, under protection of inert gas, add and be loaded with in the high-pure anhydrous hydrofluoric airtight liner PFA reactor of 2.26kg, obtained 2.44kg hydrogen fluoride lithium solution; The quality such as hydrogen fluoride lithium solution are squeezed into 1 of top connection
#, 2
#in liner PFA reactor;
3) in airtight liner PFA reactor, add the high-pure anhydrous hydrogen fluoride of 0.45kg, be cooled to-5 DEG C, under protection of inert gas, pass into 0.87kg industry phosphorus pentachloride react, obtained 1.32kg phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture;
At-10 DEG C, under protection of inert gas, gained phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture are passed into step 2 as the bubble flow of airflow stirring) react in gained hydrogen fluoride lithium solution, the lithium hexafluorophosphate solution of obtained 35.8wt%;
By unreacted, phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture bubble flow such as to pass at the reactor 2 of quality completely
#in carry out reacting and as lower batch 1
#reactor; After having reacted, tail gas is through fluorine-containing hydrochloric acid that is degassed, the obtained 20wt% of washing, and direct and electrolytic aluminum or photovoltaic industry by-product fluorine-containing waste residue is used for sodium aluminum fluoride and produces;
4) lithium hexafluorophosphate solution of obtained 35.8wt% is proceeded in the crystallization kettle of liner PTFE, utilize temperature gradient to carry out crystallization at-40 DEG C ~ 25 DEG C, more after filtration, washing, vacuum-drying at 30 DEG C, obtained 0.6kg crystal lithium hexafluorophosphate; After filtering, the 1.168kg anhydrous hydrogen fluoride of gained returns and prepares hydrogen fluoride lithium solution.
Embodiment 2
The preparation method of the present embodiment crystal lithium hexafluorophosphate, technical process is identical with embodiment 1, comprises the following steps:
1) pass into fluorine gas to 16kg anhydrous hydrogen fluoride for industrial use fully oxidized, obtain mixed gas; Mixed gas is carried out two-stage rectification at below 0.1Mpa; Wherein the bottom temperature of one-level rectifying is 35 DEG C, and temperature out is 25 DEG C; The bottom temperature of two-stage rectification is 25 DEG C, and temperature out is 18 DEG C; By the hydrogen fluoride after rectifying by one-level 0.2 μm of microporous membrane and secondary 0.05 μm of micro-pore-film filtration, remove the molecule impurity in commercial fluorided hydrogen raw material, the obtained high-pure anhydrous hydrogen fluoride of 14.65kg (purity >=99.999wt%);
0.8kg industrial lithium carbonate and water are prepared the slip of 3wt%, then (pass into CO through carbonic acid gas carbonization
2react, passing into speed is 5m
3/ h, reaction times is 5h) generate thick lithia water, after by thick lithia water through the macropore polystyrene chelating ion exchange resin process removing foreign ion such as calcium, magnesium, then obtain the high-purity lithia water (foreign matter content sum≤0.0005wt%) containing 1.15kg lithium bicarbonate through-40 DEG C ~ 25 DEG C gradient crystallizations; In reaction process, the 0.175kg of by-product contains lithium waste residue for the production of the Anhydrous Aluminium Chloride product containing 1wt% lithium;
Get the high-pure anhydrous hydrogen fluoride of 0.4kg and in the synthesis reactor of the airtight liner PFA of normal temperature, react the obtained slip containing 0.44kg high purity lithium fluoride containing high-purity lithia water of 1.4kg lithium bicarbonate, then obtain 0.4kg high purity lithium fluoride (purity >=99.98wt%) product through filtration, washing, vacuum-drying;
2) by high purity lithium fluoride-20 DEG C, under protection of inert gas, add and be loaded with in the high-pure anhydrous hydrofluoric airtight liner PFA reactor of 6kg, obtained 6.4kg hydrogen fluoride lithium solution; The quality such as hydrogen fluoride lithium solution are squeezed into 1 of top connection
#, 2
#in liner PFA reactor;
3) in airtight liner PFA reactor, add the high-pure anhydrous hydrogen fluoride of 1kg, be cooled to-5 DEG C, under protection of inert gas, pass into 1.6kg industry phosphorus pentachloride react, obtained 2.6kg phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture;
At 15 DEG C, under protection of inert gas, gained phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture are passed into step 2 as the bubble flow of airflow stirring) react in gained hydrogen fluoride lithium solution, the lithium hexafluorophosphate solution of obtained 20wt%;
By unreacted, phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture bubble flow such as to pass at the reactor 2 of quality completely
#in carry out reacting and as lower batch 1
#reactor; After having reacted, tail gas is through fluorine-containing hydrochloric acid that is degassed, the obtained 20wt% of washing, and direct and electrolytic aluminum or photovoltaic industry by-product fluorine-containing waste residue is used for sodium aluminum fluoride and produces;
4) lithium hexafluorophosphate solution of obtained 20wt% is proceeded in the crystallization kettle of liner PTFE, utilize the ultrasonic wave of 200W, 40KHz to carry out crystallization at-20 DEG C, more after filtration, washing, vacuum-drying at 30 DEG C, obtained 1.05kg crystal lithium hexafluorophosphate; After filtering, the 4.75kg anhydrous hydrogen fluoride of gained returns and prepares hydrogen fluoride lithium solution.
Embodiment 3
The preparation method of the present embodiment crystal lithium hexafluorophosphate, technical process is identical with embodiment 1, comprises the following steps:
1) pass into fluorine gas to 20kg anhydrous hydrogen fluoride for industrial use fully oxidized, obtain mixed gas; Mixed gas is carried out two-stage rectification at below 0.1Mpa; Wherein, the bottom temperature of one-level rectifying is 20 DEG C ~ 35 DEG C, and temperature out is 19 ~ 25 DEG C; The bottom temperature of two-stage rectification is 15 DEG C ~ 25 DEG C, and temperature out is 12 ~ 18 DEG C; By the hydrogen fluoride after rectifying by one-level 0.2 μm of microporous membrane and secondary 0.05 μm of micro-pore-film filtration, remove the molecule impurity in commercial fluorided hydrogen raw material, the obtained high-pure anhydrous hydrogen fluoride of 18.2kg (purity >=99.999wt%);
0.48kg industrial lithium carbonate and water are prepared the slip of 5wt%, then (pass into CO through carbonic acid gas carbonization
2react, passing into speed is 10m
3/ h, reaction times is 4h) generate thick lithia water, after by thick lithia water through the macropore polystyrene chelating ion exchange resin process removing foreign ion such as calcium, magnesium, then obtain the high-purity lithia water (foreign matter content sum≤0.0005wt%) containing 1.12kg lithium bicarbonate through-40 DEG C ~ 25 DEG C gradient crystallizations; In reaction process, the 0.178kg of by-product contains lithium waste residue for the production of the Anhydrous Aluminium Chloride product containing 1wt% lithium;
Get the high-pure anhydrous hydrogen fluoride of 0.4kg and in the synthesis reactor of the airtight liner PFA of normal temperature, react the obtained slip containing 0.42kg high purity lithium fluoride with the high-purity lithia water containing 1.2kg lithium bicarbonate, again through filtration, washing, vacuum-drying, obtain 0.39kg high purity lithium fluoride (purity >=99.98wt%) product;
2) by high purity lithium fluoride-30 DEG C, under protection of inert gas, add and be loaded with in the high-pure anhydrous hydrofluoric airtight liner PFA reactor of 5.85kg, obtained 6.24kg hydrogen fluoride lithium solution; The quality such as hydrogen fluoride lithium solution are squeezed into 1 of top connection
#, 2
#in liner PFA reactor;
3) in airtight liner PFA reactor, add the high-pure anhydrous hydrogen fluoride of 1.1kg, 50 DEG C, pass into 1.7kg industry phosphorus pentachloride under protection of inert gas and react, obtained 2.8kg phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture;
At 25 DEG C, under protection of inert gas, gained phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture are passed into step 2 as the bubble flow of airflow stirring) react in gained hydrogen fluoride lithium solution, the lithium hexafluorophosphate solution of obtained 19.8wt%;
By unreacted, phosphorus pentafluoride, hydrogen fluoride and hydrogen chloride mixture bubble flow such as to pass at the reactor 2 of quality completely
#in carry out reacting and as lower batch 1
#reactor; After having reacted, tail gas is through fluorine-containing hydrochloric acid that is degassed, the obtained 20wt% of washing, and direct and electrolytic aluminum or photovoltaic industry by-product fluorine-containing waste residue is used for sodium aluminum fluoride and produces;
4) lithium hexafluorophosphate solution of obtained 19.8wt% is proceeded in the crystallization kettle of liner PTFE, carry out crystallization at-40 DEG C, more after filtration, washing, vacuum-drying at 60 DEG C, obtained 1.02kg crystal lithium hexafluorophosphate; After filtering, the 4.9kg anhydrous hydrogen fluoride of gained returns and prepares hydrogen fluoride lithium solution.
Test example
The crystal lithium hexafluorophosphate of embodiment 1 ~ 3 is carried out Performance Detection, and detected result is as shown in table 1.
The performance test results of crystal lithium hexafluorophosphate prepared by table 1 embodiment 1 ~ 3
| Test item | Measure unit | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Main content | ％ | 99.98 | 99.98 | 99.90 |
| DMC insolubles | mg/kg | 156 | 115 | 300 |
| Moisture content | mg/kg | 5.07 | 0.81 | 20 |
| Free acid (HF) | mg/kg | 60 | 44 | 150 |
| Na | mg/kg | 0.13 | 0.20 | 10 |
| K | mg/kg | 0.03 | 0.04 | 1 |
| Ca | mg/kg | 0.19 | 0.27 | - |
| Mg | mg/kg | 0.01 | 0.04 | - |
| Fe | mg/kg | 0.57 | 0.15 | 10 |
| Ni | mg/kg | 0.18 | 0.02 | - |
| Cr | mg/kg | 0.19 | 0.10 | - |
| Cu | mg/kg | 0.03 | 0.01 | - |
| Pb | mg/kg | - | - | - |
| SO 4 2- | mg/kg | 1.61 | 0.75 | 10 |
| Cl - | mg/kg | 1.48 | 0.81 | 5 |
From the test-results of table 1, crystal lithium hexafluorophosphate purity prepared by the present invention is high, moisture and foreign matter content few, the technical requirements of lithium ion battery to lithium hexafluoro phosphate can be met.
Claims (8)
1. a preparation method for crystal lithium hexafluorophosphate, is characterized in that, comprises the following steps:
1) industrial lithium carbonate and water are prepared the slip that weight percent concentration is 2% ~ 5%; CO is passed in described slip
2react, obtain thick lithia water; Described thick lithia water, through resins exchange, gradient crystallization, obtains high-purity lithia water;
In described high-purity lithia water, pass into high-purity hydrogen fluoride react, reaction product more after filtration, washing, obtain high purity lithium fluoride after drying;
2), at-40 DEG C ~-20 DEG C, under protection of inert gas, in high-purity hydrogen fluoride, step 1 is added) gained high purity lithium fluoride, obtained hydrogen fluoride lithium solution;
3), at-5 ~ 50 DEG C, under protection of inert gas, in high-purity hydrogen fluoride, pass into phosphorus pentachloride react, obtain the mixture of phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride;
At-10 DEG C ~ 25 DEG C, under protection of inert gas, the mixture of gained phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride is passed into step 2 as the bubble flow of airflow stirring) carry out being obtained by reacting lithium hexafluorophosphate solution in gained hydrogen fluoride lithium solution;
4) by step 3) gained lithium hexafluorophosphate solution, obtain crystal lithium hexafluorophosphate through crystallization, filtration, drying.
2. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, is characterized in that, described high-purity hydrogen fluoride is oxidized by fluorine gas by commercial fluorided hydrogen, rectifying and membrane filtration obtain.
3. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, it is characterized in that, also comprise: by step 3) mixture of unreacted phosphorus pentafluoride, hydrogen fluoride and hydrogenchloride continues to pass into step 2) carry out being obtained by reacting lithium hexafluorophosphate solution in gained hydrogen fluoride lithium solution, obtain crystal lithium hexafluorophosphate through crystallization, filtration, drying.
4. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, is characterized in that, step 1) mass ratio of hydrogen fluoride and lithium bicarbonate is 1:(3 ~ 3.5).
5. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, is characterized in that, step 3) phosphorus pentachloride and hydrofluoric mass ratio be (1.4 ~ 2.1): 1.
6. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, is characterized in that, step 2) lithium fluoride and hydrofluoric mass ratio be 1:(5 ~ 15).
7. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, is characterized in that, step 4) described crystallization is for being temperature gradient or ultrasonic crystallization.
8. the preparation method of crystal lithium hexafluorophosphate as claimed in claim 1, is characterized in that, step 4) described drying is less than 60 DEG C vacuum-dryings.
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| CN106882819A (en) * | 2017-03-29 | 2017-06-23 | 东营石大胜华新能源有限公司 | A kind of lithium hexafluoro phosphate prepares purification process |
| CN108640129A (en) * | 2018-07-13 | 2018-10-12 | 森田新能源材料（张家港）有限公司 | Lithium hexafluoro phosphate preparation method |
| CN112320824A (en) * | 2020-12-02 | 2021-02-05 | 江苏九九久科技有限公司 | Production method of lithium hexafluorophosphate |
| CN113582205A (en) * | 2021-08-12 | 2021-11-02 | 浙江三美化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN114044530A (en) * | 2021-11-25 | 2022-02-15 | 山东中顼技术研究有限公司 | Preparation method of lithium hexafluorophosphate for lithium ion secondary battery |
| CN114288845A (en) * | 2022-01-19 | 2022-04-08 | 福建省龙德新能源有限公司 | Hydrogen chloride purification method and device |
| CN114602406A (en) * | 2022-05-11 | 2022-06-10 | 北京化工大学 | Production device and production method of lithium hexafluorophosphate |
| CN115636429A (en) * | 2022-12-07 | 2023-01-24 | 山东立中新能源材料有限公司 | Preparation process of lithium hexafluorophosphate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723414A (en) * | 2009-12-11 | 2010-06-09 | 多氟多化工股份有限公司 | Method for producing battery-grade lithium fluoride |
| CN101723346A (en) * | 2009-12-11 | 2010-06-09 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102320573A (en) * | 2011-09-19 | 2012-01-18 | 瓮福（集团）有限责任公司 | Method for preparing electronic grade hydrofluoric acid |
-
2015
- 2015-07-15 CN CN201510417063.1A patent/CN105036100B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723414A (en) * | 2009-12-11 | 2010-06-09 | 多氟多化工股份有限公司 | Method for producing battery-grade lithium fluoride |
| CN101723346A (en) * | 2009-12-11 | 2010-06-09 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102320573A (en) * | 2011-09-19 | 2012-01-18 | 瓮福（集团）有限责任公司 | Method for preparing electronic grade hydrofluoric acid |
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| CN105600809A (en) * | 2016-02-25 | 2016-05-25 | 多氟多化工股份有限公司 | Method and device for preparing lithium hexafluorophosphate through dynamic crystallization |
| CN106882819A (en) * | 2017-03-29 | 2017-06-23 | 东营石大胜华新能源有限公司 | A kind of lithium hexafluoro phosphate prepares purification process |
| CN106882819B (en) * | 2017-03-29 | 2018-12-25 | 东营石大胜华新能源有限公司 | A kind of lithium hexafluoro phosphate prepares purification process |
| CN108640129A (en) * | 2018-07-13 | 2018-10-12 | 森田新能源材料（张家港）有限公司 | Lithium hexafluoro phosphate preparation method |
| CN112320824A (en) * | 2020-12-02 | 2021-02-05 | 江苏九九久科技有限公司 | Production method of lithium hexafluorophosphate |
| CN113582205A (en) * | 2021-08-12 | 2021-11-02 | 浙江三美化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN114044530A (en) * | 2021-11-25 | 2022-02-15 | 山东中顼技术研究有限公司 | Preparation method of lithium hexafluorophosphate for lithium ion secondary battery |
| CN114288845A (en) * | 2022-01-19 | 2022-04-08 | 福建省龙德新能源有限公司 | Hydrogen chloride purification method and device |
| CN114288845B (en) * | 2022-01-19 | 2023-02-24 | 福建省龙德新能源有限公司 | Hydrogen chloride purification method and device |
| CN114602406A (en) * | 2022-05-11 | 2022-06-10 | 北京化工大学 | Production device and production method of lithium hexafluorophosphate |
| CN114602406B (en) * | 2022-05-11 | 2022-09-09 | 北京化工大学 | Production device and production method of lithium hexafluorophosphate |
| CN115636429A (en) * | 2022-12-07 | 2023-01-24 | 山东立中新能源材料有限公司 | Preparation process of lithium hexafluorophosphate |
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