CN105836767B - A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium - Google Patents
A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium Download PDFInfo
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- CN105836767B CN105836767B CN201610257026.3A CN201610257026A CN105836767B CN 105836767 B CN105836767 B CN 105836767B CN 201610257026 A CN201610257026 A CN 201610257026A CN 105836767 B CN105836767 B CN 105836767B
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 title claims abstract description 150
- 239000007788 liquid Substances 0.000 title claims abstract description 89
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002699 waste material Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 49
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000012452 mother liquor Substances 0.000 claims abstract description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 12
- 239000001103 potassium chloride Substances 0.000 claims abstract description 12
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- 241000370738 Chlorion Species 0.000 claims abstract description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZJGIYAGVUVFEKW-UHFFFAOYSA-N hydrogen peroxide;lithium Chemical compound [Li].OO ZJGIYAGVUVFEKW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000003814 drug Substances 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910001422 barium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000012239 gene modification Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000005017 genetic modification Effects 0.000 description 1
- 235000013617 genetically modified food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- -1 sulfuric acid Ion Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium, at least contain lithium ion, calcium ion, magnesium ion, sodium ion, potassium ion, sulfate ion and chlorion in the waste liquid containing lithium, the described method comprises the following steps：A, into the waste liquid containing lithium hydrogen peroxide is added, to remove remaining organic phase；B, add barium chloride solution and be filtrated to get mother liquor after the reaction；C, add sodium carbonate liquor into the mother liquor and be filtrated to get refinement mother liquor after the reaction；D, the refinement mother liquor is concentrated by evaporation to precipitated sodium chloride and solid potassium chloride and the sodium chloride and solid potassium chloride is filtered to remove, obtain lithium chloride clear liquid；High concentration lithium chloride solution is filtrated to get after E, the addition sodium refining agent into the lithium chloride clear liquid, stirring reaction；F, will the high concentration lithium chloride solution dry after obtain anhydrous Lithium chloride.Present invention process is simple, production cost is low, the lithium rate of recovery is high and environment-friendly.
Description
Technical field
The present invention relates to technical field prepared by lithium chloride, more particularly, it is related to one kind and prepares nothing using waste liquid containing lithium
The method of water lithium chloride.
Background technology
Lithium chloride is a kind of important lithium salts product, and in recent years, it is widely used in medicine, food, ring as mutagens
The industries such as guarantor, available for cultivation superior strain, synthesis medicine intermediate and carry out genetic modification etc. to strain, it may also be used for point
From the extraction and purifying for extracting RNA and a small amount of DNA；In terms of organic structural analysis, it is a kind of important cation again
Additive；Medically, it can be used for treatment diabetes and applied to genetic research etc.；In field of new materials, it can be answered
Production for chitin.In addition, electrolysis production lithium metal is the maximum aspect of lithium chloride consumption, also it is current production metal
Unique commercial run of lithium.Lithium metal and its alloy and compound are in metallurgical industry, battery, ceramics, glass, chemical industry, space flight work
Many fields such as industry, atomic energy industry, which are respectively provided with, to be widely applied.
At present, the preparation method of lithium chloride mainly has solvent extraction, ion exchange adsorption, salting out method and conversion method,
It is straight that conversion method is generally divided into ore direct translation method, lithium carbonate or lithium hydroxide conversion method, lithium sulfate conversion method and lithium hydroxide
Connect chloridising, wherein lithium carbonate or lithium hydroxide conversion method is topmost commercial run, China's major part lithium chloride be exactly with
The method production.But no matter, using solvent if there is the problem of high cost of material, hardly possible separation of impurity natrium potassium in which kind of above-mentioned method
Though extraction or ionic energy transfer sodium potassium separating effect are preferable, production cost is high, economically unreasonable.
Preparing anhydrous Lithium chloride using the waste liquid containing lithium produced in medicine intermediate production process for raw material can be great
Reduction cost of material simultaneously solves the problems such as its discharge of wastewater and environmental pollution.Can be using medicine therefore, it is necessary to provide one kind
The method that the waste liquid containing lithium produced in intermediate production process prepares anhydrous Lithium chloride.
The content of the invention
In order to solve problems of the prior art, it is an object of the invention to provide a kind of technique is simple, production cost
The method that the utilization waste liquid containing lithium low, the lithium rate of recovery is high and environment-friendly prepares anhydrous Lithium chloride.
The invention provides a kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium, at least contain in the waste liquid containing lithium
There are lithium ion, calcium ion, magnesium ion, sodium ion, potassium ion, sulfate ion and chlorion, the described method comprises the following steps：
A, into the waste liquid containing lithium hydrogen peroxide is added, to remove remaining organic phase；
B, add barium chloride or barium chloride solution and be filtrated to get mother liquor after the reaction；
C, add sodium carbonate or sodium carbonate liquor into the mother liquor and be filtrated to get refinement mother liquor after the reaction；
D, the refinement mother liquor is concentrated by evaporation to precipitated sodium chloride and solid potassium chloride and the sodium chloride is filtered to remove
And solid potassium chloride, obtain lithium chloride clear liquid；
High concentration lithium chloride solution is filtrated to get after E, the addition sodium refining agent into the lithium chloride clear liquid, stirring reaction；
F, will the high concentration lithium chloride solution dry after obtain anhydrous Lithium chloride.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, the waste liquid containing lithium is
The waste liquid containing lithium produced in the production process of medicine intermediate, wherein, lithium concentration in the waste liquid containing lithium for 10~
35g/L, chlorine ion concentration are that 80~200g/L, 1~15g/L of Na ion concentration, sulfate ion concentration are 0.5~5g/L, magnesium
Ion concentration is that 0.1~2g/L, calcium ion concentration are that 0.2~4g/L, potassium concentration are 0.01~0.2g/L.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, it is in step, described
The mass concentration of hydrogen peroxide is 10~50%, and the reaction time is 10~50min.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, it is in stepb, described
The concentration of barium chloride solution is 50~200g/L, and the reaction time is 30~120min.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, it is described in step C
The concentration of sodium carbonate liquor is 50~200g/L, and reaction temperature is 20~60 DEG C, and the reaction time is 30~240min.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, it is in step D, described
Na ion concentration in lithium chloride clear liquid is less than 1g/L, and potassium concentration is less than 0.5g/L.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, it is described in step E
Sodium refining agent is Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3And the addition of the sodium refining agent is in the lithium chloride clear liquid
25~30 times of sodium quality.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, in step E, reaction
Temperature is 40~95 DEG C, and the reaction time is 2~8h, and is carried out after the reaction using aperture for 0.5~1 μm of microfiltration membranes
Filter.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, it is described in step E
Na ion concentration in high concentration lithium chloride solution is less than 0.02g/L.
One embodiment of the method for anhydrous Lithium chloride is prepared using waste liquid containing lithium according to the present invention, in step F, by institute
High concentration lithium chloride solution is stated to be placed in titanium crucible and in baker in drying at 200~250 DEG C.
Compared with prior art, utilization waste liquid containing lithium of the invention, which prepares the method for anhydrous Lithium chloride, has advantages below：
1) technique is simple, production cost is low；2) the lithium rate of recovery is high；3) anhydrous Lithium chloride prepared by is up to LITHIUM BATTERY standard；4) adopted
Raw material is the waste liquid containing lithium produced in medicine intermediate production process, and cost of material is low；5) this is owned by France environmentally friendly, ring
Packing pressure is small.
Embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent by other or with similar purpose
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
.
Generally, the invention provides a kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium, in the middle of medicine
The waste liquid containing lithium produced in body production process removes remaining organic phase through hydrogen peroxide, first adds barium chloride and removes sulfate ion,
Essence is obtained after adding that sodium carbonate is agitated in mother liquor and being filtered to remove micro calcium ion, magnesium ion, barium ions, filtering precipitate
Mother liquor processed, is concentrated by evaporation and filtration from sodium chloride and potassium chloride to it, reheats gained lithium chloride clear liquid and adds sodium and refines
Agent agitation and filtration obtains high concentration lithium chloride solution, and battery-stage anhydrous lithium chloride product is obtained after drying.
The method that the present invention prepares anhydrous Lithium chloride using waste liquid containing lithium is described in detail below.
Wherein, in waste liquid containing lithium involved in the present invention at least containing lithium ion, calcium ion, magnesium ion, sodium ion, potassium from
Son, sulfate ion and chlorion.It is highly preferred that the waste liquid containing lithium contains lithium for what is produced in the production process of medicine intermediate
Waste liquid.According to one embodiment of present invention, the lithium concentration in the waste liquid containing lithium is 10~35g/L, chlorine ion concentration
For 80~200g/L, 1~15g/L of Na ion concentration, sulfate ion concentration be 0.5~5g/L, magnesium ion concentration be 0.1~
2g/L, calcium ion concentration are that 0.2~4g/L, potassium concentration are 0.01~0.2g/L, but the invention is not restricted to this.
According to the exemplary embodiment of the present invention, the method for preparing anhydrous Lithium chloride using waste liquid containing lithium includes following
Multiple steps.
Step A：
Hydrogen peroxide is added into waste liquid containing lithium, to remove remaining organic phase.
Hydrogen peroxide has strong oxidizing property, can effectively decompose the organic phase remained in waste liquid containing lithium.
According to a preferred embodiment of the invention, the mass concentration of hydrogen peroxide be 10~50%, the reaction time be 10~
50min。
Step B：
Add barium chloride or barium chloride solution and be filtrated to get mother liquor after the reaction.
Due to usually containing a certain amount of sulfate ion in waste liquid containing lithium, therefore can be by adding barium chloride or chlorination
Barium solution can make sulfate ion turn into precipitation, and then can remove sulfate ion by filtering.
According to a preferred embodiment of the invention, the concentration of barium chloride solution be 50~200g/L, the reaction time be 30~
120min。
Step C：
Sodium carbonate or sodium carbonate liquor are added into mother liquor and refinement mother liquor is filtrated to get after the reaction.
Due to the barium ions also added in waste liquid containing lithium containing micro calcium ion, magnesium ion and step B, therefore can be with
Above-mentioned metal cation is turned into precipitation by adding sodium carbonate or sodium carbonate liquor, and then can remove and obtain by filtering
Refinement mother liquor.
According to a preferred embodiment of the invention, the concentration of sodium carbonate liquor is 50~200g/L, and reaction temperature is 20~60
DEG C, the reaction time is 30~240min.
Step D：
Refinement mother liquor is concentrated by evaporation to precipitated sodium chloride and solid potassium chloride and the sodium chloride and chlorination is filtered to remove
Potassium solid, obtains lithium chloride clear liquid；
By the way that refinement mother liquor is evaporated to close to saturation point altogether, it can separate out sodium chloride and potassium chloride in mother liquor, enter
And by filtering the removal realized to a large amount of potassium ions and sodium ion.
According to the present invention, the Na ion concentration in gained lithium chloride clear liquid is less than 1g/L, and potassium concentration is less than 0.5g/L.
Step E：
High concentration lithium chloride solution is filtrated to get after adding sodium refining agent, stirring reaction into lithium chloride clear liquid.
Wherein, the main function of sodium refining agent is that depth removes remaining impurity natrium in lithium chloride clear liquid.According to the present invention
Preferred embodiment, sodium refining agent can be Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3, and the addition of sodium refining agent is chlorine
Change sodium quality in lithium clear liquid 25~30 times, for example, specifically can first be obtained before addition sodium refining agent with the detection of the means such as ICP
After sodium quality in lithium chloride clear liquid, then calculate the addition for obtaining sodium refining agent.
Preferably, in this step, need that controlling reaction temperature is 40~95 DEG C and the reaction time is 2~8h, specifically can be with
First lithium chloride clear liquid is heated to adding sodium refining agent after above-mentioned reaction temperature and reacted, and utilize hole after the reaction
Filtered for 0.5~1 μm of microfiltration membranes in footpath.Wherein, the Na ion concentration in gained high concentration lithium chloride solution is less than
0.02g/L。
Step F：
Finally, anhydrous Lithium chloride is obtained after high concentration lithium chloride solution is dried.
Specifically, high concentration lithium chloride solution can be placed in titanium crucible and in baker in baking at 200~250 DEG C
It is dry, you can to obtain the anhydrous Lithium chloride of LITHIUM BATTERY standard.
The method for preparing anhydrous Lithium chloride to present invention waste liquid containing lithium with reference to example is described further.
Example 1：
The 500mL of waste liquid containing lithium is taken, wherein, it is useless containing lithium to be produced in the production process of medicine intermediate that this contains lithium waste liquid
Liquid, and the lithium concentration contained in lithium waste liquid is that 25g/L, chlorine ion concentration are 150g/L, Na ion concentration 10g/L, sulphur
Acid ion concentration is that 3g/L, magnesium ion concentration are that 0.1g/L, calcium ion concentration are that 0.2g/L, potassium concentration are 0.01g/L.
Hydrogen peroxide and at normal temperatures stirring reaction 20min of the mass concentration for 10% are added into above-mentioned waste liquid containing lithium；Again
The barium chloride solution that concentration is 50g/L is added, it is agitated to precipitate sulfate ion, it is filtrated to get mother liquor；To in mother liquid obtained
Add the sodium carbonate liquor that concentration is 150g/L, and in 30 DEG C of stirring reaction 50min, be filtered to remove micro calcium ion, magnesium from
Son, barium ions, obtain refinement mother liquor；Refinement mother liquor is evaporated to close to saturation point altogether and substantial amounts of sodium chloride and potassium chloride is separated out
Solid, filtration from sodium chloride and solid potassium chloride, obtain lithium chloride clear liquid；Lithium chloride clear liquid is heated to 50 DEG C, added
15g sodium refining agent and stirring reaction 2h, after through 0.5 μm of micro-filtrate membrane filtration, obtain high-purity lithium chloride solution；By gained chlorination
Lithium solution is placed in titanium crucible and in drying obtains battery-stage anhydrous lithium chloride at 200 DEG C in baker.
Example 2：
The 500mL of waste liquid containing lithium is taken, wherein, it is useless containing lithium to be produced in the production process of medicine intermediate that this contains lithium waste liquid
Liquid, and the lithium concentration contained in lithium waste liquid is that 30g/L, chlorine ion concentration are 120g/L, Na ion concentration 8g/L, sulfuric acid
Ion concentration is 4g/L, and magnesium ion concentration is that 2g/L, calcium ion concentration are that 0.5g/L, potassium concentration are 0.1g/L.
Hydrogen peroxide and at normal temperatures stirring reaction 50min of the mass concentration for 50% are added into above-mentioned waste liquid containing lithium；Again
The barium chloride solution that concentration is 200g/L is added, it is agitated to precipitate sulfate ion, it is filtrated to get mother liquor；To in mother liquid obtained
Add the sodium carbonate liquor that concentration is 130g/L, and in 60 DEG C of stirring reaction 120min, be filtered to remove micro calcium ion, magnesium from
Son, barium ions, obtain refinement mother liquor；Refinement mother liquor is evaporated to close to saturation point altogether and substantial amounts of sodium chloride and potassium chloride is separated out
Solid, filtration from sodium chloride and solid potassium chloride, obtain lithium chloride clear liquid；Lithium chloride clear liquid is heated to 75 DEG C, added
7.5g sodium refining agent and stirring reaction 6h, after through 0.5 μm of micro-filtrate membrane filtration, obtain high-purity lithium chloride solution；By gained chlorine
Change lithium solution to be placed in titanium crucible and in drying obtains battery-stage anhydrous lithium chloride at 250 DEG C in baker.
Example 3：
The 500mL of waste liquid containing lithium is taken, wherein, it is useless containing lithium to be produced in the production process of medicine intermediate that this contains lithium waste liquid
Liquid, and the lithium concentration contained in lithium waste liquid is that 20g/L, chlorine ion concentration are 100g/L, Na ion concentration 12g/L, sulphur
Acid ion concentration is 2g/L, and magnesium ion concentration is that 0.5g/L, calcium ion concentration are that 4g/L, potassium concentration are 0.2g/L.
Hydrogen peroxide and at normal temperatures stirring reaction 50min of the mass concentration for 30% are added into above-mentioned waste liquid containing lithium；Again
The barium chloride solution that concentration is 100g/L is added, it is agitated to precipitate sulfate ion, it is filtrated to get mother liquor；To in mother liquid obtained
Add the sodium carbonate liquor that concentration is 160g/L, and in 40 DEG C of stirring reaction 240min, be filtered to remove micro calcium ion, magnesium from
Son, barium ions, obtain refinement mother liquor；Refinement mother liquor is evaporated to close to saturation point altogether and substantial amounts of sodium chloride and potassium chloride is separated out
Solid, filtration from sodium chloride and solid potassium chloride, obtain lithium chloride clear liquid；Lithium chloride clear liquid is heated to 65 DEG C, added
5g sodium refining agent and stirring reaction 8h, after through 0.5 μm of micro-filtrate membrane filtration, obtain high-purity lithium chloride solution；By gained chlorination
Lithium solution is placed in titanium crucible and in drying obtains battery-stage anhydrous lithium chloride at 220 DEG C in baker.
In summary, utilization waste liquid containing lithium of the invention, which prepares the method for anhydrous Lithium chloride, has advantages below：1) technique
Simply, production cost is low；2) the lithium rate of recovery is high；3) anhydrous Lithium chloride prepared by is up to LITHIUM BATTERY standard；4) original used
Expect the waste liquid containing lithium to be produced in medicine intermediate production process, cost of material is low；5) this is owned by France environmentally friendly, environmental protection pressure
It is small.
The invention is not limited in foregoing embodiment.The present invention, which is expanded to, any in this manual to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (9)
1. a kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that at least contain in the waste liquid containing lithium
Lithium ion, calcium ion, magnesium ion, sodium ion, potassium ion, sulfate ion and chlorion, the waste liquid containing lithium are middle for medicine
The waste liquid containing lithium produced in the production process of body, wherein, lithium concentration in the waste liquid containing lithium is 10~35g/L, chlorine from
Sub- concentration is that 80~200g/L, 1~15g/L of Na ion concentration, sulfate ion concentration are that 0.5~5g/L, magnesium ion concentration are
0.1~2g/L, calcium ion concentration are that 0.2~4g/L, potassium concentration are 0.01~0.2g/L, and methods described includes following step
Suddenly：
A, into the waste liquid containing lithium hydrogen peroxide is added, to remove remaining organic phase；
B, add barium chloride or barium chloride solution and be filtrated to get mother liquor after the reaction；
C, add sodium carbonate or sodium carbonate liquor into the mother liquor and be filtrated to get refinement mother liquor after the reaction；
D, the refinement mother liquor is concentrated by evaporation to precipitated sodium chloride and solid potassium chloride and the sodium chloride and chlorine is filtered to remove
Change potassium solid, obtain lithium chloride clear liquid；
High concentration lithium chloride solution is filtrated to get after E, the addition sodium refining agent into the lithium chloride clear liquid, stirring reaction；
F, will the high concentration lithium chloride solution dry after obtain anhydrous Lithium chloride.
2. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step A
In, the mass concentration of the hydrogen peroxide is 10~50%, and the reaction time is 10~50min.
3. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step B
In, the concentration of the barium chloride solution is 50~200g/L, and the reaction time is 30~120min.
4. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step C
In, the concentration of the sodium carbonate liquor is 50~200g/L, and reaction temperature is 20~60 DEG C, and the reaction time is 30~240min.
5. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step D
In, the Na ion concentration in the lithium chloride clear liquid is less than 1g/L, and potassium concentration is less than 0.5g/L.
6. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step E
In, the sodium refining agent is Li1.3Zr0.8Ce0.4Si0.5Al0.3(PO4)3And the addition of the sodium refining agent is the chlorination
25~30 times of sodium quality in lithium clear liquid.
7. the method according to claim 6 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step E
In, reaction temperature is 40~95 DEG C, and the reaction time is 2~8h, and utilizes the microfiltration membranes that aperture is 0.5~1 μm after the reaction
Filtered.
8. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step E
In, the Na ion concentration in the high concentration lithium chloride solution is less than 0.02g/L.
9. the method according to claim 1 for preparing anhydrous Lithium chloride using waste liquid containing lithium, it is characterised in that in step F
In, the high concentration lithium chloride solution is placed in titanium crucible and in baker in drying at 200~250 DEG C.
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| CN201610257026.3A CN105836767B (en) | 2016-04-22 | 2016-04-22 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
| PCT/CN2017/072970 WO2017181759A1 (en) | 2016-04-22 | 2017-02-06 | Method for manufacturing anhydrous lithium chloride using lithium-containing wastewater |
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| CN201610257026.3A CN105836767B (en) | 2016-04-22 | 2016-04-22 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
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| CN105836767B (en) * | 2016-04-22 | 2017-10-31 | 天齐锂业股份有限公司 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
| CN106565956B (en) * | 2016-10-21 | 2018-09-28 | 天津科技大学 | By-product slurry comprehensive reutilization method in a kind of polyphenylene sulfide production process |
| CN108220625B (en) * | 2016-12-21 | 2020-08-14 | 天齐锂业股份有限公司 | Method for recovering lithium from lithium-containing waste liquid |
| CN107954455A (en) * | 2017-12-06 | 2018-04-24 | 天齐锂业股份有限公司 | A kind of method for preparing battery-level lithium carbonate using waste liquid containing lithium |
| CN108264063B (en) * | 2018-01-13 | 2019-12-24 | 安徽金禾实业股份有限公司 | Method for extracting salt from sewage in maltol production |
| CN109574047B (en) * | 2018-10-22 | 2021-03-12 | 天齐锂业（江苏）有限公司 | Method for recovering high-purity efavirenz and lithium chloride from medical lithium-containing waste liquid |
| CN110304642B (en) * | 2019-08-15 | 2021-10-29 | 赣州有色冶金研究所有限公司 | Method for removing impurity sodium in lithium chloride and preparation method of battery-grade anhydrous lithium chloride |
| CN111017965B (en) * | 2019-11-29 | 2022-06-10 | 湖北金泉新材料有限公司 | Preparation method of industrial-grade lithium chloride |
| CN115465932A (en) * | 2022-10-24 | 2022-12-13 | 中化学朗正环保科技有限公司 | Method for removing sulfate ions in calcium salt concentrated solution |
| CN118388066A (en) * | 2024-04-10 | 2024-07-26 | 珠海万锂新材料有限公司 | Method for removing chlorine in lithium precipitation mother liquor by ion exchange method |
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| US6921522B2 (en) * | 1998-07-16 | 2005-07-26 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
| CN1230380C (en) * | 2003-07-28 | 2005-12-07 | 东北大学 | Process for purifying lithium chloride |
| CN1781847A (en) * | 2004-11-24 | 2006-06-07 | 中国石化集团巴陵石油化工有限责任公司 | Process for producing lithium chloride using waste liquid containing lithium |
| CN100469696C (en) * | 2007-09-18 | 2009-03-18 | 四川天齐锂业股份有限公司 | Preparation method of battery grade anhydrous lithium chloride |
| CN102874849B (en) * | 2012-09-11 | 2014-04-23 | 奉新赣锋锂业有限公司 | Method for producing anhydrous lithium chloride special for electrolyzing by using lithium recovered from lithium-containing pharmaceutical waste water |
| CN103738984B (en) * | 2013-12-26 | 2016-02-24 | 江苏久吾高科技股份有限公司 | A kind of extracting method of bitten lithium chloride and device |
| CN105152187A (en) * | 2015-07-23 | 2015-12-16 | 韦海棉 | Method for extracting lithium chloride from high lithium salt lake brine |
| CN105836767B (en) * | 2016-04-22 | 2017-10-31 | 天齐锂业股份有限公司 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
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Effective date of registration: 20191021 Address after: 629200, Suining County, Sichuan City, Shehong Province Taihe Town, North Qi Li lithium Limited by Share Ltd Co-patentee after: Tianqi lithium industry (Jiangsu) Co., Ltd. Patentee after: Tianqi Lithium Industry Co., Ltd. Co-patentee after: Tianqi Lithium Industry (Shehong) Co., Ltd. Address before: Suining City, Sichuan province 629200 Taihe Town Shehong County North Tianqi lithium Industrial Park Patentee before: Tianqi Lithium Industry Co., Ltd. |
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Address after: 215634, 5, Dongxin Road, Yangzi International Chemical Industry Park, Suzhou, Jiangsu, Zhangjiagang Co-patentee after: Tianqi Lithium Industry Co., Ltd. Patentee after: Tianqi lithium industry (Jiangsu) Co., Ltd. Co-patentee after: Tianqi Lithium Industry (Shehong) Co., Ltd. Address before: 629200, Suining County, Sichuan City, Shehong Province Taihe Town, North Qi Li lithium Limited by Share Ltd Co-patentee before: Tianqi lithium industry (Jiangsu) Co., Ltd. Patentee before: Tianqi Lithium Industry Co., Ltd. Co-patentee before: Tianqi Lithium Industry (Shehong) Co., Ltd. |