CN110453092A - Lithium salt solution treatment process - Google Patents
Lithium salt solution treatment process Download PDFInfo
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- CN110453092A CN110453092A CN201910779099.2A CN201910779099A CN110453092A CN 110453092 A CN110453092 A CN 110453092A CN 201910779099 A CN201910779099 A CN 201910779099A CN 110453092 A CN110453092 A CN 110453092A
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- reverse osmosis
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- salt solution
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of lithium salt solution treatment process, comprising: lithium hydroxide solution, acid solution is prepared in lithium salt solution decomposition；Lithium hydroxide solution is concentrated to get concentration lithium hydroxide solution by alkaline-resisting reverse osmosis membrane, and lithium hydroxide cleaner liquid is obtained by filtration；Acid solution is concentrated to get concentration acid solution by acidproof reverse osmosis membrane, and acidleach clear liquid is obtained by filtration；It is mixed lithium hydroxide cleaner liquid and acidleach clear liquid to obtain mixed once liquid；Mixed once liquid is obtained and is used for by first-stage reverse osmosis the industrial pure water and first-stage reverse osmosis concentrate of reuse；The first-stage reverse osmosis concentrate that gained raffinate and first-stage reverse osmosis obtain after salting liquid is decomposed is mixed to obtain secondary mixed liquor；The secondary mixed liquor of gained is obtained into two-pass reverse osmosis concentrate and two-pass reverse osmosis clear liquid by two-pass reverse osmosis, two-pass reverse osmosis concentrate returns to decomposition step, and two-pass reverse osmosis clear liquid resume at step carries out first-stage reverse osmosis again.Present invention reduces energy consumption, acid and alkali consumption, costs.
Description
Technical field
The present invention relates to salting liquid processing technology fields, and in particular to a kind of lithium salt solution treatment process.
Background technique
Existing Production By Sulfuric Acid Process lithium hydroxide technique needs to obtain essence by processes such as roasting leaching, sinker, acidification, purifications
Sulphuric acid lithium, refined sulfuric acid lithium are added sodium hydroxide and decomposite lithium hydroxide, and chilled analysis sodium removes sodium sulphate, analysis mother liquid of sodium warp
The processes such as flush distillation crystallization, the molten purification of weight, double evaporation-cooling crystallization, finally obtain lithium hydroxide product.Above-mentioned entire production stream
Journey process is more, wherein crystallizing comprising twice evaporation, energy consumption is very big, and sulfuric acid and sodium hydroxide consumption are also very big.
Summary of the invention
The main purpose of the present invention is to provide a kind of lithium salt solution treatment process, to solve lithium salt solution in the prior art
Treatment process consumes energy problem big, at high cost.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of lithium salt solution treatment process, packet
It includes:
(a) lithium salt solution decomposition is prepared into lithium hydroxide solution, acid solution；
(b) it decomposes gained lithium hydroxide solution and concentration lithium hydroxide solution, and mistake is concentrated to get by alkaline-resisting reverse osmosis membrane
Filter obtains lithium hydroxide cleaner liquid；
(c) it decomposes gained acid solution and concentration acid solution is concentrated to get by acidproof reverse osmosis membrane, and it is clear that acidleach is obtained by filtration
Liquid；
(d) it is mixed the lithium hydroxide cleaner liquid and acidleach clear liquid to obtain mixed once liquid；
(e) by the mixed once liquid by first-stage reverse osmosis obtain and be used for reuse industrial pure water and level-one it is anti-
Osmosis concentration liquid；
(f) first-stage reverse osmosis that gained raffinate and step (e) first-stage reverse osmosis obtain after decomposing step (a) salting liquid
Concentrate is mixed to obtain secondary mixed liquor；
(g) secondary mixed liquor obtained by step (f) is obtained into two-pass reverse osmosis concentrate and second level by two-pass reverse osmosis
Counter-infiltration clear liquid, the two-pass reverse osmosis concentrate, which returns in step (a), to be decomposed, and the two-pass reverse osmosis clear liquid returns to step
Suddenly (e) carries out first-stage reverse osmosis again.
Further, step (a) carries out salting liquid decomposition using bipolar membrane electrodialysis.
Further, the molecular cut off of the alkaline-resisting reverse osmosis membrane filtration device is 80~120D.
Further, the molecular cut off of the acidproof reverse osmosis membrane filtration device is 200~300D.
Further, the pressure resistance of the alkaline-resisting reverse osmosis membrane is 120bar, and putamina specification uses 8040 or 4040 standard films
Shell, resistance to alkali ability are tolerance 20%NaOH；The pressure resistance of the acidproof reverse osmosis membrane is 120bar, putamina specification using 8040 or
4040 standard putaminas, acid-fast ability are tolerance 25%H2SO4。
Further, the first-stage reverse osmosis is using coiled reverse osmosis membrane to Na2SO4Rejection >=98%.
Further, the two-pass reverse osmosis is using high pressure reverse osmosis membrane to Na2SO4Rejection >=96%.
Further, step (d) further includes carrying out pH adjusting to gained mixed once liquid.
Further, step (d) adjusts pH of mixed lithium hydroxide solution as obtained by salting liquid decomposition preparation or acid is molten
Liquid is adjusted.
Further, lithium hydroxide solution concentration > 2mol/L is concentrated in alkaline-resisting reverse osmosis membrane concentration gained；It is acidproof reverse osmosis
Acid solutions > 2mol/L is concentrated in film concentration gained.
According to an aspect of the invention, there is provided a kind of lithium salt solution processing system, comprising:
Salting liquid decomposer is equipped with lithium hydroxide for salting liquid decomposition to be prepared into lithium hydroxide solution, acid solution
Taphole, acid solution outlet and raffinate outlet；
Alkaline-resisting reverse osmosis membrane filtration device is equipped with lithium hydroxide solution entrance, the outlet of lithium hydroxide concentrated solution, lithium hydroxide
Cleaner liquid outlet, the solution inlet of resistance to lithium hydroxide are connected with lithium hydroxide solution outlet；
Acidproof reverse osmosis membrane filtration device is equipped with acidic solution inlet, sour concentrated solution outlet, acidleach purified liquor outlet, described resistance to
Acidic solution inlet is connected with acid solution outlet；
Level-one mixed stirring device is connected, for mixing respectively with lithium hydroxide cleaner liquid outlet, acidleach purified liquor outlet
It closes lithium hydroxide cleaner liquid and acidleach clear liquid obtains mixed once liquid；
First-stage reverse osmosis device is equipped with mixed once liquid entrance, first-stage reverse osmosis concentrated solution outlet, pure water outlet, described
Entry to mixed solution is connected with the outlet of level-one mixed stirring device；
Second level mixed stirring device is connected, for mixing raffinate respectively with raffinate outlet and reverse osmosis concentrated liquid outlet
And first-stage reverse osmosis concentrate obtains secondary mixed liquor；
Second level reverse osmosis apparatus is equipped with secondary entry to mixed solution, two-pass reverse osmosis concentrated solution outlet, two-pass reverse osmosis clear liquid
Outlet, the two-pass reverse osmosis concentrated solution outlet are connected with the entrance of salting liquid decomposer, and the two-pass reverse osmosis clear liquid goes out
Mouth is connected with the mixed once liquid entrance of first-stage reverse osmosis device.
Further, the salting liquid decomposer is bipolar membrane electrodialysis device.
Further, the bipolar membrane electrodialysis device includes the Bipolar Membrane being arranged successively, anionic membrane, cationic membrane,
Wherein Bipolar Membrane cation side is towards anionic membrane, and Bipolar Membrane anion side is towards cationic membrane, Bipolar Membrane, anionic membrane, sun
Ionic membrane constitutes processing unit, and processing unit outermost is respectively equipped with anode plate and cathode plate, further includes that positive grade connects anode plate, bears
Pole connects the fairing of cathode plate, the combustion being respectively connected with cavity and fairing where cavity, negative plate plate where anode plate
Expect battery.
Further, the molecular cut off of the alkaline-resisting reverse osmosis membrane filtration device is 80~120D.
Further, the molecular cut off of the acidproof reverse osmosis membrane filtration device is 200~300D.
Further, the pressure resistance of the alkaline-resisting reverse osmosis membrane is 120bar, and putamina specification uses 8040 or 4040 standard films
Shell, resistance to alkali ability are tolerance 20%NaOH；The pressure resistance of the acidproof reverse osmosis membrane is 120bar, putamina specification using 8040 or
4040 standard putaminas, acid-fast ability 25%H2SO4。
Further, the first-stage reverse osmosis device uses coiled reverse osmosis membrane.
Further, the second level reverse osmosis apparatus uses high pressure reverse osmosis membrane.
Further, the level-one mixed stirring device is connected with soda balance valve, the acid balance valve for adjusting level-one pH of mixed.
Further, the lye import of the soda balance valve is connected with lithium hydroxide solution outlet, the acid balance valve
Acid solution import is connected with acid solution import.
Lithium salts is directly decomposed into lithium hydroxide solution and acid solution by the present invention, to eliminate sodium hydroxide consumption, section
About reagent cost, water content reduction can after the concentration of alkaline-resisting reverse osmosis unit for preparation gained lithium hydroxide solution, acid solution
To reduce evaporation capacity, and step evaporation is only needed to be achieved with lithium hydroxide product, energy consumption declines to a great extent, obtained acid solution,
After membrane concentration, it can be recycled for leaching, reduce the consumption of acid solution.Thus the present invention greatly reduce energy consumption and
Acid and alkali consumption reduces the production cost of lithium hydroxide.
The present invention is suitable for lithium salt solution processing technology field, is equally applicable to sodium salt solution, ammonium salt solution, potassium salt soln
Treatment process.
As it can be seen that the present invention is described further with reference to the accompanying drawings and detailed description.The additional side of the present invention
Face and advantage will be set forth in part in the description, and partially will become apparent from the description below, or through the invention
Practice is recognized.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to assist the understanding of the present invention, content provided in attached drawing and its
Related explanation can be used for explaining the present invention in the present invention, but not constitute an undue limitation on the present invention.In the accompanying drawings:
Fig. 1 is the equipment flowsheet schematic diagram of lithium salt solution treatment process of the present invention.
Fig. 2 is the structural schematic diagram of bipolar membrane electrodialysis device in the present invention.
Related label in above-mentioned attached drawing are as follows:
1: bipolar membrane electrodialysis device；
11: fairing；
12: fuel cell；
13: anode plate；
14: cathode plate；
15: Bipolar Membrane；
16: anionic membrane；
17: cationic membrane；
2: alkaline-resisting reverse osmosis membrane filtration device；
3: soda balance valve；
4: acid balance valve；
5: acidproof reverse osmosis membrane filtration device；
6: level-one mixed stirring device；
7: first-stage reverse osmosis device；
8: second level mixed stirring device；
9: second level reverse osmosis apparatus.
Specific embodiment
Clear, complete explanation is carried out to the present invention with reference to the accompanying drawing.Those of ordinary skill in the art are being based on these
The present invention will be realized in the case where explanation.Before in conjunction with attached drawing, the present invention will be described, of particular note is that:
The technical solution provided in each section including following the description and technical characteristic in the present invention are not rushing
In the case where prominent, these technical solutions and technical characteristic be can be combined with each other.
In addition, the embodiment of the present invention being related in following the description is generally only the embodiment of a branch of the invention, and
The embodiment being not all of.Therefore, based on the embodiments of the present invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, should fall within the scope of the present invention under the premise of labour.
About term in the present invention and unit.Term in description and claims of this specification and related part
" comprising ", " having " and their any deformation, it is intended that cover and non-exclusive include.
As shown in Figure 1, to achieve the goals above, according to an aspect of the invention, there is provided at a kind of lithium salt solution
Science and engineering skill, comprising:
(a) lithium salt solution decomposition is prepared into lithium hydroxide solution, acid solution；
(b) it decomposes gained lithium hydroxide solution and concentration lithium hydroxide solution, and mistake is concentrated to get by alkaline-resisting reverse osmosis membrane
Filter obtains lithium hydroxide cleaner liquid；
(c) it decomposes gained acid solution and concentration acid solution is concentrated to get by acidproof reverse osmosis membrane, and it is clear that acidleach is obtained by filtration
Liquid；
(d) it is mixed the lithium hydroxide cleaner liquid and acidleach clear liquid to obtain mixed once liquid；
(e) by the mixed once liquid by first-stage reverse osmosis obtain and be used for reuse industrial pure water and level-one it is anti-
Osmosis concentration liquid；
(f) first-stage reverse osmosis that gained raffinate and step (e) first-stage reverse osmosis obtain after decomposing step (a) salting liquid
Concentrate is mixed to obtain secondary mixed liquor；
(g) secondary mixed liquor obtained by step (f) is obtained into two-pass reverse osmosis concentrate and second level by two-pass reverse osmosis
Counter-infiltration clear liquid, the two-pass reverse osmosis concentrate, which returns in step (a), to be decomposed, and the two-pass reverse osmosis clear liquid returns to step
Suddenly (e) carries out first-stage reverse osmosis again.
Step (a) carries out salting liquid decomposition using bipolar membrane electrodialysis.
The molecular cut off of the alkaline-resisting reverse osmosis membrane filtration device is about 80~120D.
The molecular cut off of the acidproof reverse osmosis membrane filtration device is about 200~300D.
The main function of alkaline-resisting reverse osmosis membrane and alkaline-resisting reverse osmosis membrane is concentration, when selecting molecular weight cut off, this hair
Bright acid-resistant disintegration used and alkaline-resisting film < 90% equal to the rejection of solute in target solution, make part solute penetrate UF membrane layer,
To reduce the pressure difference of film two sides solution osmotic pressure, concentrated water more higher than the film of high rejection can get under identical operating pressure
Side solution concentration.
The model of the alkaline-resisting reverse osmosis membrane, performance parameter: pressure-resistant 120bar, 80~120D of molecular cut off, putamina
Specification: 8040 or 4040 standard putaminas, resistance to alkali ability: tolerance 20%NaOH.
The model of the acidproof reverse osmosis membrane, performance parameter: pressure-resistant 120bar, 200~300D of molecular cut off, putamina
Specification: 8040 or 4040 standard putaminas, acid-fast ability: tolerance 25%H2SO4。
Different film producers are different to the numbering of film, and the film different manufacturers of similar performance have different numbers, therefore this hair
The type and performance of bright description film, not specified model and producer.
The first-stage reverse osmosis use coiled reverse osmosis membrane, molecular cut off be the same level it is reverse osmosis selection when be investigate film
To the rejection of specific molecular, the first-stage reverse osmosis film used in this technique is to Na2SO4Rejection >=98%.
The two-pass reverse osmosis use high pressure reverse osmosis membrane, molecular cut off be the same level it is reverse osmosis selection when be investigate film
To the rejection of specific molecular, the two-pass reverse osmosis film used in this technique is to Na2SO4Rejection >=96%.
Step (d) further includes carrying out pH adjusting to gained mixed once liquid.
Step (d) adjusts pH of mixed lithium hydroxide solution as obtained by salting liquid decomposition preparation or acid solution is adjusted
Section.
Lithium hydroxide solution concentration > 2mol/L is concentrated in alkaline-resisting reverse osmosis membrane concentration gained；Acidproof reverse osmosis membrane concentration gained
Acid solutions > 2mol/L is concentrated.
Lithium salt solution processing system of the present invention, comprising:
Salting liquid decomposer is equipped with lithium hydroxide for salting liquid decomposition to be prepared into lithium hydroxide solution, acid solution
Taphole, acid solution outlet and raffinate outlet；
Alkaline-resisting reverse osmosis membrane filtration device 2 is equipped with lithium hydroxide solution entrance, the outlet of lithium hydroxide concentrated solution, hydroxide
The outlet of lithium cleaner liquid, the solution inlet of resistance to lithium hydroxide are connected with lithium hydroxide solution outlet；
Acidproof reverse osmosis membrane filtration device 5 is equipped with acidic solution inlet, sour concentrated solution outlet, acidleach purified liquor outlet, described resistance to
Acidic solution inlet is connected with acid solution outlet；
Level-one mixed stirring device 6 is connected with lithium hydroxide cleaner liquid outlet, acidleach purified liquor outlet respectively, is used for
Mixing lithium hydroxide cleaner liquid and acidleach clear liquid obtain mixed once liquid；
First-stage reverse osmosis device 7 is equipped with mixed once liquid entrance, first-stage reverse osmosis concentrated solution outlet, pure water outlet, described
Entry to mixed solution is connected with the outlet of level-one mixed stirring device 6；
Second level mixed stirring device 8 is connected with raffinate outlet and reverse osmosis concentrated liquid outlet respectively, residual for mixing
Liquid and first-stage reverse osmosis concentrate obtain secondary mixed liquor；
It is clear to be equipped with secondary entry to mixed solution, two-pass reverse osmosis concentrated solution outlet, two-pass reverse osmosis for second level reverse osmosis apparatus 9
Liquid outlet, the two-pass reverse osmosis concentrated solution outlet are connected with the entrance of salting liquid decomposer, the two-pass reverse osmosis clear liquid
Outlet is connected with the mixed once liquid entrance of first-stage reverse osmosis device 7.
The salting liquid decomposer is bipolar membrane electrodialysis device 1.
The bipolar membrane electrodialysis device 1 include be arranged successively Bipolar Membrane 15, anionic membrane 16, cationic membrane 17,
The cationic side of middle Bipolar Membrane 15 towards anionic membrane 16,15 anion side of Bipolar Membrane towards cationic membrane 17, Bipolar Membrane 15, yin from
Sub- film 16, cationic membrane 17 constitute processing unit, and processing unit outermost is respectively equipped with anode plate 13 and cathode plate 14, further includes
Positive grade connects anode plate 13, cathode connect cathode plate 14 fairing 11, with cavity where 13 place cavity of anode plate, negative plate plate with
And the fuel cell 12 that fairing 11 is respectively connected with.
Further, the molecular cut off of the alkaline-resisting reverse osmosis membrane filtration device is 80~120D.
Further, the molecular cut off of the acidproof reverse osmosis membrane filtration device is 200~300D.
Further, the pressure resistance of the alkaline-resisting reverse osmosis membrane is 120bar, and putamina specification uses 8040 or 4040 standard films
Shell, resistance to alkali ability are tolerance 20%NaOH；The pressure resistance of the acidproof reverse osmosis membrane is 120bar, putamina specification using 8040 or
4040 standard putaminas, acid-fast ability 25%H2SO4。
The first-stage reverse osmosis device 7 uses coiled reverse osmosis membrane.
The second level reverse osmosis apparatus 9 uses high pressure reverse osmosis membrane.
The level-one mixed stirring device 6 is connected with soda balance valve 3, the acid balance valve 4 for adjusting level-one pH of mixed.
The lye import of the soda balance valve 3 is connected with lithium hydroxide solution outlet, the acid solution import of the acid balance valve 4
It is connected with acid solution import.
As shown in Figure 1, salting liquid MaX (wherein M represents monovalent metallic ion, and X represents acid ion, such as: work as M=Li
+, a=2, X=SO42-When, salting liquid is lithium sulfate) enter bipolar membrane electrodialysis device brine inlet 1, divide under the function of current
Solution is MOH weak solution and HaX weak solution, and wherein MOH is flowed out from lye export, and HaX is exported from acid solution to flow out, undecomposed MaX
It is exported and is flowed out from raffinate in the form of raffinate；Most of dilute MOH solution flows into alkaline-resisting 2 raw water mouth of reverse osmosis membrane, through alkaline-resisting reverse osmosis
The MaX solution that concentration > 2mol/L is formed after film concentration is flowed out from alkaline-resisting permeable membrane film concentrated water spout；Most of dilute HaX solution flows into
Acidproof 4 raw water mouth of reverse osmosis membrane forms the HaX solution of concentration > 2mol/L from acidproof reverse osmosis after the concentration of acidproof reverse osmosis membrane
The outflow of permeable membrane film concentrated water spout；Alkaline-resisting permeable membrane film produces the solution of mouth of a river outflow and acidproof reverse osmosis membrane produces the solution that the mouth of a river is flowed out
It enters in neutralization chamber 6 and is neutralized, a small amount of MOH weak solution is added to neutralization chamber by soda balance valve 3 or pass through acid balance valve 4
A small amount of HaX weak solution is added to neutralization chamber, controls the pH value of solution 6~8 in neutralization chamber；Regulated in neutralization chamber the solution of pH value from
The outflow of neutralization chamber water outlet enters 7 raw water mouth of coiled reverse osmosis membrane, the production water of coiled reverse osmosis membrane as industrial pure water reuse,
The concentrated water of coiled reverse osmosis membrane with mixed in mixing channel 8 from the raffinate that bipolar membrane electrodialysis device comes out after to enter high pressure anti-
9 raw water mouth of permeable membrane forms the MaX solution of concentration > 2mol/L from high pressure reverse osmosis membrane concentrated water after the concentration of high pressure reverse osmosis membrane
It mouthful comes out and to return to bipolar membrane electrodialysis device, high pressure reverse osmosis membrane, which produces water and produces the mouth of a river from high pressure reverse osmosis membrane, comes out that return to rolling anti-
Permeable membrane is recycled.
As shown in Fig. 2, Bipolar Membrane 15, anionic membrane 16, cationic membrane 17 are arranged successively, wherein Bipolar Membrane cation side court
To anionic membrane, Bipolar Membrane anion side is towards cationic membrane, and so as to form processing unit, multiple groups processing unit can mutually be gone here and there
Connection is connected 4~20 grades of series；Series unit outermost is anode plate 13 and cathode plate 14 respectively, plate material can be graphite,
Alloy or metal-plated laminate, wherein it is adjacent for positive step with outermost Bipolar Membrane cathode side, with 15 anode of outermost Bipolar Membrane
Side is adjacent for cathode plate 14；The cavity that Bipolar Membrane 15 and anionic membrane 16 are constituted is acid compartment, Bipolar Membrane 15 and cationic membrane 17
The cavity of composition is alkaline chamber, and the cavity that anionic membrane 16 and cationic membrane 17 are constituted is salt room, and 13 place cavity of anode plate is sun
Pole room, negative 14 place cavity of plate plate are cathode chamber, and different types of room is mutually isolated, and the room of same type is connected to by pipeline.
The positive grade of fairing 11 connects anode plate 13, and fairing cathode connects cathode plate, and cathode chamber exhaust outlet connects hydrogen-oxygen combustion
Expect battery 2. hydrogen inlet, anode chamber's exhaust outlet connects 12 oxygen intake of hydrogen-oxygen fuel cell, the positive grade of hydrogen-oxygen fuel cell 12 and negative
Pole takes back fairing current feed terminal positive and negative anodes respectively.
Principle:
Bipolar Membrane 15 is made of anion exchange layer and cation exchange layer, anion exchange layer and cation exchange layer it
Between form boundary layer, outside pole plate plus reversed electric field effect under, anion shifts to anion exchange layer in boundary layer, cation
Shift to cation exchange layer, so that zwitterion in boundary layer be made to exhaust, when boundary layer hydrogen ion and hydroxide ion it is dense
When degree product is less than the ionic product of water, water is dissociated in Bipolar Membrane boundary layer, hydrogen ion across cation exchange layer, hydroxyl from
Son passes through anion exchange layer, as long as external electric field persistently exists, water will persistently dissociate into hydrogen ion and hydroxide ion；
The allocated pipeline of MaX salting liquid enter each salt room, under the DC Electric Field of pole plate, M+ ion cross sun from
Sub- film enters alkaline chamber, is combined into MOH with the hydroxide ion from Bipolar Membrane, flows out after pipe influx from lye export, Xa-
Ion crosses anionic membrane and enters acid compartment, is combined into HaX with the hydrogen ion from Bipolar Membrane, exports after pipe influx from acid solution
It flows out, remaining solution flows out after pipe influx from raffinate mouth in salt room；
On anode plate 13, hydroxide ion occurs electrochemical reaction and generates oxygen, and on cathode plate 14, hydrogen ion occurs
Electrochemical reaction generates hydrogen, and hydrogen enters 12 hydrogen of hydrogen-oxygen fuel cell out from hydrogen outlet and enter after cathode chamber aggregation
Mouthful, after oxygen is assembled in anode chamber, is come out from oxygen outlet and enter hydrogen-oxygen fuel cell oxygen intake, hydrogen and oxygen are in fuel cell
In regenerate water and discharge electric energy.
Fairing is with the following functions:
1, direct current is converted by external power supply；
2, the voltage between cathode plate and anode plate is adjusted；
3, the electric energy of fuel cell release is recycled by current feed terminal, to reduce external power load, reduces energy consumption.
Lithium salts is decomposed into lithium hydroxide solution and acid solution through the above technical solution by the present invention, to eliminate hydrogen-oxygen
Change sodium waste, saved reagent cost, preparation gained lithium hydroxide solution, acid solution contain after the concentration of alkaline-resisting reverse osmosis unit
Discharge reduction can reduce evaporation capacity, and step evaporation is only needed to be achieved with lithium hydroxide product, and energy consumption declines to a great extent, and obtain
Acid solution can be recycled for leaching after membrane concentration, reduce the consumption of acid solution.Thus the present invention substantially reduces
Energy consumption and acid and alkali consumption, reduce the production cost of lithium hydroxide.
Related content of the invention is illustrated above.Those of ordinary skill in the art are in the feelings illustrated based on these
The present invention will be realized under condition.Based on above content of the invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, should fall within the scope of the present invention under the premise of labour.
Claims (10)
1. lithium salt solution treatment process characterized by comprising
(a) lithium salt solution decomposition is prepared into lithium hydroxide solution, acid solution；
(b) it decomposes gained lithium hydroxide solution and concentration lithium hydroxide solution is concentrated to get by alkaline-resisting reverse osmosis membrane, and filter
To lithium hydroxide cleaner liquid；
(c) it decomposes gained acid solution and concentration acid solution is concentrated to get by acidproof reverse osmosis membrane, and acidleach clear liquid is obtained by filtration；
(d) it is mixed the lithium hydroxide cleaner liquid and acidleach clear liquid to obtain mixed once liquid；
(e) the mixed once liquid is obtained and is used for the industrial pure water and first-stage reverse osmosis of reuse by first-stage reverse osmosis
Concentrate；
(f) first-stage reverse osmosis that gained raffinate and step (e) first-stage reverse osmosis obtain after decomposing step (a) salting liquid is concentrated
Liquid is mixed to obtain secondary mixed liquor；
(g) secondary mixed liquor obtained by step (f) is obtained into two-pass reverse osmosis concentrate and second level reverse osmosis by two-pass reverse osmosis
Saturating clear liquid, the two-pass reverse osmosis concentrate, which returns in step (a), to be decomposed, the two-pass reverse osmosis clear liquid resume at step
(e) first-stage reverse osmosis is carried out again.
2. lithium salt solution treatment process as described in claim 1, which is characterized in that step (a) using bipolar membrane electrodialysis into
Row salting liquid decomposes.
3. lithium salt solution treatment process as described in claim 1, which is characterized in that the alkaline-resisting reverse osmosis membrane filtration device
Molecular cut off is 80~120D.
4. lithium salt solution treatment process as described in claim 1, which is characterized in that the acidproof reverse osmosis membrane filtration device
Molecular cut off is 200~300D.
5. lithium salt solution treatment process as described in claim 1, which is characterized in that
The pressure resistance of the alkaline-resisting reverse osmosis membrane is 120bar, and putamina specification uses 8040 or 4040 standard putaminas, and resistance to alkali ability is
It is resistant to 20%NaOH；The pressure resistance of the acidproof reverse osmosis membrane is 120bar, and putamina specification uses 8040 or 4040 standard putaminas, resistance to
Sour ability is tolerance 25%H2SO4。
6. lithium salt solution treatment process as described in claim 1, which is characterized in that the first-stage reverse osmosis uses rolling reverse osmosis
Permeable membrane is to Na2SO4Rejection >=98%.
7. lithium salt solution treatment process as described in claim 1, which is characterized in that the two-pass reverse osmosis uses high pressure reverse osmosis
Permeable membrane is to Na2SO4Rejection >=96%.
8. lithium salt solution treatment process as described in claim 1, which is characterized in that step (d) further includes once mixing to gained
It closes liquid and carries out pH adjusting.
9. lithium salt solution treatment process as claimed in claim 8, which is characterized in that step (d) adjusts pH of mixed and passes through salt
Solution decomposes preparation gained lithium hydroxide solution or acid solution is adjusted.
10. lithium salt solution treatment process as described in claim 1, which is characterized in that alkaline-resisting reverse osmosis membrane concentration gained concentration
Lithium hydroxide solution concentration > 2mol/L；Acid solutions > 2mol/L is concentrated in acidproof reverse osmosis membrane concentration gained.
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| CN201910779099.2A CN110453092A (en) | 2019-08-22 | 2019-08-22 | Lithium salt solution treatment process |
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