CN106379919B - A kind of method of comprehensive utilization of the waste liquid containing lithium - Google Patents
A kind of method of comprehensive utilization of the waste liquid containing lithium Download PDFInfo
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- CN106379919B CN106379919B CN201610748429.8A CN201610748429A CN106379919B CN 106379919 B CN106379919 B CN 106379919B CN 201610748429 A CN201610748429 A CN 201610748429A CN 106379919 B CN106379919 B CN 106379919B
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- desalination
- electrodialysis
- stoste
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of method of comprehensive utilization of waste liquid containing lithium.Prepared using the lithium carbonate wash water in lithium carbonate preparation technology, carbonization decomposition method and mother liquor is pyrolyzed caused by pure Lithium Carbonate or with the two there is the liquid being similarly composed to be used as raw material, through one-level or two-stage electrodialysis process, using cation-exchange membrane and anion-exchange membrane, on the one hand cause Li+Enrichment method is obtained, obtains Li+Content is 10g/L~20g/L rich lithium concentrate；On the other hand water can be produced to single stage desalting to purify, obtains deionized water of the TDS values less than 20mg/L and carry out reuse.Electrodialysis and counter-infiltration coupling are combined by the present invention, form close circulation technology so that Li+Comprehensive yield close to 100%, water loss zero, thus achieve Li in lithium carbonate wash water and solution with close composition+Synchronous, the complete recovery with water.
Description
Technical field
The invention belongs to solution isolation and purification technical field, specifically, is related to a kind of comprehensive profit of waste liquid containing lithium
Use method.
Background technology
Grand strategy resource of the new energy lithium metal as the New Times mankind, in lithium electricity, glass and ceramics, lithium base lubrication
The multiple fields such as fat, refrigeration, medicine, metallurgy and nuclear industry have a wide range of applications.In recent years, lithium electricity is in electronic product, new
The explosive growth of the application field such as energy automobile and extensive energy storage, drives domestic and international Li2CO3, the base such as LiCl, LiOH
The fast development of plinth lithium salts alkali product demand.
Lithium is mainly present in nature in the form of two kinds of solid mineral and liquid ore deposit, and wherein solid mineral lithium resource includes lithium brightness
The sedimentary rock ore deposit such as the pegmatite such as stone, petalite, lepidolite, amblygonite, eucryptite ore deposit and lithium montmorillonite, Ya Daer stones；Lithium
Pyroxene is most important solid lithium ore deposit, is typically calcined by ore dressing, 1100 DEG C of high temperature above, 250 DEG C of sulfuric acid bakings, leaching, essences
The steps such as removal of impurities, conversion are made to produce Li2CO3, the product such as LiCl, LiOH, but the preparation technology energy and supplies consumption are high, raw
It is higher to produce cost.Liquid ore deposit lithium resource mainly includes salt lake, underground heat, oil field water lithium resource, totally accounts for more than 2/3, salt lake is most
Main liquid lithium ore deposit；Natural bittern is Li+Coexisted with a large amount of alkali metal, alkaline-earth metal, chloride is the same as sulfate and borate
The complicated salting liquid system of a large amount of associations, the wherein extraction of lithium salts need to typically separate step by step by the natural phase separation in salt pan
The accompanying impurities such as sodium salt, sylvite, magnesium salts in bittern, the higher concentrated brine of lithium content is obtained, then carried by specific separation
Take, refining and edulcoration, precipitation conversion etc. step obtain Li2CO3, the basic lithium salts product such as LiCl.Due to different brine deposits composition and
Chemical type varies, and its separation and Extraction processing technology is different, is corresponding with the precipitation method, absorption method, selective electric osmose
Analysis method, calcining leaching method, solvent extraction, multiple routes that nano filtering process is technical characteristics；Wherein absorption method, selectivity electricity
Dialysis, calcining leaching, nano filtering process are the technologies developed for high contents of calcium and magnesium, low grade brine lithium resource.
Either still produced using Gu Kuang such as spodumenes using the liquid ore deposit such as salt lake as raw material to produce the basic lithium salts such as lithium carbonate
Product, or prepare by carbonization-decomposition technique the production process of pure Lithium Carbonate, inevitably comprising clean, wash and starch and
The steps such as elution, to remove Li2CO3Parcel, the mother liquor of entrainment or other soluble impurities in precipitation or concentrate, this will be produced
Raw substantial amounts of lithium carbonate wash water；Especially LITHIUM BATTERY, high-purity Li2CO3Production process in, Li per ton2CO35~20 tons need to be consumed
Deionized water.In addition, carbonization-decomposition method prepares high-purity Li2CO3Production process can also produce substantial amounts of pyrolysis mother liquor.Due to
Li2CO3Microsolubility, these lithium carbonate wash waters and pyrolysis mother liquor in be dissolved with a large amount of Li+, its content is from hundreds of ppm to 3g/L
Left and right, other cations are mainly a small amount of Na+With micro K+、Ca2+、Mg2+, anion is mainly CO3 2-、HCO3 -, and a small amount of
Cl-、SO4 2-With micro boron；If these ions are not recycled, substantial amounts of fresh water or deionized water are not only wasted, and
Lithium loss amount costs dearly up to 10%~20%, causes resource utilization low, production cost improves.
At present, Li is contained for this+The relatively low lithium carbonate wash water of concentration or pyrolysis mother liquor, prior art are mostly by lithium carbonate
Fraction lithium carbonate wash water all directly discharge or is returned to soda ash preparation steps by wash water, instead of soda ash preparation water, when returning
When using technique leading portion, a part of Li in lithium carbonate wash water+It will be analysed with other impurity in soda ash in the form of Crude lithium Carbonate
Go out, be separated by filtration, a small amount of Li+Remain in soda ash liquid and be used to refine the steps such as removing calcium and magnesium, precipitation lithium carbonate, most of carbonic acid
Lithium wash water still makees emission treatment；And a caused pyrolysis mother liquor part such as returns to washup, sized mixing at the step in carbonization-decomposition technique
Suddenly, remainder directly discharges.Meanwhile in the prior art also by adding HF, Na in lithium carbonate wash water or pyrolysis mother liquor3PO4
Deng precipitating reagent, to obtain LiF or Li3PO4Deng slightly solubility lithium salts, but LiF and Li3PO4Market demand very little, and precipitate female
Still contain a small amount of Li in liquid+, water therein also do not reclaimed effectively.In addition, also have lithium carbonate wash water in the prior art
Or pyrolysis mother liquor is discharged into salt Tanaka, by Li therein+Recovery is concentrated by evaporation, but due to Li in treatment fluid+Concentration is relatively low, steams
Shampoo amount is big, and salt pan investment is of a relatively high, and loses most waters, and this is relative for freshwater resources such as salt lake, oil fields
For the arid area of shortage, huge waste is undoubtedly caused.Therefore, for lithium carbonate wash water, pyrolysis mother liquor or there is phase
The solution closely formed, develop Li+Enrichment method and synchronously reclaim fresh water therein method it is particularly significant.
Although there are some to handle feed liquid containing lithium (generally bittern) in the prior art, wherein Li is extracted+Report,
Such as：(1) a kind of method of the adsorbing and extracting lithium chloride from solution, by the way that eluent is recycled for multiple times in this method, will elute
Li in liquid+Concentration bring up to more than 1.6g/L, then Ca therein is removed using cationic ion-exchange resin2+、Mg2+, finally use
Electrodialysis is by Li in eluent+Content be concentrated to more than 16g/L, and electrodialysis desalination production water returns to desorption workshop section as solution
Smoke water；But this method flow is longer, it is related to multiple steps such as absorption, ion exchange, electrodialysis, saliferous in the desalinization liquor of reuse
Amount is higher, it is impossible to is used as fresh water or deionized water；(2) a kind of technology that separating magnesium and lithium is realized using NF membrane, nanofiltration institute
Obtain rich lithium solution and realize Li through counter-infiltration+Concentration, fresh water obtained by counter-infiltration is back to use stoste dilution process；But this method by
The limitation of concentrated water osmotic pressure, counter-infiltration is to Li+Actual concentrating degree be far below 5g/L, by counter-infiltration reclaim fresh water only account for
There are relatively low ratio, and the Ca in counter-infiltration raw water2+And SO4 2-Easily crystallization precipitate into film surface, shortens the service life of film；
(3) a kind of method that concentration lithium solution is obtained from seawater or bittern, this method carry lithium using the absorption of lithium manganate adsorbent, institute
Obtain eluent to concentrate through the electrodialysis of two-stage routine, Li can be obtained+Content be 1.5% or so concentrate, first order electrodialysis
Desalination produces water after other one-level electrodialysis advanced desalination, obtains lithium content 10ppm~100ppm desalinization liquor, returns to absorption
Lithium step is put forward to use as absorption raw water；But this method can not directly handle lithium carbonate wash water or the meta-alkalescence with similar composition
Solution, as Ca in raw water2+、Mg2+、SO4 2-When plasma content raises, easily formed and precipitated in enriched chamber's film surface；Obtained desalination
TDS (total dissolved solidss) value in liquid is still higher, it is impossible to is used as fresh water or deionized water；(4) it is a kind of from high Mg/Li ratio salt
The method of lake bittern water separating magnesium and concentration lithium, using monovalent ion selective ion exchange membrane electrodialysis, while realizes magnesium lithium
Separation and Li+Concentration, Li in concentrate+Content can bring up to 10g/L or higher, but the technology only limits stoste
For Mg/Li ratio (i.e. Mg in stoste2+With Li+Mass ratio) for 1~300 salt lake bittern and its evaporation gained concentrated brine.
Above technology is only for Li in feed liquid containing lithium+Recovery, but without for lithium carbonate wash water, pyrolysis mother liquor so
Contain more CO3 2-And HCO3 -Or the waste liquid containing lithium of the meta-alkalescence with similar composition is reclaimed, it can not realize Li+With
The synchronous recovery of fresh water (or deionized water).
The content of the invention
To solve the above-mentioned problems of the prior art, the invention provides a kind of comprehensive utilization side of the waste liquid containing lithium
Method, these waste liquids containing lithium are come from caused lithium carbonate wash water in the preparation technology of lithium carbonate, prepared using carbonization-decomposition method
Mother liquor is pyrolyzed caused by pure Lithium Carbonate or is given up with the lithium carbonate wash water or similar other of pyrolysis mother liquor composition containing lithium
Abandon liquid；The method of comprehensive utilization can realize Li+Enrichment method and deionized water recovery, be greatly reduced lithium resource and water money
The waste in source.
In order to reach foregoing invention purpose, present invention employs following technical scheme：
A kind of method of comprehensive utilization of waste liquid containing lithium, the waste liquid containing lithium, institute are recycled using electrodialysis plant
State membrane stack that electrodialysis plant formed by the cation-exchange membrane and anion-exchange membrane that are alternately arranged and positioned at the membrane stack
The anode chamber of both sides and cathode chamber are formed；Formed between wherein described cation-exchange membrane and the anion-exchange membrane and alternately arranged
The enriched chamber and desalting chamber of row；The waste liquid containing lithium include lithium carbonate preparation technology in lithium carbonate wash water and/or carbonization-point
Solution prepares pyrolysis mother liquor caused by pure Lithium Carbonate；Wherein, the waste liquid containing lithium contains Li+Concentration for 500mg/L~
5000mg/L, CO3 2-And HCO3 -Total concentration be 2000mg/L~40000mg/L；The method of comprehensive utilization includes following step
Suddenly：
Prepare the first desalination stoste step：Remove the CO in the waste liquid containing lithium3 2-And HCO3 -, and adjust pH value for 3~
7, then filter, obtain the first desalination stoste；
One-level electrodialysis step：The first desalination stoste is passed through in the desalting chamber of the electrodialysis plant and described
Circulated in electrodialysis plant, form the first desalinization liquor；The water inlet of the first concentrate is passed through into the enriched chamber of the electrodialysis plant
And circulated in the electrodialysis plant；In the presence of DC electric field, the Li in first desalinization liquor+By it is described sun from
Proton exchange is migrated to the enriched chamber from the desalting chamber, and primary concentration production water is obtained in the enriched chamber and is concentrated as rich lithium
Liquid, single stage desalting production water is obtained in the desalting chamber；
Reverse osmosis step：Reverse-osmosis treated is carried out to single stage desalting production water, obtains desalination by reverse osmosis production water；
High-purity lithium salts preparation process：Using rich lithium concentrate described in base extraction, refined lithium chloride solution is obtained；Go forward side by side one
Step handles the refined lithium chloride solution, obtains high-purity lithium salts.
Further, two level electric osmose is also included between the one-level electrodialysis step and high-purity lithium salts preparation process
Analyse step：It is using the electrodialysis plant, second desalination is former using primary concentration production water as the second desalination stoste
Liquid is passed through in the desalting chamber of the electrodialysis plant and circulated in the electrodialysis plant, forms the second desalinization liquor；To described
The second concentrate is passed through in the enriched chamber of electrodialysis plant to intake and circulate in the electrodialysis plant；In the work of DC electric field
Under, the Li in second desalinization liquor+Migrated by the cation-exchange membrane from the desalting chamber to the enriched chamber,
The enriched chamber obtains secondary concentration production water as the rich lithium concentrate, and two level desalination production water is obtained in the desalting chamber；Its
In, the one-level electrodialysis step and the two level electrodialysis step are carried out in different electrodialysis plants.
Further, the two level desalination production water is back in the one-level electrodialysis step and the first desalination stoste
Merge.
Further, in the one-level electrodialysis step and/or the two level electrodialysis step, using constant voltage or perseverance
Current practice, it is 50A/m to control average current density2~550A/m2；The enriched chamber and/or the apparent velocity of the desalting chamber
For 2cm/s~6cm/s.
Further, in the one-level electrodialysis step, the first concentrate water inlet is deionized water, the one-level
The dilution of concentration production water or primary concentration production water；In the two level electrodialysis step, the second concentrate water inlet
Water is produced for deionized water, the secondary concentration or the secondary concentration produces the dilution of water.
Further, in the reverse osmosis step, after carrying out reverse-osmosis treated to single stage desalting production water, also obtain
Reverse osmosis concentration produces water；The reverse osmosis concentration production water is back in the one-level electrodialysis step and the first desalination stoste
Merge.
Further, the ratio between the first desalination stoste and the volume of first concentrate water inlet is controlled to be not less than 10；
The ratio between the second desalination stoste and the volume of second concentrate water inlet is controlled to be not less than 10.
Further, the one-level electrodialysis step and the two level electrodialysis step process use NaNO3The aqueous solution
Or Na2SO4The aqueous solution is as electrode cycle liquid.
Further, the cation-exchange membrane is monovalent ion selectivity anode membrane, and the anion-exchange membrane is monovalence
Ion selectivity cavity block.
Further, HCl/water solution or H are added into the waste liquid containing lithium2SO4The aqueous solution, to be given up described in removal containing lithium
The CO abandoned in liquid3 2-And HCO3 -；Solid suspension content in the first desalination stoste is controlled to be not higher than 5mg/L.
Beneficial effects of the present invention：
(1) method of comprehensive utilization of the invention is lithium carbonate wash water, is pyrolyzed mother liquor and has Li in the solution of close composition+The recovery of enrichment method and water provide a kind of cleaning, efficient technical scheme, realize Li+It is same with deionized water
Step, completely recovery；Obtain rich lithium concentrate and deionized water fully meets Li2CO3Will etc. the use in basic lithium salts preparation technology
Ask.
(2) Ca is contained using the processing of monovalent ion selective ion exchange membrane2+、Mg2+、SO4 2-The first higher desalination stoste,
Solves CaSO in electrodialytic process4Saturation Deng indissoluble salt separates out problem.
(3) by the method for electrodialysis-counter-infiltration coupling combination and respective interstage coupling, close circulation technology is formed,
Li+With the comprehensive yield of deionized water close to 100%, obtain that the purity of deionized water is also very high, improve resource utilizes effect
Rate, reduce Li2CO3Etc. the production cost of basic lithium salts.
(4) according to the method for comprehensive utilization of the present invention, having process, continuously, stably simple to operate, floor space is small, throws
Money saves, the plurality of advantages such as cost is low.
(5) it is applied to produce Li as raw material using various solid minerals and liquid ore deposit according to the method for comprehensive utilization of the present invention2CO3
Etc. the production process of basic lithium salts, great popularization.
Brief description of the drawings
The following description carried out in conjunction with the accompanying drawings, above and other aspect, feature and the advantage of embodiments of the invention
It will become clearer, in accompanying drawing：
Fig. 1 is the process chart according to the method for comprehensive utilization of the waste liquid containing lithium of the present invention；
Fig. 2 is the process chart in a-quadrant in Fig. 1；
Fig. 3 is the process chart in B area in Fig. 1.
Embodiment
Hereinafter, with reference to the accompanying drawings to embodiments of the invention are described in detail.However, it is possible to come in many different forms real
Apply the present invention, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these implementations
Example is in order to explain the principle and its practical application of the present invention, so that others skilled in the art are it will be appreciated that the present invention
Various embodiments and be suitable for the various modifications of specific intended application.
It will be appreciated that although can be used term " first ", " second " etc. to describe various materials herein, but these
Material should not be limited by these terms.These terms are only used for making a distinction a material with another material.
As shown in Figure 1-Figure 3, the present invention provides a kind of method of comprehensive utilization of the waste liquid containing lithium, comprises the following steps：
Step 1：The acquisition and pretreatment of raw material.
Waste liquid containing lithium of the present invention derive from lithium carbonate preparation technology in clean, elute, wash and starch caused by
Lithium carbonate wash water, prepared using carbonization-decomposition method and mother liquor be pyrolyzed caused by pure Lithium Carbonate, or with above-mentioned lithium carbonate wash water,
Being pyrolyzed mother liquor has the feed liquid of similar composition, and these waste liquids containing lithium are typically in alkalescence, wherein dissolved with more Li+, a small amount of Na+、
Micro K+、Ca2+、Mg2+, anion is mainly CO3 2-Or HCO3 -, a small amount of Cl-、SO4 2-With micro B (OH)4 -；Wherein, Li+Concentration
For 500mg/L~5000mg/L, CO3 2-And HCO3 -Total concentration be 2000mg/L~40000mg/L.
What deserves to be explained is in Fig. 1, to prevent above-mentioned method of comprehensive utilization from forming one " endless loop ", it is difficult to keep thing
Material balance, is caused unnecessary misunderstanding, the lithium carbonate system in the above-mentioned source of waste liquid containing lithium is represented with " the main production process of lithium carbonate "
Standby technological process.
First CO is removed in basis waste liquid containing lithium3 2-Or HCO3 -Outer Main Anions are Cl-Or SO4 2-, it is corresponding to containing lithium
HCl/water solution or H are added in waste liquid2SO4The aqueous solution, to remove CO therein3 2-、HCO3 -；Specifically, when this gives up containing lithium
When to abandon liquid be chloride system, HCl/water solution is added thereto, when the waste liquid containing lithium is sulfate system, is added thereto
Enter H2SO4The aqueous solution.
Then it is 3~7 to adjust its pH value, while by temperature control below 30 DEG C.
The solid impurity in the waste liquid containing lithium is finally filtered, obtains the first desalination stoste, and makes what is obtained after filtering
The content of solid suspension (SS) is not higher than 5mg/L in first desalination stoste.
Step 2：Electrodialysis concentrates.
The mode that one-level electrodialysis or one-level electrodialysis, two level electrodialysis combine is used in the present invention to play Li+It is dense
Contract the purpose being enriched with.
Specifically, Li is realized by electrodialysis plant+Enrichment method.The electrodialysis plant by be alternately arranged sun from
The membrane stack and the anode chamber of membrane stack both sides and cathode chamber composition that proton exchange and anion-exchange membrane are formed；Its cationic is handed over
Change the enriched chamber and desalting chamber for being formed and being alternately arranged between film and anion-exchange membrane.
First desalination stoste is passed through in the desalting chamber of the electrodialysis plant, and circulated in the electrodialysis plant, is formed
First desalinization liquor；The first concentrate is passed through into the enriched chamber of the electrodialysis plant simultaneously to intake and follow in electrodialysis plant
Ring.
Specifically, the electrodialysis plant be also circumscribed with desalinization liquor circulating pump, desalinization liquor circulating slot, concentrate circulating pump,
Concentrate circulating slot, connected, concentrated by desalination circulation line between desalting chamber, desalinization liquor circulating pump and desalinization liquor circulating slot
Connected between room, concentrate circulating pump and concentrate circulating slot by concentration cycles pipeline.The first desalination stoste is logical first
Enter into desalinization liquor circulating slot, then by desalinization liquor circulating pump and desalination circulation line between desalting chamber and desalinization liquor circulating slot
Circulation, and form the first desalinization liquor；First concentrate enters concentrate circulating slot, and passes through concentrate circulating pump and concentration
Circulation line circulates between enriched chamber and concentrate circulating slot, and forms the first concentrate.
Electrodialysis step process uses 0.5mol/L NaNO3The aqueous solution or Na2SO4The aqueous solution is as electrode cycle liquid, tool
For body, if the first desalination stoste is chloride system, using 0.5mol/L NaNO3The aqueous solution as electrode cycle liquid,
If the first desalination stoste is sulfate system, using 0.25mol/L Na2SO4The aqueous solution is as electrode cycle liquid.In direct current
In the presence of electric field, the Li in first desalinization liquor+Migrated by cation-exchange membrane from desalting chamber to enriched chamber, described
Enriched chamber obtains primary concentration production water, and single stage desalting production water is obtained in the desalting chamber.
What deserves to be explained is as Ca in the first desalination stoste2+、Mg2+Deng high-valence cationic and SO4 2-Etc. high-valence anion
(such as Ca when content is higher2+And SO4 2-Concentration be all higher than 50mg/L), then cation-exchange membrane preferably using monovalent ion select
Property anode membrane, anion-exchange membrane preferably uses monovalent ion selectivity cavity block or common cavity block, to avoid CaSO4Deng indissoluble salt
Saturation separates out in enriched chamber and film surface.
The monovalent ion selectivity anode membrane can use the CIMS types or K192 types film, rising sun nitre of the production of Japanese ASTOM companies
The CSO types or CSV types film of subsidiary's production or other companies have close selective anode membrane；Monovalent ion selectivity cavity block
ACS types or A192 types film, the ASV types film of Asahi Glass company production or other companies of the production of ASTOM companies, which can be used, has phase
The cavity block of nearly selectivity.
Usually, the mechanism control voltage of the DC electric field is 9V~20V, but is had closely with specific device parameter
Relation, voltage difference is larger needed for distinct device size.Control electric current density average is 50A/m in practical operation2~550A/
m2.In order to ensure concentration stream normal circulation and conduction, at least in one-level electrodialytic startup stage, circulated in the concentrate
A small amount of first concentrate water inlet is passed through in groove, first concentrate water inlet composition can be primary concentration liquid production water or deionized water
Or the dilution of primary concentration liquid production water.Using the electro-osmosis phenomenon of one-level electrodialytic process reclaimed water, one in desalting chamber is small
Partial moisture is penetrated into primary concentration production water, so as to realize primary concentration production water volume and wherein Li+The Synchronous lifting of content.
The first desalination stoste volume (or flow) is controlled to enter the ratio between water volume (or flow) not less than 10 with first concentrate.
The apparent velocity of the enriched chamber and/or the desalting chamber is preferably 2cm/s~6cm/s.
If the primary concentration production water obtained after one-level electrodialysis step can reach target (Li+Concentration be
14g/L~19g/L), then primary concentration production water can be used to enter LITHIUM BATTERY Li2CO3In preparation process；The single stage desalting production
Water then enters in reverse osmosis step, to purify single stage desalting production water, desalination by reverse osmosis production water is obtained, for use as deionized water or light
Water, the recycling of desalination by reverse osmosis production water is thus achieved, greatlys save fresh water cost, while improved lithium synthesis and receive
Rate.
If failing to reach target, the electrodialysis steps of one-levels can be set again more, primary concentration production water is entered
Row two level electrodialysis operation.
One-level electrodialysis is designed in the present invention and two level electrodialysis step combines.Concrete operations conduct：The one-level is dense
Contracting production, using the electrodialysis plant, the second desalination stoste is passed through the desalination of electrodialysis plant as the second desalination stoste
Circulated in room and in electrodialysis plant, form the second desalinization liquor；Second to be passed through into the enriched chamber of electrodialysis plant dense simultaneously
Contracting liquid is intake and circulated in electrodialysis plant.
Specifically, with one-level electrodialytic process analogously, the second desalination stoste is passed through desalinization liquor circulating slot
In, the second desalination stoste is circulated by desalinization liquor circulating pump and desalination circulation line between desalting chamber and desalinization liquor circulating slot,
Form the second desalinization liquor；The water inlet of second concentrate is passed through in concentrate circulating slot, the water inlet of the second concentrate is followed by concentrate
Ring pump and concentration cycles pipeline circulate between following pendular ring groove in enriched chamber and concentration, form the second concentrate.In DC electric field
Under effect, the Li in second desalinization liquor+Migrated by ion selectivity anode membrane from desalting chamber to enriched chamber, in the concentration
Room obtains secondary concentration production water, and two level desalination production water is obtained in the desalting chamber.
More specifically, the primary concentration production water is made to enter the desalting chamber of two level electrodialysis plant, by the function of current
Afterwards, Li+Migrate to the enriched chamber of two level electrodialysis plant, secondary concentration production water is obtained, after secondary concentration production water can then enter
Continuous LITHIUM BATTERY Li2CO3In preparation process；Desalting chamber obtains two level desalination production water and can then returned to converge with the first desalination stoste
Reentered after conjunction and Li is carried out in one-level electrodialysis step+Separation.This formation interstage coupling, the lithium that can improve this step are received
Rate, by coupling the matching and adaptation of material, the stability of electrodialysis influent quality is improved, so as to ensure operation and production water
The stability of water quality.
What deserves to be explained is the one-level electrodialysis step and two level electrodialysis step are in different electrodialysis plants
Carry out.
According to actual conditions, primary concentration is produced into water or secondary concentration produces water as rich lithium concentrate, as follow-up high-purity
The preparation of lithium salts.
Step 3：Reverse osmosis step.
Water is produced as feed water by reverse osmosis using single stage desalting, through first-stage reverse osmosis, obtains the counter-infiltration that TDS values are less than 20mg/L
Desalination production water and Li+The reverse osmosis concentration that content is 250mg/L~500mg/L produces water；Wherein, desalination by reverse osmosis production water can be made
For deionized water reuse, and reverse osmosis concentration production water is then back in step 1, is incorporated in the first desalination stoste.
Certainly, if above-mentioned standard can not be reached by first-stage reverse osmosis, two level can be also further added by after first-stage reverse osmosis
Counter-infiltration, water is produced to handle single stage desalting by two steps ro, can be light as the counter-infiltration that deionized water is used using acquisition
Change production water.
Step 4：The preparation of high-purity lithium salts；Using rich lithium concentrate described in base extraction, refined lithium chloride solution is obtained；
And the refined lithium chloride solution is further handled, obtain high-purity lithium salts.
In the present embodiment, LITHIUM BATTERY Li is prepared using above-mentioned rich lithium concentrate2CO3, referring in particular to following step：
(1) LiCl solution is refined.
The preparation and purification of 28% soda ash solution：The refined and lithium carbonate step of converting of rich lithium concentrate all uses soda ash
The aqueous solution contains a small amount of Mg as precipitating reagent in calcined soda for industry2+, high volence metal ion salt and other slightly solubility impurity,
It must remove in advance, in case it enters directly into LITHIUM BATTERY Li in sinker conversion procedure2CO3In.When preparing the soda ash aqueous solution,
Na per ton2CO3Middle addition 2.0kg~2.5kg NaOH, be configured under agitation with deionized water 28% soda ash it is water-soluble
Liquid, it is filtered to complete purification.
At 55 DEG C~60 DEG C and under the conditions of being sufficiently stirred, by the rich lithium concentrate and the 28% soda ash aqueous solution, 30%
Caustic-soda aqueous solution be mixed to form reaction solution, and make the reaction solution pH be more than 12.5, preferably pH be 12.5~13.0；Continue
Separation of solid and liquid is carried out after stirring reaction 40min, obtains refined LiCl solution, can be directly used for producing LITHIUM BATTERY Li2CO3Product.This
The depth that act as of step removes Ca2+、Mg2+, control added in every cube of rich lithium concentrate of gained 28% soda ash aqueous solution 7L~
9L is preferred.
(2) LITHIUM BATTERY Li2CO3Acquisition.
More than 90 DEG C and under conditions of being sufficiently stirred, according to Na2CO3With Li in the refined LiCl solution+Chemistry meter
Amount is than being 1:2 are added slowly to the described 28% soda ash aqueous solution in the refined LiCl solution, insulation reaction 30min with
On, obtain sinker reaction product.
The sinker reaction product is subjected to vacuum filter, obtains filter cake and filtrate.Filter cake uses and is heated to 85 DEG C in advance
~90 DEG C of deionized water elution, then with deionized water by 20%~30% solid-to-liquid ratio in 90 DEG C and the condition that is sufficiently stirred
Under wash and starch, filtered after washing and starching 30min, filter cake is fully eluted using the deionized water of same temperature.Used in washing and starching and eluting
Deionized water total amount is stoichiometrically counted Li to be obtained in refined LiCl solution2CO310~18 times of weight.Will be through filtering
Gained filter cake is dried at 240 DEG C~280 DEG C and is cooled to less than 40 DEG C after washing and washing and starching, and produces purity and is not less than 99.5%
LITHIUM BATTERY Li2CO3。
What deserves to be explained is the preparation water of the soda ash aqueous solution, caustic-soda aqueous solution etc. can use above-mentioned step in step 4
The rapid three desalination by reverse osmosis production water obtained, meanwhile, elution now, slurry scouring water can also use this part desalination by reverse osmosis production
Water；In view of dosage is less herein, remaining most desalination by reverse osmosis production water is then back in the main production process of lithium carbonate, is used for
Prepare solution or as slurry.
Gained filtrate can remove the CO wherein remained in this step3 2-Wherein most sodium salts are removed by salt pan evaporation
It is used for Li afterwards2CO3Or the preparation of LiCl products, so as to improve the comprehensive yield of lithium.
Washing water in this step and to wash and starch water be the object comprehensively utilized in the application, can return to step 1
In, and mixed with caused lithium carbonate wash water in the main production process of lithium carbonate, as waste liquid containing lithium, to be handled and through electricity
Dialysis concentrates, so as to improve the comprehensive yield of lithium.
What deserves to be explained is above-mentioned steps three and step 4 are two relatively independent different paths, one-level is taken off respectively
Salt produces water and primary concentration production water or secondary concentration production water is handled；Realized according to the method for comprehensive utilization of the present invention
Li in waste liquid containing lithium+Enrichment method and fresh water recovery synchronous progress, significantly improve Li2CO3Extracted etc. basic lithium salts
With the level of resources utilization of preparation process, lithium salts production cost is reduced.
Below, usefulness of the present invention is shown by several embodiments.
The embodiment 1~5 of table 1 concentrates Li+The response parameter of process
Note：In table 1, " anode membrane " refers to above-mentioned " cation-exchange membrane ", and " cavity block " refers to above-mentioned " anion-exchange membrane ".
The chemical composition of the waste liquid containing lithium of 2 embodiment of table 1, the first desalination stoste and each production water
With reference to shown in table 2, the results showed that, Li+Concentration by the (lithium carbonate formed as shown in table 2 of waste liquid containing lithium
Wash water) in 503mg/L concentration bring up to primary concentration production water in 6.93g/L, Li+Primary recovery be up to 90%, Li+
Significantly concentrated, and TDS values are 371mg/L in primary concentration production water.
The chemical composition of the waste liquid containing lithium of 3 embodiment of table 2, the first desalination stoste and each production water
With reference to shown in table 3, the results showed that, compared with waste liquid containing lithium (the lithium carbonate wash water formed as shown in table 3),
Li+Concentration 14.65g/L has been brought up to by 5088mg/L, a high income of lithium up to 97%, and by single stage desalting produce water in
Li+Concentration be reduced to 214mg/L.
At the same time, in view of single stage desalting produces Li in water in the table 3 of embodiment 2+Concentration still can be reduced further, can be one
Level electrodialysis step adds one section of electrodialysis and is used for advanced desalination, and in extra segment, it is additional to produce water using the single stage desalting in table 3
The desalination stoste of section, extra segment concentration production water returns to be merged with the first desalination stoste, thus further improves the yield of lithium.
The chemical composition of the waste liquid containing lithium of 4 embodiment of table 3, the first desalination stoste and each production water
With reference to shown in table 4, the results showed that, compared with waste liquid containing lithium (waste liquid containing lithium formed as shown in table 4),
Li+Concentration 14.1g/L has been brought up to by 3433mg/L, a high income of lithium up to 97%, and by single stage desalting produce water in
Li+Concentration be reduced to 121mg/L.
What deserves to be explained is in example 4, in view of Mg in the first desalination stoste2+、Ca2+And SO4 2-Plasma contains
Amount is higher, has exceeded 50mg/L, therefore cation-exchange membrane and anion-exchange membrane difference employed in the present embodiment
For monovalent ion selectivity anode membrane and monovalent ion selectivity cavity block, in this way, the monovalent ion selectivity due to the two so that
Mg2+、Ca2+、SO4 2-、B(OH)4 -It is trapped within etc. most of foreign ion in desalting chamber, forms single stage desalting production water, so as to
Avoid these ions to enter in enriched chamber, prevent from generating CaSO4Deng indissoluble salt, saturation separates out.
The chemical composition of the waste liquid containing lithium of 5 embodiment of table 4, the first desalination stoste and each production water
With reference to shown in table 5, the results showed that, Li+Concentration by the (lithium carbonate formed as shown in table 5 of waste liquid containing lithium
Wash water) in 1480mg/L concentration bring up to primary concentration production water in 9097mg/L, Li+Primary recovery be up to 92%,
Li+Significantly concentrated；And TDS values are 894mg/L in primary concentration production water.
The chemical composition of the waste liquid containing lithium of 6 embodiment of table 5, the first desalination stoste and each production water
What deserves to be explained is the primary concentration production that the first desalination stoste in embodiment 5 is obtained from embodiment 4
Water, in this way, also can combine embodiment 4 with embodiment 5, it is believed that the operation in embodiment 5 is one-level electric osmose in example 4
The two level electrodialysis operation carried out after step is analysed, thus, single stage desalting production water and primary concentration production water in embodiment 5 also may be used
It is considered the two level desalination production water and secondary concentration production water of embodiment 4.
With reference to the result of table 5 and table 6, it can be seen that (lithium carbonate formed as shown in table 5 is washed with waste liquid containing lithium
Water) compare, the Li in secondary concentration produces water+Concentration bring up to 18.2g/L.
Li in single stage desalting production water (i.e. embodiment 4 carries out the two level desalination production water after two level electrodialysis) in embodiment 5+
Concentration be down to 1435mg/L, equivalent to Li in the first desalination stoste+The 9% of total amount, it may return to one-level electrodialysis, i.e., it is same
The first desalination stoste in embodiment 4 enters one-level electrodialysis step after merging, and forms material coupling.
Embodiment 6
The present embodiment is that the single stage desalting obtained in embodiment 4 production water is carried out into reverse-osmosis treated, higher to obtain purity
Deionized water (i.e. desalination by reverse osmosis production water).
The single stage desalting production water 300L that Example 4 obtains, the concrete composition of single stage desalting production water are shown in Table 5；Adopt
With Dow Chemical FILMTEC BW30-2540 type membrane modules, two steps ro processing is carried out：Using single stage desalting production water as
First-stage reverse osmosis is intake, and is handled by first-stage reverse osmosis and is obtained first-stage reverse osmosis desalination production water and first-stage reverse osmosis concentration production water；
First-stage reverse osmosis desalination production water is intake as two-pass reverse osmosis, is handled by two-pass reverse osmosis and is obtained two-pass reverse osmosis desalination production water
Production water is concentrated with two-pass reverse osmosis.Wherein, first-stage reverse osmosis concentration production water then returns mixes with the first desalination stoste, is thusly-formed
The coupling combination of electrodialysis-counter-infiltration；Two-pass reverse osmosis desalination production water can be used as deionized water and be used to prepare solvent, washing
The purposes such as product；And two-pass reverse osmosis concentration production water is then returned and mixed with single stage desalting production water, intake as first-stage reverse osmosis, such as
This forms two steps ro coupling.
Through multiple circulation experiment, yield and production water index to each stage are determined, as shown in table 7.
Each stage yield of the two steps ro of table 7 and production water index
Index according to water is respectively produced in table 7 can be seen that first-stage reverse osmosis desalination production water and can be used as Li2CO3Preparation technology
The purposes such as the preparations of reagent such as middle caustic-soda aqueous solution, the soda ash aqueous solution；And the purity of two-pass reverse osmosis desalination production water has met electricity
Pond level Li2CO3Slurry.
In this way, by electrodialysis and counter-infiltration coupling combination, close circulation technology is formed so that Li+Comprehensive yield approach
100%, water loss zero；Therefore can realize lithium carbonate wash water and with close composition solution in Li+It is same with water
Step, completely recovery, and circulating and recovering is to Li2CO3In preparation technology etc. basic lithium salts.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (10)
1. a kind of method of comprehensive utilization of waste liquid containing lithium, the waste liquid containing lithium is recycled using electrodialysis plant, it is described
Membrane stack that electrodialysis plant is formed by the cation-exchange membrane and anion-exchange membrane that are alternately arranged and positioned at the membrane stack two
The anode chamber of side and cathode chamber are formed；Formed and be alternately arranged between wherein described cation-exchange membrane and the anion-exchange membrane
Enriched chamber and desalting chamber；The waste liquid containing lithium includes lithium carbonate wash water and/or carbonization-decomposition in lithium carbonate preparation technology
Method prepares pyrolysis mother liquor caused by pure Lithium Carbonate；Wherein, the waste liquid containing lithium contains Li+Concentration for 500mg/L~
5000mg/L, CO3 2-And HCO3 -Total concentration be 2000mg/L~40000mg/L；Characterized in that, the method for comprehensive utilization
Comprise the following steps：
Prepare the first desalination stoste step：Remove the CO in the waste liquid containing lithium3 2-And HCO3 -, and it is 3~7 to adjust pH value, so
After filter, obtain the first desalination stoste；
One-level electrodialysis step：The first desalination stoste is passed through in the desalting chamber of the electrodialysis plant and in the electric osmose
Circulated in analysis apparatus, form the first desalinization liquor；Be passed through into the enriched chamber of the electrodialysis plant the first concentrate water inlet and
Circulated in the electrodialysis plant；In the presence of DC electric field, the Li in first desalinization liquor+Handed over by the cation
Change film to migrate to the enriched chamber from the desalting chamber, primary concentration production water obtained in the enriched chamber as rich lithium concentrate,
Single stage desalting production water is obtained in the desalting chamber；Control volume that the first desalination stoste and first concentrate intake it
Than not less than 10；
Reverse osmosis step：Reverse-osmosis treated is carried out to single stage desalting production water, obtains desalination by reverse osmosis production water；
High-purity lithium salts preparation process：Using rich lithium concentrate described in base extraction, refined lithium chloride solution is obtained；And further locate
The refined lithium chloride solution is managed, obtains high-purity lithium salts.
2. method of comprehensive utilization according to claim 1, it is characterised in that in the one-level electrodialysis step and the height
Also include two level electrodialysis step between pure lithium salts preparation process：Using primary concentration production water as the second desalination stoste, profit
With the electrodialysis plant, the second desalination stoste is passed through in the desalting chamber of the electrodialysis plant and in the electrodialysis
Circulated in device, form the second desalinization liquor；The water inlet of the second concentrate is passed through into the enriched chamber of the electrodialysis plant and in institute
State in electrodialysis plant and circulate；In the presence of DC electric field, the Li in second desalinization liquor+Pass through the cation exchange
Film is migrated to the enriched chamber from the desalting chamber, and secondary concentration production water is obtained in the enriched chamber and is concentrated as the rich lithium
Liquid, two level desalination production water is obtained in the desalting chamber；Wherein, the one-level electrodialysis step and the two level electrodialysis step exist
Carried out in different electrodialysis plants.
3. method of comprehensive utilization according to claim 2, it is characterised in that the two level desalination production water is back to described one
Merge in level electrodialysis step with the first desalination stoste.
4. method of comprehensive utilization according to claim 2, it is characterised in that in the one-level electrodialysis step and/or institute
State in two level electrodialysis step, operated using constant voltage or constant current, it is 50A/m to control average current density2~550A/m2；Institute
The apparent velocity for stating enriched chamber and/or the desalting chamber is 2cm/s~6cm/s.
5. method of comprehensive utilization according to claim 2, it is characterised in that described in the one-level electrodialysis step
The water inlet of first concentrate is deionized water, the primary concentration produces water or the primary concentration produces the dilution of water；
In the two level electrodialysis step, the second concentrate water inlet is deionized water, the secondary concentration produces water or institute
State the dilution of secondary concentration production water.
6. according to any described method of comprehensive utilization of claim 1-5, it is characterised in that right in the reverse osmosis step
After the single stage desalting production water carries out reverse-osmosis treated, reverse osmosis concentration production water is also obtained；The reverse osmosis concentration production water returns
Merge into the one-level electrodialysis step with the first desalination stoste.
7. the method for comprehensive utilization according to claim 2 or 5, it is characterised in that control the second desalination stoste and institute
State the ratio between volume of the second concentrate water inlet and be not less than 10.
8. method of comprehensive utilization according to claim 2, it is characterised in that the one-level electrodialysis step and the two level
Electrodialysis step process uses NaNO3The aqueous solution or Na2SO4The aqueous solution is as electrode cycle liquid.
9. method of comprehensive utilization according to claim 1, it is characterised in that the cation-exchange membrane selects for monovalent ion
Selecting property anode membrane, the anion-exchange membrane are monovalent ion selectivity cavity block.
10. method of comprehensive utilization according to claim 1, it is characterised in that add HCl/water into the waste liquid containing lithium
Solution or H2SO4The aqueous solution, to remove the CO in the waste liquid containing lithium3 2-And HCO3 -；
Solid suspension content in the first desalination stoste is controlled to be not higher than 5mg/L.
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| KR101700684B1 (en) * | 2015-04-30 | 2017-01-31 | 재단법인 포항산업과학연구원 | Method and apparatus for manufacturing lithium hydroxide, and lithium carbonate |
| CN109020001A (en) * | 2018-09-10 | 2018-12-18 | 青海瑞能新型燃料科技有限公司 | Alcohol-containing waste liquid comprehensive recovering process in a kind of Production Process of Lithium Battery |
| CN109574356A (en) * | 2018-12-26 | 2019-04-05 | 合肥恒力装备有限公司 | A kind of ternary material cleaning wastewater zero emission treatment method |
| CN114380431A (en) * | 2022-01-17 | 2022-04-22 | 桐乡市思远环保科技有限公司 | Method for recovering lithium from seawater |
| CN114890512B (en) * | 2022-04-02 | 2023-03-31 | 倍杰特集团股份有限公司 | Lithium-containing wastewater treatment system and method based on electrically driven membrane |
| CN114590826B (en) * | 2022-04-18 | 2023-07-18 | 四川兴晟锂业有限责任公司 | Treatment process and equipment for potassium-rich mother liquor of lithium hydroxide production system |
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